Low concentrations of Al(III) accelerate the formation of biofilm: Multiple effects of hormesis and flocculation.

PubMed

Cui, Xiaochun; Huo, Mingxin; Chen, Congli; Yu, Zhisen; Zhou, Chen; Li, Anran; Qiao, Bingqian; Zhou, Dandan; Crittenden, John C

2018-09-01

Residual Al(III) (at low concentration) is common in water treatment plants (WTPs) and is associated with bacteria. We hypothesize that Al(III) accelerate biofouling due to its hydrolysis and hormesis characteristics, as compared with other cations. To verify this, we elaborated the roles of Al(III) at low concentrations on the biofilm formation. Al(III) hormesis (<2.0mg/L) stimulated bacteria growth increased by ~3.7 times, and extracellular polymeric substances production also enhanced. Al(III) flocculation resulted in the suspended cells precipitation instantly, for Al(III) dosages of 0.6 and 2.0mg/L and the concentration of Al(III) decreased by 0.07 and 0.14mg/L, respectively. Al(III) poisoned the bridged bacterial cells and decreased their ATP by 22.36% and 55.91%, respectively. Al(III) formed polymer presented strong affinity with bacterial outer membrane, and this damaged the bacterial outer membrane. This caused proteins to leak at the combined point. Al-polymer bound to NH 2 and/or NH on the leaked protein, contributed to biofilm formation. Biofilm maturity was aided by polysaccharides, which shielded Al(III) toxicity for the formed biofilm. Thus, the biofilm exhibited a distinguished double-layer microstructure, principally with proteins and inactivated cells at the bottom, polysaccharides and activated cells at the top. Thus, hormesis and flocculation caused by low concentration Al(III) mutually promoted each other, and together accelerated biofilm formation. Copyright © 2018 Elsevier B.V. All rights reserved.

III-V-on-silicon solar cells reaching 33% photoconversion efficiency in two-terminal configuration

NASA Astrophysics Data System (ADS)

Cariou, Romain; Benick, Jan; Feldmann, Frank; Höhn, Oliver; Hauser, Hubert; Beutel, Paul; Razek, Nasser; Wimplinger, Markus; Bläsi, Benedikt; Lackner, David; Hermle, Martin; Siefer, Gerald; Glunz, Stefan W.; Bett, Andreas W.; Dimroth, Frank

2018-04-01

Silicon dominates the photovoltaic industry but the conversion efficiency of silicon single-junction solar cells is intrinsically constrained to 29.4%, and practically limited to around 27%. It is possible to overcome this limit by combining silicon with high-bandgap materials, such as III-V semiconductors, in a multi-junction device. Significant challenges associated with this material combination have hindered the development of highly efficient III-V/Si solar cells. Here, we demonstrate a III-V/Si cell reaching similar performances to standard III-V/Ge triple-junction solar cells. This device is fabricated using wafer bonding to permanently join a GaInP/GaAs top cell with a silicon bottom cell. The key issues of III-V/Si interface recombination and silicon's weak absorption are addressed using poly-silicon/SiOx passivating contacts and a novel rear-side diffraction grating for the silicon bottom cell. With these combined features, we demonstrate a two-terminal GaInP/GaAs//Si solar cell reaching a 1-sun AM1.5G conversion efficiency of 33.3%.

Highly efficient hydrogenation of carbon dioxide to formate catalyzed by iridium(iii) complexes of imine-diphosphine ligands.

PubMed

Liu, Chong; Xie, Jian-Hua; Tian, Gui-Long; Li, Wei; Zhou, Qi-Lin

2015-05-01

A new iridium catalyst containing an imine-diphosphine ligand has been developed, which showed high efficiency for the hydrogenation of CO 2 to formate (yield up to 99%, TON up to 450 000). A possible catalytic mechanism is proposed, in which the imine group of the catalyst plays a key role in the cleavage of H 2 and the activation of CO 2 .

Hydroxyl Radical Formation in Solutions of Fe(III) and Hydrogen Peroxide - Impact of Freezing and Thawing Process

NASA Astrophysics Data System (ADS)

Arakaki, T.; Kinjo, M.; Shiroma, K.; Shibata, M.; Miyake, T.; Hirakawa, T.; Sakugawa, H.

2003-12-01

Hydroxyl radical formation was studied by detecting concentration of formate in solutions of hydrated formaldehyde, HOOH, and Fe(III) or Cu(II). Oxidation of hydrated formaldehyde by OH radical is known to form formate. Formate formation increased by about 4 times when the solution underwent freezing and thawing. Although the reaction mechanisms are not clearly understood, we believe that the concentration effect of freezing enhanced the catalytic reactions between HOOH and Fe(III) or Cu(II) and the reduction of transition metals, i.e., Fe(III) to Fe(II) and Cu(II) to Cu(I). The concentration effect also enhanced reactions between Fe(II) and HOOH or Cu(I) and HOOH, which generated OH radical (freeze-Fenton reaction). Study of the effects of pH showed that formate formation was the highest at pH = 4.0, indicating that the speciation of Fe(III) affected the formation of formate. Concentration-dependent experiments demonstrated that Fe is probably the limiting agent under typical atmospheric conditions. Our results suggested that the freezing process could be an important source of hydroxyl radical in high cloud, winter fog, rime ice and freezing acidic rain, and more importantly, a potentially additional oxidation mechanism in the atmosphere.

High-efficiency Light-emitting Devices based on Semipolar III-Nitrides

NASA Astrophysics Data System (ADS)

Oh, Sang Ho

In the future, the light-emitting diodes (LEDs) are expected to fully penetrate into the lighting market. A tremendous amount of energy will be saved through the LED-based lighting. Apparently, the amount of the energy saving strongly depends on the efficiency of the LEDs: this dissertation is all about the efficiency. First, the III-nitride LEDs grown on free-standing semipolar (202¯1¯) GaN substrates will be discussed. In many studies, LEDs grown on semipolar III-nitride substrates exhibited high efficiency at high current density. In this dissertation, "droop-free" (202¯1¯) blue LEDs will be demonstrated, especially for the standard industrial chip size. In addition, contact optimization process for (202¯1¯) LEDs will be discussed. Series resistance of the (202¯1¯) LED devices has been improved through the contact optimization. As a result, the wall-plug efficiency (WPE) of the device was boosted by ˜50%, compared to that of the previously reported (202¯1¯) LEDs. Also, chip shaping for the semipolar LEDs to enhance the extraction efficiency will be covered as well. A new mesa design will be introduced, and the cleaving scheme for semipolar LED wafers will be thoroughly discussed. Lastly, as a future work, selective area growth of ZnO light extraction features will be introduced and its preliminary result will be demonstrated.

Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

ERIC Educational Resources Information Center

Prasad, Rajendra; Prasad, Surendra

2009-01-01

The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)…

Efficiency of compensatory orthodontic treatment of mild Class III malocclusion with two different bracket systems

PubMed Central

Aragón, Mônica L. C.; Bichara, Lívia M.; Flores-Mir, Carlos; Almeida, Guilherme; Normando, David

2017-01-01

ABSTRACT Objective: The purpose of this study was to assess the efficiency of compensatory orthodontic treatment of patients with mild Class III malocclusion with two preadjusted bracket systems. Method: Fifty-six matched patients consecutively treated for mild Class III malocclusion through compensatory dentoalveolar movements were retrospectively evaluated after analysis of orthodontic records. The sample was divided into two groups according to the brackets used: Group 1 = non-Class III compensated preadjusted brackets, Roth prescription (n = 28); Group 2 = compensated Class III preadjusted brackets, Capelozza III prescription (n = 28). Cephalometric analysis, number of appointments and missed appointments, months using Class III elastics, and bond/band failures were considered. Treatment time, Peer Assessment Rating (PAR) index at the beginning (PAR T1) and end of treatment (PAR T2) were used to calculate treatment efficiency. Comparison was performed using a MANOVA at p< 0.05. Results: Missed appointments, bond or band failures, number of months using the Class III intermaxillary elastics, and cephalometric measurements showed no statistically significant difference (p> 0.05) between groups. Patients treated with Roth brackets had a treatment time 7 months longer (p= 0.01). Significant improvement in the patient’s occlusion (PAR T2-T1) was observed for both groups without difference (p= 0.22). Conclusions: Orthodontic brackets designed for compensation of mild Class III malocclusions appear to be more efficient than non-compensated straight-wire prescription brackets. Treatment time for Class III patients treated with brackets designed for compensation was shorter than with Roth prescription and no difference in the quality of the occlusal outcome was observed. A prospective randomized study is suggested to provide a deeper look into this subject. PMID:29364379

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

PubMed

Brown, Elizabeth S; Robinson, Jerome R; McCoy, Aaron M; McGaff, Robert W

2011-06-14

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

CHEMICAL ENRICHMENT OF DAMPED Ly{alpha} SYSTEMS AS A DIRECT CONSTRAINT ON POPULATION III STAR FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Girish; Hennawi, Joseph F.; Rollinde, Emmanuel

2013-08-01

Observations of damped Ly{alpha} absorbers (DLAs) can be used to measure gas-phase metallicities at large cosmological look-back times with high precision. Furthermore, relative abundances can still be measured accurately deep into the reionization epoch (z > 6) using transitions redward of Ly{alpha}, even though Gunn-Peterson absorption precludes measurement of neutral hydrogen. In this paper, we study the chemical evolution of DLAs using a model for the coupled evolution of galaxies and the intergalactic medium (IGM), which is constrained by a variety of observations. Our goal is to explore the influence of Population III stars on the abundance patterns of DLAsmore » to determine the degree to which abundance measurements can discriminate between different Population III stellar initial mass functions (IMFs). We include effects, such as inflows onto galaxies due to cosmological accretion and outflows from galaxies due to supernova feedback. A distinct feature of our model is that it self-consistently calculates the effect of Population III star formation on the reionization of an inhomogeneous IGM, thus allowing us to calculate the thermal evolution of the IGM and implement photoionization feedback on low-mass galaxy formation. We find that if the critical metallicity of Population III to II/I transition is {approx}< 10{sup -4} Z{sub Sun }, then the cosmic Population III star formation rate drops to zero for z < 8. Nevertheless, at high redshift (z {approx} 6), chemical signatures of Population III stars remain in low-mass galaxies (halo mass {approx}< 10{sup 9} M{sub Sun }). This is because photoionization feedback suppresses star formation in these galaxies until relatively low redshift (z {approx} 10), and the chemical record of their initial generation of Population III stars is retained. We model DLAs as these low-mass galaxies, and assign to them a mass-dependent H I absorption cross-section in order to predict the expected distribution of DLA abundance

Nonuniversal star formation efficiency in turbulent ISM

DOE PAGES

Semenov, Vadim A.; Kravtsov, Andrey V.; Gnedin, Nickolay Y.

2016-07-29

Here, we present a study of a star formation prescription in which star formation efficiency depends on local gas density and turbulent velocity dispersion, as suggested by direct simulations of SF in turbulent giant molecular clouds (GMCs). We test the model using a simulation of an isolated Milky Way-sized galaxy with a self-consistent treatment of turbulence on unresolved scales. We show that this prescription predicts a wide variation of local star formation efficiency per free-fall time,more » $$\\epsilon_{\\rm ff} \\sim 0.1 - 10\\%$$, and gas depletion time, $$t_{\\rm dep} \\sim 0.1 - 10$$ Gyr. In addition, it predicts an effective density threshold for star formation due to suppression of $$\\epsilon_{\\rm ff}$$ in warm diffuse gas stabilized by thermal pressure. We show that the model predicts star formation rates in agreement with observations from the scales of individual star-forming regions to the kiloparsec scales. This agreement is non-trivial, as the model was not tuned in any way and the predicted star formation rates on all scales are determined by the distribution of the GMC-scale densities and turbulent velocities $$\\sigma$$ in the cold gas within the galaxy, which is shaped by galactic dynamics. The broad agreement of the star formation prescription calibrated in the GMC-scale simulations with observations, both gives credence to such simulations and promises to put star formation modeling in galaxy formation simulations on a much firmer theoretical footing.« less

The Formation of Supermassive Black Holes from Population III.1 Seeds. I. Cosmic Formation Histories and Clustering Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Banik, Nilanjan; Tan, Jonathan C.; Monaco, Pierluigi

We calculate the cosmic distributions in space and time of the formation sites of the first, "Pop III.1" stars, exploring a model in which these are the progenitors of all supermassive black holes (SMBHs). Pop III.1 stars are defined to form from primordial composition gas in dark matter minihalos withmore » $$\\sim10^6\\:M_\\odot$$ that are isolated from neighboring astrophysical sources by a given isolation distance, $$d_{\\rm{iso}}$$. We assume Pop III.1 sources are seeds of SMBHs, based on protostellar support by dark matter annihilation heating that allows them to accrete a large fraction of their minihalo gas, i.e., $$\\sim 10^5\\:M_\\odot$$. Exploring $$d_{\\rm{iso}}$$ from 10--$$100\\:\\rm{kpc}$$ (proper distances), we predict the redshift evolution of Pop III.1 source and SMBH remnant number densities. The local, $z=0$ density of SMBHs constrains $$d_{\\rm{iso}}\\lesssim 100\\:\\rm{kpc}$$ (i.e., $$3\\:\\rm{Mpc}$$ comoving distance at $$z\\simeq30$$). In our simulated ($$\\sim60\\:\\rm{Mpc}$$)$^3$ comoving volume, Pop III.1 stars start forming just after $z=40$. Their formation is largely complete by $$z\\simeq25$$ to 20 for $$d_{\\rm{iso}}=100$$ to $$50\\:\\rm{kpc}$$. We follow source evolution to $z=10$, by which point most SMBHs reside in halos with $$\\gtrsim10^8\\:M_\\odot$$. Over this period, there is relatively limited merging of SMBHs for these values of $$d_{\\rm{iso}}$$. We also predict SMBH clustering properties at $z=10$$: feedback suppression of neighboring sources leads to relatively flat angular correlation functions. Finally, we consider a simple "Str\\"omgren" model for $$d_{\\rm iso}$, based on ionizing feedback from zero age main sequence supermassive Pop III.1 stars that may be the direct progenitors of SMBHs in this scenario. Such models naturally produce feedback effects on scales of $$\\sim100\\:$$kpc and thus self-consistently generate a SMBH number density similar to the observed value.« less

Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes.

PubMed

Hennig, Christoph; Ikeda-Ohno, Atsushi; Kraus, Werner; Weiss, Stephan; Pattison, Philip; Emerich, Hermann; Abdala, Paula M; Scheinost, Andreas C

2013-10-21

Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(μ3-O)4(μ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(μ3-O)4(μ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process.

Remarkable high efficiency of red emitters using Eu(iii) ternary complexes.

PubMed

Kalyakina, Alena S; Utochnikova, Valentina V; Zimmer, Manuel; Dietrich, Fabian; Kaczmarek, Anna M; Van Deun, Rik; Vashchenko, Andrey A; Goloveshkin, Alexander S; Nieger, Martin; Gerhards, Markus; Schepers, Ute; Bräse, Stefan

2018-05-17

We have synthesized Eu(iii) ternary complexes possessing record photoluminescence yields up to 90%. This high luminescence performance resulted from the absence of quenching moieties in the Eu coordination environment and an efficient energy transfer between ligands, combined with a particular symmetry of the coordination environment.

Reactions of a Chromium(III)-Superoxo Complex and Nitric Oxide That Lead to the Formation of Chromium(IV)-Oxo and Chromium(III)-Nitrito Complexes

PubMed Central

Yokoyama, Atsutoshi; Cho, Kyung-Bin

2013-01-01

The reaction of an end-on Cr(III)-superoxo complex bearing a 14-membered tetraazamacrocyclic TMC ligand, [CrIII(14-TMC)(O2)(Cl)]+, with nitric oxide (NO) resulted in the generation of a stable Cr(IV)-oxo species, [CrIV(14-TMC)(O)(Cl)]+, via the formation of a Cr(III)-peroxynitrite intermediate and homolytic O-O bond cleavage of the peroxynitrite ligand. Evidence for the latter comes from EPR spectroscopy, computational chemistry, and the observation of phenol nitration chemistry. The Cr(IV)-oxo complex does not react with nitrogen dioxide (NO2), but reacts with NO to afford a Cr(III)-nitrito complex, [CrIII(14-TMC)(NO2)(Cl)]+. The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally. PMID:24066924

Diagnostic efficiency of demographically corrected Wechsler Adult Intelligence Scale-III and Wechsler Memory Scale-III indices in moderate to severe traumatic brain injury and lower education levels.

PubMed

Walker, Alexandra J; Batchelor, Jennifer; Shores, E Arthur; Jones, Mike

2009-11-01

Despite the sensitivity of neuropsychological tests to educational level, improved diagnostic accuracy for demographically corrected scores has yet to be established. Diagnostic efficiency statistics of Wechsler Adult Intelligence Scale-III (WAIS-III) and Wechsler Memory Scale-III (WMS-III) indices that were corrected for education, sex, and age (demographically corrected) were compared with age corrected indices in individuals aged 16 to 75 years with moderate to severe traumatic brain injury (TBI) and 12 years or less education. TBI participants (n = 100) were consecutive referrals to an outpatient rehabilitation service and met careful selection criteria. Controls (n = 100) were obtained from the WAIS-III/WMS-III standardization sample. Demographically corrected indices did not provide higher diagnostic efficiency than age corrected indices and this result was supported by reanalysis of the TBI group against a larger and unmatched control group. Processing Speed Index provided comparable diagnostic accuracy to that of combined indices. Demographically corrected indices were associated with higher cut-scores to maximize overall classification, reflecting the upward adjustment of those scores in a lower education sample. This suggests that, in clinical practice, the test results of individuals with limited education may be more accurately interpreted with the application of demographic corrections. Diagnostic efficiency statistics are presented, and future research directions are discussed.

Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha

The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cellmore » parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.« less

Efficient Energy Transfer from Near-Infrared Emitting Gold Nanoparticles to Pendant Ytterbium(III).

PubMed

Crawford, Scott E; Andolina, Christopher M; Kaseman, Derrick C; Ryoo, Bo Hyung; Smith, Ashley M; Johnston, Kathryn A; Millstone, Jill E

2017-12-13

Here, we demonstrate efficient energy transfer from near-infrared-emitting ortho-mercaptobenzoic acid-capped gold nanoparticles (AuNPs) to pendant ytterbium(III) cations. These functional materials combine the high molar absorptivity (1.21 × 10 6 M -1 cm -1 ) and broad excitation features (throughout the UV and visible regions) of AuNPs with the narrow emissive properties of lanthanides. Interaction between the AuNP ligand shell and ytterbium is determined using both nuclear magnetic resonance and electron microscopy measurements. In order to identify the mechanism of this energy transfer process, the distance of the ytterbium(III) from the surface of the AuNPs is systematically modulated by changing the size of the ligand appended to the AuNP. By studying the energy transfer efficiency from the various AuNP conjugates to pendant ytterbium(III) cations, a Dexter-type energy transfer mechanism is suggested, which is an important consideration for applications ranging from catalysis to energy harvesting. Taken together, these experiments lay a foundation for the incorporation of emissive AuNPs in energy transfer systems.

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Design High-Efficiency III-V Nanowire/Si Two-Junction Solar Cell.

PubMed

Wang, Y; Zhang, Y; Zhang, D; He, S; Li, X

2015-12-01

In this paper, we report the electrical simulation results of a proposed GaInP nanowire (NW)/Si two-junction solar cell. The NW physical dimensions are determined for optimized solar energy absorption and current matching between each subcell. Two key factors (minority carrier lifetime, surface recombination velocity) affecting power conversion efficiency (PCE) of the solar cell are highlighted, and a practical guideline to design high-efficiency two-junction solar cell is thus provided. Considering the practical surface and bulk defects in GaInP semiconductor, a promising PCE of 27.5 % can be obtained. The results depict the usefulness of integrating NWs to construct high-efficiency multi-junction III-V solar cells.

Impact of Type III Secretion Effectors and of Phenoxyacetamide Inhibitors of Type III Secretion on Abscess Formation in a Mouse Model of Pseudomonas aeruginosa Infection

PubMed Central

Berube, Bryan J.; Murphy, Katherine R.; Torhan, Matthew C.; Bowlin, Nicholas O.; Williams, John D.; Bowlin, Terry L.; Moir, Donald T.

2017-01-01

ABSTRACT Pseudomonas aeruginosa is a leading cause of intra-abdominal infections, wound infections, and community-acquired folliculitis, each of which may involve macro- or microabscess formation. The rising incidence of multidrug resistance among P. aeruginosa isolates has increased both the economic burden and the morbidity and mortality associated with P. aeruginosa disease and necessitates a search for novel therapeutics. Previous work from our group detailed novel phenoxyacetamide inhibitors that block type III secretion and injection into host cells in vitro. In this study, we used a mouse model of P. aeruginosa abscess formation to test the in vivo efficacy of these compounds against the P. aeruginosa type III secretion system (T3SS). Bacteria used the T3SS to intoxicate infiltrating neutrophils to establish abscesses. Despite this antagonism, sufficient numbers of functioning neutrophils remained for proper containment of the abscesses, as neutrophil depletion resulted in an increased abscess size, the formation of dermonecrotic lesions on the skin, and the dissemination of P. aeruginosa to internal organs. Consistent with the specificity of the T3SS-neutrophil interaction, P. aeruginosa bacteria lacking a functional T3SS were fully capable of causing abscesses in a neutropenic host. Phenoxyacetamide inhibitors attenuated abscess formation and aided in the immune clearance of the bacteria. Finally, a P. aeruginosa strain resistant to the phenoxyacetamide compound was fully capable of causing abscess formation even in the presence of the T3SS inhibitors. Together, our results further define the role of type III secretion in murine abscess formation and demonstrate the in vivo efficacy of phenoxyacetamide inhibitors in P. aeruginosa infection. PMID:28807906

Highly Efficient Cooperative Catalysis by Co III (Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Zekai; Zhang, Zhi-Ming; Chen, Yu-Sheng

2016-12-02

A series of porous twofold interpenetrated In-Co III(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent Co III(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In-Co III(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated Co III(porphyrin) centers, thus highlightingmore » the potential application of MOFs in cooperative catalysis.« less

Antigen I/II encoded by integrative and conjugative elements of Streptococcus agalactiae and role in biofilm formation.

PubMed

Chuzeville, Sarah; Dramsi, Shaynoor; Madec, Jean-Yves; Haenni, Marisa; Payot, Sophie

2015-11-01

Streptococcus agalactiae (i.e. Group B streptococcus, GBS) is a major human and animal pathogen. Genes encoding putative surface proteins and in particular an antigen I/II have been identified on Integrative and Conjugative Elements (ICEs) found in GBS. Antigens I/II are multimodal adhesins promoting colonization of the oral cavity by streptococci such as Streptococcus gordonii and Streptococcus mutans. The prevalence and diversity of antigens I/II in GBS were studied by a bioinformatic analysis. It revealed that antigens I/II, which are acquired by horizontal transfer via ICEs, exhibit diversity and are widespread in GBS, in particular in the serotype Ia/ST23 invasive strains. This study aimed at characterizing the impact on GBS biology of proteins encoded by a previously characterized ICE of S. agalactiae (ICE_515_tRNA(Lys)). The production and surface exposition of the antigen I/II encoded by this ICE was examined using RT-PCR and immunoblotting experiments. Surface proteins of ICE_515_tRNA(Lys) were found to contribute to GBS biofilm formation and to fibrinogen binding. Contribution of antigen I/II encoded by SAL_2056 to biofilm formation was also demonstrated. These results highlight the potential for ICEs to spread microbial adhesins between species. Copyright © 2015 Elsevier Ltd. All rights reserved.

Impact of the Motor and Tail Domains of Class III Myosins on Regulating the Formation and Elongation of Actin Protrusions*

PubMed Central

Quintero, Omar A.; Weck, Meredith L.; Unrath, William C.; Gallagher, James W.; Cui, Runjia; Kachar, Bechara; Tyska, Matthew J.; Yengo, Christopher M.

2016-01-01

Class III myosins (MYO3A and MYO3B) are proposed to function as transporters as well as length and ultrastructure regulators within stable actin-based protrusions such as stereocilia and calycal processes. MYO3A differs from MYO3B in that it contains an extended tail domain with an additional actin-binding motif. We examined how the properties of the motor and tail domains of human class III myosins impact their ability to enhance the formation and elongation of actin protrusions. Direct examination of the motor and enzymatic properties of human MYO3A and MYO3B revealed that MYO3A is a 2-fold faster motor with enhanced ATPase activity and actin affinity. A chimera in which the MYO3A tail was fused to the MYO3B motor demonstrated that motor activity correlates with formation and elongation of actin protrusions. We demonstrate that removal of individual exons (30–34) in the MYO3A tail does not prevent filopodia tip localization but abolishes the ability to enhance actin protrusion formation and elongation in COS7 cells. Interestingly, our results demonstrate that MYO3A slows filopodia dynamics and enhances filopodia lifetime in COS7 cells. We also demonstrate that MYO3A is more efficient than MYO3B at increasing formation and elongation of stable microvilli on the surface of cultured epithelial cells. We propose that the unique features of MYO3A, enhanced motor activity, and an extended tail with tail actin-binding motif, allow it to play an important role in stable actin protrusion length and ultrastructure maintenance. PMID:27582493

Formation of Environmentally Persistent Free Radical (EPFR) in Iron(III) Cation-Exchanged Smectite Clay

PubMed Central

Nwosu, Ugwumsinachi G.; Roy, Amitava; dela Cruz, Albert Leo N.; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm−1 and 1595 cm−1, and at lower frequencies between 694 cm−1 and 806 cm−1, as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHp-p of 6.1 G at an average concentration of 7.5 × 1017 spins/g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10−2 spins/Fe(II) atom. PMID:26647158

Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

PubMed

Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom.

Multicopper Oxidase Involvement in Both Mn(II) and Mn(III) Oxidation during Bacterial Formation of MnO2

PubMed Central

Soldatova, Alexandra V.; Butterfield, Cristina; Oyerinde, Oyeyemi F.; Tebo, Bradley M.; Spiro, Thomas G.

2013-01-01

Global cycling of environmental manganese requires catalysis by bacteria and fungi for MnO2 formation, since abiotic Mn(II) oxidation is slow under ambient conditions. Genetic evidence from several bacteria implicates multicopper oxidases (MCOs) as being required for MnO2 formation. However, MCOs catalyze one-electron oxidations, whereas conversion of Mn(II) to MnO2 is a two-electron process. Trapping experiments with pyrophosphate (PP), a Mn(III) chelator, have demonstrated that Mn(III) is an intermediate in Mn(II) oxidation when mediated by exosporium from the Mn-oxidizing bacterium Bacillus SG-1. The reaction of Mn(II) depends on O2 and is inhibited by azide, consistent with MCO catalysis. We show that the subsequent conversion of Mn(III) to MnO2 also depends on O2 and is inhibited by azide. Thus, both oxidation steps appear to be MCO-mediated, likely by the same enzyme, indicated by genetic evidence to be the MnxG gene product. We propose a model of how the manganese oxidase active site may be organized to couple successive electron transfers to the formation of polynuclear Mn(IV) complexes as precursors to MnO2 formation. PMID:22892957

Magnetic Fields in Population III Star Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turk, Matthew J.; Oishi, Jeffrey S.; Abel, Tom

2012-02-22

We study the buildup of magnetic fields during the formation of Population III star-forming regions, by conducting cosmological simulations from realistic initial conditions and varying the Jeans resolution. To investigate this in detail, we start simulations from identical initial conditions, mandating 16, 32 and 64 zones per Jeans length, and studied the variation in their magnetic field amplification. We find that, while compression results in some amplification, turbulent velocity fluctuations driven by the collapse can further amplify an initially weak seed field via dynamo action, provided there is sufficient numerical resolution to capture vortical motions (we find this requirement tomore » be 64 zones per Jeans length, slightly larger than, but consistent with previous work run with more idealized collapse scenarios). We explore saturation of amplification of the magnetic field, which could potentially become dynamically important in subsequent, fully-resolved calculations. We have also identified a relatively surprising phenomena that is purely hydrodynamic: the higher-resolved simulations possess substantially different characteristics, including higher infall-velocity, increased temperatures inside 1000 AU, and decreased molecular hydrogen content in the innermost region. Furthermore, we find that disk formation is suppressed in higher-resolution calculations, at least at the times that we can follow the calculation. We discuss the effect this may have on the buildup of disks over the accretion history of the first clump to form as well as the potential for gravitational instabilities to develop and induce fragmentation.« less

Chimeric antigen receptor containing ICOS signaling domain mediates specific and efficient antitumor effect of T cells against EGFRvIII expressing glioma

PubMed Central

2013-01-01

Background Adoptive transfer of chimeric antigen receptor (CAR)-modified T cells appears to be a promising immunotherapeutic strategy. CAR combines the specificity of antibody and cytotoxicity of cytotoxic T lymphocytes, enhancing T cells’ ability to specifically target antigens and to effectively kill cancer cells. Recent efforts have been made to integrate the costimulatory signals in the CAR to improve the antitumor efficacy. Epidermal growth factor receptor variant III (EGFRvIII) is an attractive therapeutic target as it frequently expresses in glioma and many other types of cancers. Our current study aimed to investigate the specific and efficient antitumor effect of T cells modified with CAR containing inducible costimulator (ICOS) signaling domain. Methods A second generation of EGFRvIII/CAR was generated and it contained the EGFRvIII single chain variable fragment, ICOS signaling domain and CD3ζ chain. Lentiviral EGFRvIII/CAR was prepared and human CD3+ T cells were infected by lentivirus encoding EGFRvIII/CAR. The expression of EGFRvIII/CAR on CD3+ T cells was confirmed by flow cytometry and Western blot. The functions of EGFRvIII/CAR+ T cells were evaluated using in vitro and in vivo methods including cytotoxicity assay, cytokine release assay and xenograft tumor mouse model. Results Chimeric EGFRvIIIscFv-ICOS-CD3ζ (EGFRvIII/CAR) was constructed and lentiviral EGFRvIII/CAR were made to titer of 106 TU/ml. The transduction efficiency of lentiviral EGFRvIII/CAR on T cells reached around 70% and expression of EGFRvIII/CAR protein was verified by immunoblotting as a band of about 57 kDa. Four hour 51Cr release assays demonstrated specific and efficient cytotoxicity of EGFRvIII/CAR+ T cells against EGFRvIII expressing U87 cells. A robust increase in the IFN-γ secretion was detected in the co-culture supernatant of the EGFRvIII/CAR+ T cells and the EGFRvIII expressing U87 cells. Intravenous and intratumor injection of EGFRvIII/CAR+ T cells inhibited the in

Chimeric antigen receptor containing ICOS signaling domain mediates specific and efficient antitumor effect of T cells against EGFRvIII expressing glioma.

PubMed

Shen, Chan-Juan; Yang, Yu-Xiu; Han, Ethan Q; Cao, Na; Wang, Yun-Fei; Wang, Yi; Zhao, Ying-Ying; Zhao, Li-Ming; Cui, Jian; Gupta, Puja; Wong, Albert J; Han, Shuang-Yin

2013-05-09

Adoptive transfer of chimeric antigen receptor (CAR)-modified T cells appears to be a promising immunotherapeutic strategy. CAR combines the specificity of antibody and cytotoxicity of cytotoxic T lymphocytes, enhancing T cells' ability to specifically target antigens and to effectively kill cancer cells. Recent efforts have been made to integrate the costimulatory signals in the CAR to improve the antitumor efficacy. Epidermal growth factor receptor variant III (EGFRvIII) is an attractive therapeutic target as it frequently expresses in glioma and many other types of cancers. Our current study aimed to investigate the specific and efficient antitumor effect of T cells modified with CAR containing inducible costimulator (ICOS) signaling domain. A second generation of EGFRvIII/CAR was generated and it contained the EGFRvIII single chain variable fragment, ICOS signaling domain and CD3ζ chain. Lentiviral EGFRvIII/CAR was prepared and human CD3+ T cells were infected by lentivirus encoding EGFRvIII/CAR. The expression of EGFRvIII/CAR on CD3+ T cells was confirmed by flow cytometry and Western blot. The functions of EGFRvIII/CAR+ T cells were evaluated using in vitro and in vivo methods including cytotoxicity assay, cytokine release assay and xenograft tumor mouse model. Chimeric EGFRvIIIscFv-ICOS-CD3ζ (EGFRvIII/CAR) was constructed and lentiviral EGFRvIII/CAR were made to titer of 106 TU/ml. The transduction efficiency of lentiviral EGFRvIII/CAR on T cells reached around 70% and expression of EGFRvIII/CAR protein was verified by immunoblotting as a band of about 57 kDa. Four hour 51Cr release assays demonstrated specific and efficient cytotoxicity of EGFRvIII/CAR+ T cells against EGFRvIII expressing U87 cells. A robust increase in the IFN-γ secretion was detected in the co-culture supernatant of the EGFRvIII/CAR+ T cells and the EGFRvIII expressing U87 cells. Intravenous and intratumor injection of EGFRvIII/CAR+ T cells inhibited the in vivo growth of the EGFRvIII

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

The formation of light absorbing insoluble organic compounds from the reaction of biomass burning precursors and Fe(III)

NASA Astrophysics Data System (ADS)

Lavi, Avi; Lin, Peng; Bhaduri, Bhaskar; Laskin, Alexander; Rudich, Yinon

2017-04-01

Dust particles and volatile organic compounds from fuel or biomass burning are two major components that affect air quality in urban polluted areas. We characterized the products from the reaction of soluble Fe(III), a reactive transition metal originating from dust particles dissolution processes, with phenolic compounds , namely, guaiacol, syringol, catechol, o- and p- cresol that are known products of incomplete fuel and biomass combustion but also from other natural sources such as humic compounds degradation. We found that under acidic conditions comparable to those expected on a dust particle surface, phenolic compounds readily react with dissolved Fe(III), leading to the formation of insoluble polymeric compounds. We characterized the insoluble products by x-ray photoelectron microscopy, UV-Vis spectroscopy, mass spectrometry, elemental analysis and thermo-gravimetric analysis. We found that the major chromophores formed are oligomers (from dimers to pentamers) of the reaction precursors that efficiently absorb light between 300nm and 500nm. High variability of the mass absorption coefficient of the reaction products was observed with catechol and guaiacol showing high absorption at the 300-500nm range that is comparable to that of brown carbon (BrC) from biomass burning studies. The studied reaction is a potential source for the in-situ production of secondary BrC material under dark conditions. Our results suggest a reaction path for the formation of bio-available iron in coastal polluted areas where dust particles mix with biomass burning pollution plumes. Such mixing can occur, for instance in the coast of West Africa or North Africa during dust and biomass burning seasons

Market Analysis and Consumer Impacts Source Document. Part III. Consumer Behavior and Attitudes Toward Fuel Efficient Vehicles

DOT National Transportation Integrated Search

1980-12-01

This source document on motor vehicle market analysis and consumer impacts consists of three parts. Part III consists of studies and reviews on: consumer awareness of fuel efficiency issues; consumer acceptance of fuel efficient vehicles; car size ch...

State-of-the-art Architectures and Technologies of High-Efficiency Solar Cells Based on III-V Heterostructures for Space and Terrestrial Applications

NASA Astrophysics Data System (ADS)

Pakhanov, N. A.; Andreev, V. M.; Shvarts, M. Z.; Pchelyakov, O. P.

2018-03-01

Multi-junction solar cells based on III-V compounds are the most efficient converters of solar energy to electricity and are widely used in space solar arrays and terrestrial photovoltaic modules with sunlight concentrators. All modern high-efficiency III-V solar cells are based on the long-developed triple-junction III-V GaInP/GaInAs/Ge heterostructure and have an almost limiting efficiency for a given architecture — 30 and 41.6% for space and terrestrial concentrated radiations, respectively. Currently, an increase in efficiency is achieved by converting from the 3-junction to the more efficient 4-, 5-, and even 6-junction III-V architectures: growth technologies and methods of post-growth treatment of structures have been developed, new materials with optimal bandgaps have been designed, and crystallographic parameters have been improved. In this review, we consider recent achievements and prospects for the main directions of research and improvement of architectures, technologies, and materials used in laboratories to develop solar cells with the best conversion efficiency: 35.8% for space, 38.8% for terrestrial, and 46.1% for concentrated sunlight. It is supposed that by 2020, the efficiency will approach 40% for direct space radiation and 50% for concentrated terrestrial solar radiation. This review considers the architecture and technologies of solar cells with record-breaking efficiency for terrestrial and space applications. It should be noted that in terrestrial power plants, the use of III-V SCs is economically advantageous in systems with sunlight concentrators.

Fe(III):S(-II) concentration ratio controls the pathway and the kinetics of pyrite formation during sulfidation of ferric hydroxides

NASA Astrophysics Data System (ADS)

Wan, Moli; Schröder, Christian; Peiffer, Stefan

2017-11-01

The formation of pyrite has been extensively studied because of its abundance in many anoxic environments. Yet, there is no consensus on the underlying pathways and kinetics of its formation. We studied the formation of pyrite during the reaction between reactive ferric hydroxides (goethite and lepidocrocite) and aqueous sulfide in an anoxic glove box at neutral pH. The formation of pyrite was monitored with Mössbauer spectroscopy using 57Fe isotope-enriched ferric (hydr)oxides. The initial molar ratios of Fe(III):S(-II) were adjusted to be 'high' with Fe(III) concentrations in excess of sulfide (HR) and 'low' (LR) with excess of sulfide. Approximately the same surface area was applied in all HR runs in order to compare the mineral reactivity of ferric hydroxides. Electron transfer between aqueous sulfide and ferric hydroxides in the first 2 h led to the formation of ferrous iron and methanol-extractable oxidized sulfur (MES). Metastable FeSx formed in all of the experiments. Pyrite formed at a different rate in HR and LR runs although the MES and ferrous iron concentrations were rather similar. In all HR runs, pyrite formation started after 48 h and achieved a maximum concentration after 1 week. In contrast, pyrite started to form only after 2 months in LR runs (Fe(III):S(-II) ∼ 0.2) with goethite and no pyrite formation was observed in LR with lepidocrocite after 6 months. Rates in LR runs were at least 2-3 orders of magnitude slower than in HR runs. Sulfide oxidation rates were higher with lepidocrocite than with goethite, but no influence of the mineral type on pyrite formation rates in HR runs could be observed. Pyrite formation rates in HR runs could not be predicted by the classical model of Rickard (1975). We therefore propose a novel ferric-hydroxide-surface (FHS) pathway for rapid pyrite formation that is based on the formation of a precursor species >FeIIS2-. Its formation is competitive to FeSx precipitation at high aqueous sulfide concentrations and

LuIII Parvovirus Selectively and Efficiently Targets, Replicates in, and Kills Human Glioma Cells

PubMed Central

Paglino, Justin C.; Ozduman, Koray

2012-01-01

Because productive infection by parvoviruses requires cell division and is enhanced by oncogenic transformation, some parvoviruses may have potential utility in killing cancer cells. To identify the parvovirus(es) with the optimal oncolytic effect against human glioblastomas, we screened 12 parvoviruses at a high multiplicity of infection (MOI). MVMi, MVMc, MVM-G17, tumor virus X (TVX), canine parvovirus (CPV), porcine parvovirus (PPV), rat parvovirus 1A (RPV1A), and H-3 were relatively ineffective. The four viruses with the greatest oncolytic activity, LuIII, H-1, MVMp, and MVM-G52, were tested for the ability, at a low MOI, to progressively infect the culture over time, causing cell death at a rate higher than that of cell proliferation. LuIII alone was effective in all five human glioblastomas tested. H-1 progressively infected only two of five; MVMp and MVM-G52 were ineffective in all five. To investigate the underlying mechanism of LuIII's phenotype, we used recombinant parvoviruses with the LuIII capsid replacing the MVMp capsid or with molecular alteration of the P4 promoter. The LuIII capsid enhanced efficient replication and oncolysis in MO59J gliomas cells; other gliomas tested required the entire LuIII genome to exhibit enhanced infection. LuIII selectively infected glioma cells over normal glial cells in vitro. In mouse models, human glioblastoma xenografts were selectively infected by LuIII when administered intratumorally; LuIII reduced tumor growth by 75%. LuIII also had the capacity to selectively infect subcutaneous or intracranial gliomas after intravenous inoculation. Intravenous or intracranial LuIII caused no adverse effects. Intracranial LuIII caused no infection of mature mouse neurons or glia in vivo but showed a modest infection of developing neurons. PMID:22553327

LuIII parvovirus selectively and efficiently targets, replicates in, and kills human glioma cells.

PubMed

Paglino, Justin C; Ozduman, Koray; van den Pol, Anthony N

2012-07-01

Because productive infection by parvoviruses requires cell division and is enhanced by oncogenic transformation, some parvoviruses may have potential utility in killing cancer cells. To identify the parvovirus(es) with the optimal oncolytic effect against human glioblastomas, we screened 12 parvoviruses at a high multiplicity of infection (MOI). MVMi, MVMc, MVM-G17, tumor virus X (TVX), canine parvovirus (CPV), porcine parvovirus (PPV), rat parvovirus 1A (RPV1A), and H-3 were relatively ineffective. The four viruses with the greatest oncolytic activity, LuIII, H-1, MVMp, and MVM-G52, were tested for the ability, at a low MOI, to progressively infect the culture over time, causing cell death at a rate higher than that of cell proliferation. LuIII alone was effective in all five human glioblastomas tested. H-1 progressively infected only two of five; MVMp and MVM-G52 were ineffective in all five. To investigate the underlying mechanism of LuIII's phenotype, we used recombinant parvoviruses with the LuIII capsid replacing the MVMp capsid or with molecular alteration of the P4 promoter. The LuIII capsid enhanced efficient replication and oncolysis in MO59J gliomas cells; other gliomas tested required the entire LuIII genome to exhibit enhanced infection. LuIII selectively infected glioma cells over normal glial cells in vitro. In mouse models, human glioblastoma xenografts were selectively infected by LuIII when administered intratumorally; LuIII reduced tumor growth by 75%. LuIII also had the capacity to selectively infect subcutaneous or intracranial gliomas after intravenous inoculation. Intravenous or intracranial LuIII caused no adverse effects. Intracranial LuIII caused no infection of mature mouse neurons or glia in vivo but showed a modest infection of developing neurons.

THE WIDESPREAD OF Fe(III)-REDUCING BACTERIA IN NATURAL ECOSYSTEMS OF ECUADOR.

PubMed

Tashyrev, O B; Govorukha, V M

2015-01-01

The widespread of Fe(III)-reducing microorganisms in natural ecosystems of Ecuador of La Favorita, Tungurahua volcano and Papallacta areas was experimentally proved. High efficiency of microbial precipitation of soluble iron compounds was also demonstrated. Obtained results indicate the potential ability of Fe(III)-reducing microorganisms to influence the formation of carbon and iron vector fluxes in ecosystems, as well as development of effective biotechnologies of water purification from iron compounds.

Raising the one-sun conversion efficiency of III-V/Si solar cells to 32.8% for two junctions and 35.9% for three junctions

NASA Astrophysics Data System (ADS)

Essig, Stephanie; Allebé, Christophe; Remo, Timothy; Geisz, John F.; Steiner, Myles A.; Horowitz, Kelsey; Barraud, Loris; Ward, J. Scott; Schnabel, Manuel; Descoeudres, Antoine; Young, David L.; Woodhouse, Michael; Despeisse, Matthieu; Ballif, Christophe; Tamboli, Adele

2017-09-01

Today's dominant photovoltaic technologies rely on single-junction devices, which are approaching their practical efficiency limit of 25-27%. Therefore, researchers are increasingly turning to multi-junction devices, which consist of two or more stacked subcells, each absorbing a different part of the solar spectrum. Here, we show that dual-junction III-V//Sidevices with mechanically stacked, independently operated III-V and Si cells reach cumulative one-sun efficiencies up to 32.8%. Efficiencies up to 35.9% were achieved when combining a GaInP/GaAs dual-junction cell with a Si single-junction cell. These efficiencies exceed both the theoretical 29.4% efficiency limit of conventional Si technology and the efficiency of the record III-V dual-junction device (32.6%), highlighting the potential of Si-based multi-junction solar cells. However, techno-economic analysis reveals an order-of-magnitude disparity between the costs for III-V//Si tandem cells and conventional Si solar cells, which can be reduced if research advances in low-cost III-V growth techniques and new substrate materials are successful.

Development and Implementation of Efficiency-Improving Analysis Methods for the SAGE III on ISS Thermal Model Originating

NASA Technical Reports Server (NTRS)

Liles, Kaitlin; Amundsen, Ruth; Davis, Warren; Scola, Salvatore; Tobin, Steven; McLeod, Shawn; Mannu, Sergio; Guglielmo, Corrado; Moeller, Timothy

2013-01-01

The Stratospheric Aerosol and Gas Experiment III (SAGE III) instrument is the fifth in a series of instruments developed for monitoring aerosols and gaseous constituents in the stratosphere and troposphere. SAGE III will be delivered to the International Space Station (ISS) via the SpaceX Dragon vehicle in 2015. A detailed thermal model of the SAGE III payload has been developed in Thermal Desktop (TD). Several novel methods have been implemented to facilitate efficient payload-level thermal analysis, including the use of a design of experiments (DOE) methodology to determine the worst-case orbits for SAGE III while on ISS, use of TD assemblies to move payloads from the Dragon trunk to the Enhanced Operational Transfer Platform (EOTP) to its final home on the Expedite the Processing of Experiments to Space Station (ExPRESS) Logistics Carrier (ELC)-4, incorporation of older models in varying unit sets, ability to change units easily (including hardcoded logic blocks), case-based logic to facilitate activating heaters and active elements for varying scenarios within a single model, incorporation of several coordinate frames to easily map to structural models with differing geometries and locations, and streamlined results processing using an Excel-based text file plotter developed in-house at LaRC. This document presents an overview of the SAGE III thermal model and describes the development and implementation of these efficiency-improving analysis methods.

Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

PubMed

Bari, Sara E; Amorebieta, Valentín T; Gutiérrez, María M; Olabe, José A; Doctorovich, Fabio

2010-01-01

The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

A possible formation scenario for dwarf spheroidal galaxies - III. Adding star formation histories to the fiducial model

NASA Astrophysics Data System (ADS)

Alarcón Jara, A. G.; Fellhauer, M.; Matus Carrillo, D. R.; Assmann, P.; Urrutia Zapata, F.; Hazeldine, J.; Aravena, C. A.

2018-02-01

Dwarf spheroidal galaxies are regarded as the basic building blocks in the formation of larger galaxies and are the most dark matter dominated systems in the Universe, known so far. There are several models that attempt to explain their formation and evolution, but they have problems modelling the formation of isolated dwarf spheroidal galaxies. Here, we will explain a possible formation scenario in which star clusters form inside the dark matter halo of a dwarf spheroidal galaxy. These star clusters suffer from low star formation efficiency and dissolve while orbiting inside the dark matter halo. Thereby, they build the faint luminous components that we observe in dwarf spheroidal galaxies. In this paper, we study this model by adding different star formation histories to the simulations and compare the results with our previous work and observational data to show that we can explain the formation of dwarf spheroidal galaxies.

Selectively Modulating Triplet Exciton Formation in Host Materials for Highly Efficient Blue Electrophosphorescence.

PubMed

Li, Huanhuan; Bi, Ran; Chen, Ting; Yuan, Kai; Chen, Runfeng; Tao, Ye; Zhang, Hongmei; Zheng, Chao; Huang, Wei

2016-03-23

The concept of limiting the triplet exciton formation to fundamentally alleviate triplet-involved quenching effects is introduced to construct host materials for highly efficient and stable blue phosphorescent organic light-emitting diodes (PhOLEDs). The low triplet exciton formation is realized by small triplet exciton formation fraction and rate with high binding energy and high reorganization energy of triplet exciton. Demonstrated in two analogue molecules in conventional donor-acceptor molecule structure for bipolar charge injection and transport with nearly the same frontier orbital energy levels and triplet excited energies, the new concept host material shows significantly suppressed triplet exciton formation in the host to avoid quenching effects, leading to much improved device efficiencies and stabilities. The low-voltage-driving blue PhOLED devices exhibit maximum efficiencies of 43.7 cd A(-1) for current efficiency, 32.7 lm W(-1) for power efficiency, and 20.7% for external quantum efficiency with low roll-off and remarkable relative quenching effect reduction ratio up to 41%. Our fundamental solution for preventing quenching effects of long-lived triplet excitons provides exciting opportunities for fabricating high-performance devices using the advanced host materials with intrinsically small triplet exciton formation cross section.

Manganese(III) Formate: A Three-Dimensional Framework That Traps Carbon Dioxide Molecules.

PubMed

Cornia, Andrea; Caneschi, Andrea; Dapporto, Paolo; Fabretti, Antonio C; Gatteschi, Dante; Malavasi, Wanda; Sangregorio, Claudio; Sessoli, Roberta

1999-06-14

Carbon dioxide, formic acid, and water molecules are trapped in the crystal lattice of manganese(III) formate (see 1), which was obtained by reducing permanganate with formic acid. Each CO 2 guest molecule exhibits four C-H⋅⋅⋅O-C-O interactions with the three-dimensional host framework of Mn(HCOO) 3 units. Compound 1 undergoes an antiferromagnetic phase transition at 27 K. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Highly efficient star formation in NGC 5253 possibly from stream-fed accretion.

PubMed

Turner, J L; Beck, S C; Benford, D J; Consiglio, S M; Ho, P T P; Kovács, A; Meier, D S; Zhao, J-H

2015-03-19

Gas clouds in present-day galaxies are inefficient at forming stars. Low star-formation efficiency is a critical parameter in galaxy evolution: it is why stars are still forming nearly 14 billion years after the Big Bang and why star clusters generally do not survive their births, instead dispersing to form galactic disks or bulges. Yet the existence of ancient massive bound star clusters (globular clusters) in the Milky Way suggests that efficiencies were higher when they formed ten billion years ago. A local dwarf galaxy, NGC 5253, has a young star cluster that provides an example of highly efficient star formation. Here we report the detection of the J = 3→2 rotational transition of CO at the location of the massive cluster. The gas cloud is hot, dense, quiescent and extremely dusty. Its gas-to-dust ratio is lower than the Galactic value, which we attribute to dust enrichment by the embedded star cluster. Its star-formation efficiency exceeds 50 per cent, tenfold that of clouds in the Milky Way. We suggest that high efficiency results from the force-feeding of star formation by a streamer of gas falling into the galaxy.

An Investigation into III-V Compounds to Reach 20% Efficiency with Minimum Cell Thickness in Ultrathin-Film Solar Cells

NASA Astrophysics Data System (ADS)

Haque, K. A. S. M. Ehteshamul; Galib, Md. Mehedi Hassan

2013-10-01

III-V single-junction solar cells have already achieved very high efficiency levels. However, their use in terrestrial applications is limited by the high fabrication cost. High-efficiency, ultrathin-film solar cells can effectively solve this problem, as their material requirement is minimum. This work presents a comparison among several III-V compounds that have high optical absorption capability as well as optimum bandgap (around 1.4 eV) for use as solar cell absorbers. The aim is to observe and compare the ability of these materials to reach a target efficiency level of 20% with minimum possible cell thickness. The solar cell considered has an n-type ZnSe window layer, an n-type Al0.1Ga0.9As emitter layer, and a p-type Ga0.5In0.5P back surface field (BSF) layer. Ge is used as the substrate. In the initial design, a p-type InP base was sandwiched between the emitter and the BSF layer, and the design parameters for the device were optimized by analyzing the simulation outcomes with ADEPT/F, a one-dimensional (1D) simulation tool. Then, the minimum cell thickness that achieves 20% efficiency was determined by observing the efficiency variation with cell thickness. Afterwards, the base material was changed to a few other selected III-V compounds, and for each case, the minimum cell thickness was determined in a similar manner. Finally, these cell thickness values were compared and analyzed to identify more effective base layer materials for III-V single-junction solar cells.

Bacterial Formation of As(V) and As(III) Ferric Oxyhydroxides in Acid Mine Drainage.

NASA Astrophysics Data System (ADS)

Morin, G.; Juillot, F.; Lebrun, S.; Casiot, C.; Elbaz-Poulichet, F.; Bruneel, O.; Personne, J.; Leblanc, M.; Ildefonse, P.; Calas, G.

2002-12-01

The oxidation of dissolved Fe(II) which is often promoted by acidophilic bacteria in acid mine drainage (AMD) and some hot springs, leads to the precipitation of Fe(III) oxy-hydroxides which incorporate toxic elements within their structure or adsorb them at their surface, thus limiting their mobility. In such complex natural systems, synchrotron-based techniques as X-ray absorption spectroscopy offer the opportunity to monitor surface/solution interactions as well as redox changes affecting the mobility and toxicity of trace elements as arsenic. Spatial and seasonal variations of the (bio-) oxidation of Fe(II) and As(III), and the subsequent precipitation of As-Fe gels, were followed by XANES, XRD, and SEM along the CarnoulŠs AMD (Gard, France). Chemical and mineralogical data collected on sediments, stromatolite, and bioassay samples showed that some indigenous bacteria living in the As-rich CarnoulŠs water ([As] = up to 350 mg.l-1) play an important role in the nature and composition of the solid phases that sequester arsenic at the site. The formation of nano-crystalline and amorphous As(III) ferric oxy-hydroxides has been related to the presence of bacteria able to oxidize Fe(II) but not As(III), which are only present in winter in the upstream area. A rare ferric arsenite sulfate oxy-hydroxide mineral was discovered in this context. Other types of bacteria, occurring in the downstream area whatever the season, are able to catalyze As(III) to As(V) oxidation and, provided that enough Fe(II) oxidizes, promote the formation of amorphous As(V) rich ferric oxy-hydroxides. These bacterially mediated reactions significantly reduce the concentration of dissolved As(III), which is more toxic and mobile than As(V), and might thus be helpful for designing As-removal processes. This work was supported by the French PEVS and ACI Ecologie Quantitative Programs and the PIRAMID EC program. ?Deceased, 26 October 1999 Juillot F., Ildefonse Ph., Morin G., Calas G., De

Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.

Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96%more » N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.« less

Alternative Formats to Achieve More Efficient Energy Codes for Commercial Buildings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conover, David R.; Rosenberg, Michael I.; Halverson, Mark A.

2013-01-26

This paper identifies and examines several formats or structures that could be used to create the next generation of more efficient energy codes and standards for commercial buildings. Pacific Northwest National Laboratory (PNNL) is funded by the U.S. Department of Energy’s Building Energy Codes Program (BECP) to provide technical support to the development of ANSI/ASHRAE/IES Standard 90.1. While the majority of PNNL’s ASHRAE Standard 90.1 support focuses on developing and evaluating new requirements, a portion of its work involves consideration of the format of energy standards. In its current working plan, the ASHRAE 90.1 committee has approved an energy goalmore » of 50% improvement in Standard 90.1-2013 relative to Standard 90.1-2004, and will likely be considering higher improvement targets for future versions of the standard. To cost-effectively achieve the 50% goal in manner that can gain stakeholder consensus, formats other than prescriptive must be considered. Alternative formats that include reducing the reliance on prescriptive requirements may make it easier to achieve these aggressive efficiency levels in new codes and standards. The focus on energy code and standard formats is meant to explore approaches to presenting the criteria that will foster compliance, enhance verification, and stimulate innovation while saving energy in buildings. New formats may also make it easier for building designers and owners to design and build the levels of efficiency called for in the new codes and standards. This paper examines a number of potential formats and structures, including prescriptive, performance-based (with sub-formats of performance equivalency and performance targets), capacity constraint-based, and outcome-based. The paper also discusses the pros and cons of each format from the viewpoint of code users and of code enforcers.« less

Soliton communication lines based on spectrally efficient modulation formats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yushko, O V; Redyuk, A A

2014-06-30

We report the results of mathematical modelling of optical-signal propagation in soliton fibre-optic communication lines (FOCLs) based on spectrally efficient signal modulation formats. We have studied the influence of spontaneous emission noise, nonlinear distortions and FOCL length on the data transmission quality. We have compared the characteristics of a received optical signal for soliton and conventional dispersion compensating FOCLs. It is shown that in the presence of strong nonlinearity long-haul soliton FOCLs provide a higher data transmission performance, as well as allow higher order modulation formats to be used as compared to conventional communication lines. In the context of amore » coherent data transmission, soliton FOCLs allow the use of phase modulation with many levels, thereby increasing the spectral efficiency of the communication line. (optical communication lines)« less

Kernel based machine learning algorithm for the efficient prediction of type III polyketide synthase family of proteins.

PubMed

Mallika, V; Sivakumar, K C; Jaichand, S; Soniya, E V

2010-07-13

Type III Polyketide synthases (PKS) are family of proteins considered to have significant roles in the biosynthesis of various polyketides in plants, fungi and bacteria. As these proteins shows positive effects to human health, more researches are going on regarding this particular protein. Developing a tool to identify the probability of sequence being a type III polyketide synthase will minimize the time consumption and manpower efforts. In this approach, we have designed and implemented PKSIIIpred, a high performance prediction server for type III PKS where the classifier is Support Vector Machines (SVMs). Based on the limited training dataset, the tool efficiently predicts the type III PKS superfamily of proteins with high sensitivity and specificity. The PKSIIIpred is available at http://type3pks.in/prediction/. We expect that this tool may serve as a useful resource for type III PKS researchers. Currently work is being progressed for further betterment of prediction accuracy by including more sequence features in the training dataset.

College of American Pathologists Cancer Protocols: Optimizing Format for Accuracy and Efficiency.

PubMed

Strickland-Marmol, Leah B; Muro-Cacho, Carlos A; Barnett, Scott D; Banas, Matthew R; Foulis, Philip R

2016-06-01

-The data in College of American Pathologists cancer protocols have to be presented effectively to health care providers. There is no consensus on the format of those protocols, resulting in various designs among pathologists. Cancer protocols are independently created by site-specific experts, so there is inconsistent wording and repetition of data. This lack of standardization can be confusing and may lead to interpretation errors. -To define a synopsis format that is effective in delivering essential pathologic information and to evaluate the aesthetic appeal and the impact of varying format styles on the speed and accuracy of data extraction. -We queried individuals from several health care backgrounds using varying formats of the fallopian tube protocol of the College of American Pathologists without content modification to investigate their aesthetic appeal, accuracy, efficiency, and readability/complexity. Descriptive statistics, an item difficulty index, and 3 tests of readability were used. -Columned formats were aesthetically more appealing than justified formats (P < .001) and were associated with greater accuracy and efficiency. Incorrect assumptions were made about items not included in the protocol. Uniform wording and short sentences were associated with better performance by participants. -Based on these data, we propose standardized protocol formats for cancer resections of the fallopian tube and the more-familiar colon, employing headers, short phrases, and uniform terminology. This template can be easily and minimally modified for other sites, standardizing format and verbiage and increasing user accuracy and efficiency. Principles of human factors engineering should be considered in the display of patient data.

Fuel Efficient Strategies for Reducing Contrail Formations in United States Air Space

NASA Technical Reports Server (NTRS)

Sridhar, Banavar; Chen, Neil Y.; Ng, Hok K.

2010-01-01

This paper describes a class of strategies for reducing persistent contrail formation in the United States airspace. The primary objective is to minimize potential contrail formation regions by altering the aircraft's cruising altitude in a fuel-efficient way. The results show that the contrail formations can be reduced significantly without extra fuel consumption and without adversely affecting congestion in the airspace. The contrail formations can be further reduced by using extra fuel. For the day tested, the maximal reduction strategy has a 53% contrail reduction rate. The most fuel-efficient strategy has an 8% reduction rate with 2.86% less fuel-burnt compared to the maximal reduction strategy. Using a cost function which penalizes extra fuel consumed while maximizing the amount of contrail reduction provides a flexible way to trade off between contrail reduction and fuel consumption. It can achieve a 35% contrail reduction rate with only 0.23% extra fuel consumption. The proposed fuel-efficient contrail reduction strategy provides a solution to reduce aviation-induced environmental impact on a daily basis.

N-type molecular electrical doping in organic semiconductors: formation and dissociation efficiencies of charge transfer complex

NASA Astrophysics Data System (ADS)

Kim, Jae-Min; Yoo, Seung-Jun; Moon, Chang-Ki; Sim, Bomi; Lee, Jae-Hyun; Lim, Heeseon; Kim, Jeong Won; Kim, Jang-Joo

2016-09-01

Electrical doping is an important method in organic electronics to enhance device efficiency by controlling Fermi level, increasing conductivity, and reducing injection barrier from electrode. To understand the charge generation process of dopant in doped organic semiconductors, it is important to analyze the charge transfer complex (CTC) formation and dissociation into free charge carrier. In this paper, we correlate charge generation efficiency with the CTC formation and dissociation efficiency of n-dopant in organic semiconductors (OSs). The CTC formation efficiency of Rb2CO3 linearly decreases from 82.8% to 47.0% as the doping concentration increases from 2.5 mol% to 20 mol%. The CTC formation efficiency and its linear decrease with doping concentration are analytically correlated with the concentration-dependent size and number of dopant agglomerates by introducing the degree of reduced CTC formation. Lastly, the behavior of dissociation efficiency is discussed based on the picture of the statistical semiconductor theory and the frontier orbital hybridization model.

Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst.

PubMed

Ahn, Steven T; Bielinski, Elizabeth A; Lane, Elizabeth M; Chen, Yanqiao; Bernskoetter, Wesley H; Hazari, Nilay; Palmore, G Tayhas R

2015-04-07

An iridium(III) trihydride complex supported by a pincer ligand with a hydrogen bond donor in the secondary coordination sphere promotes the electrocatalytic reduction of CO2 to formate in water/acetonitrile with excellent Faradaic efficiency and low overpotential. Preliminary mechanistic experiments indicate formate formation is facile while product release is a kinetically difficult step.

SAGE III

Atmospheric Science Data Center

2017-10-27

SAGE III Data and Information The Stratospheric Aerosol and Gas ... on the spacecraft. SAGE III produced L1 and L2 scientific data from 5/07/2002 until 12/31/2005. The second instrument is as an ... Additional Info:  Data Format: HDF-EOS or Big Endian/IEEE Binary SCAR-B Block:  ...

Method for making graded I-III-VI.sub.2 semiconductors and solar cell obtained thereby

DOEpatents

Devaney, Walter E.

1987-08-04

Improved cell photovoltaic conversion efficiencies are obtained by the simultaneous elemental reactive evaporation process of Mickelsen and Chen for making semiconductors by closer control of the evaporation rates and substrate temperature during formation of the near contact, bulk, and near junction regions of a graded I-III-VI.sub.2, thin film, semiconductor, such as CuInSe.sub.2 /(Zn,Cd)S or another I-III-VI.sub.2 /II-VI heterojunction.

Revisiting The First Galaxies: The effects of Population III stars on their host galaxies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muratov, Alexander L.; Gnedin, Oleg Y.; Gnedin, Nickolay Y.

2013-07-12

We revisit the formation and evolution of the first galaxies using new hydrodynamic cosmological simulations with the adaptive refinement tree code. Our simulations feature a recently developed model for H 2 formation and dissociation, and a star formation recipe that is based on molecular rather than atomic gas. Here, we develop and implement a recipe for the formation of metal-free Population III (Pop III) stars in galaxy-scale simulations that resolve primordial clouds with sufficiently high density. We base our recipe on the results of prior zoom-in simulations that resolved the protostellar collapse in pre-galactic objects. We find the epoch duringmore » which Pop III stars dominated the energy and metal budget of the first galaxies to be short-lived. Galaxies that host Pop III stars do not retain dynamical signatures of their thermal and radiative feedback for more than 10 8 years after the lives of the stars end in pair-instability supernovae, even when we consider the maximum reasonable efficiency of the feedback. Though metals ejected by the supernovae can travel well beyond the virial radius of the host galaxy, they typically begin to fall back quickly, and do not enrich a large fraction of the intergalactic medium. Galaxies with a total mass in excess of 3 × 10 6 M ⊙ re-accrete most of their baryons and transition to metal-enriched Pop II star formation.« less

REVISITING THE FIRST GALAXIES: THE EFFECTS OF POPULATION III STARS ON THEIR HOST GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muratov, Alexander L.; Gnedin, Oleg Y.; Zemp, Marcel

2013-08-01

We revisit the formation and evolution of the first galaxies using new hydrodynamic cosmological simulations with the adaptive refinement tree code. Our simulations feature a recently developed model for H{sub 2} formation and dissociation, and a star formation recipe that is based on molecular rather than atomic gas. Here, we develop and implement a recipe for the formation of metal-free Population III (Pop III) stars in galaxy-scale simulations that resolve primordial clouds with sufficiently high density. We base our recipe on the results of prior zoom-in simulations that resolved the protostellar collapse in pre-galactic objects. We find the epoch duringmore » which Pop III stars dominated the energy and metal budget of the first galaxies to be short-lived. Galaxies that host Pop III stars do not retain dynamical signatures of their thermal and radiative feedback for more than 10{sup 8} years after the lives of the stars end in pair-instability supernovae, even when we consider the maximum reasonable efficiency of the feedback. Though metals ejected by the supernovae can travel well beyond the virial radius of the host galaxy, they typically begin to fall back quickly, and do not enrich a large fraction of the intergalactic medium. Galaxies with a total mass in excess of 3 Multiplication-Sign 10{sup 6} M{sub Sun} re-accrete most of their baryons and transition to metal-enriched Pop II star formation.« less

A Simple Non-equilibrium Model of Star Formation and Scatter in the Kennicutt-Schmidt Relation and Star Formation Efficiencies in Galaxies

NASA Astrophysics Data System (ADS)

Orr, Matthew; Hopkins, Philip F.

2018-06-01

I will present a simple model of non-equilibrium star formation and its relation to the scatter in the Kennicutt-Schmidt relation and large-scale star formation efficiencies in galaxies. I will highlight the importance of a hierarchy of timescales, between the galaxy dynamical time, local free-fall time, the delay time of stellar feedback, and temporal overlap in observables, in setting the scatter of the observed star formation rates for a given gas mass. Further, I will talk about how these timescales (and their associated duty-cycles of star formation) influence interpretations of the large-scale star formation efficiency in reasonably star-forming galaxies. Lastly, the connection with galactic centers and out-of-equilibrium feedback conditions will be mentioned.

Carbon-sulfur bond formation by reductive elimination of gold(iii) thiolates.

PubMed

Currie, Lucy; Rocchigiani, Luca; Hughes, David L; Bochmann, Manfred

2018-05-08

Whereas the reaction of the gold(iii) pincer complex (C^N^C)AuCl with 1-adamantyl thiol (AdSH) in the presence of base affords (C^N^C)AuSAd, the same reaction in the absence of base leads to formation of aryl thioethers as the products of reductive elimination of the Au-C and Au-S ligands (C^N^C = dianion of 2-6-diphenylpyridine or 2-6-diphenylpyrazine). Although high chemical stability is usually taken as a characteristic of pincer complexes, results show that thiols are capable of cleaving one of the pincer Au-C bonds. This reaction is not simply a function of S-H acidity, since no cleavage takes place with other more acidic X-H compounds, such as carbazole, amides, phenols and malonates. The reductive C-S elimination follows a second-order rate law, -d[1a]/dt = k[1a][AdSH]. Reductive elimination is enabled by displacement of the N-donor by thiol; this provides the conformational flexibility necessary for C-S bond formation to occur. Alternatively, reductive C-S bond formation can be induced by reaction of pre-formed thiolates (C^N^C)AuSR with a strong Brønsted acid, followed by addition of SMe2 as base. On the other hand, treatment of (C^N^C)AuR (R = Me, aryl, alkynyl) with thiols under similar conditions leads to selective C-C rather than C-S bond formation. The reaction of (C^N^C)AuSAd with H+ in the absence of a donor ligand affords the thiolato-bridged complex [{(C^N-CH)Au(μ-SAd)}2]2+ which was crystallographically characterised.

Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining

PubMed Central

Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L.; Tomkinson, Alan E.; Tainer, John A.; Ellenberger, Tom

2015-01-01

Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. PMID:26130724

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

PubMed

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Optical Features of Efficient Europium(III) Complexes with β-Diketonato and Auxiliary Ligands and Mechanistic Investigation of Energy Transfer Process.

PubMed

Bala, Manju; Kumar, Satish; Taxak, V B; Boora, Priti; Khatkar, S P

2016-09-01

Two new europium (III) complexes have been synthesized with 1,3-[bis(4-methoxyphenyl)]propane-1,3-dionato (HBMPD) as main ligand and 2,2'-bipyridyl (bipy) or 1,10-phenanthroline (phen) as an auxiliary ligand. The main ligand HBMPD has been synthesized by ecofriendly microwave approach and complexes by solution precipitation method. The resulting materials are characterized by IR, (1)H-NMR, elemental analysis, X-ray diffraction, UV-visible and TG-DTG techniques. The photoluminescence (PL) spectroscopy depicts the detail analysis of photophysical properties of the complexes, their results show that the ligand interact with Eu (III) ion which act as antenna and transfers the absorbed energy to the central europium(III) ion via sensitization process efficiently. As a consequence of this interaction, these materials exhibit excellent luminescent intensity, long decay time (τ), high quantum efficiency (η) and Judd-Ofelt intensity parameter (Ω2). The CIE coordinates fall under the deep red region, matching well with the NTSC (National Television Standard Committee) standard. Hence, these highly efficient optical materials can be used as a red component in organic light emitting diodes (OLEDs) and full color flat panel displays.

SAGE III-ISS

Atmospheric Science Data Center

2017-12-27

SAGE III-ISS Data and Information Launched on February 19, 2017 on a SpaceX ... vertical profiles of the stratosphere and mesosphere. The data provided by SAGE III-ISS includes key components of atmospheric ... Additional Info:  Data Format: HDF4 or Big Endian/IEEE Binary SCAR-B Block:  ...

When Feedback Fails: The Scaling and Saturation of Star Formation Efficiency

NASA Astrophysics Data System (ADS)

Y Grudic, Michael; Hopkins, Philip F.; Faucher-Giguere, Claude-Andre; Quataert, Eliot; Murray, Norman W.; Keres, Dusan

2017-06-01

We present a suite of 3D multi-physics MHD simulations following star formation in isolated turbulent molecular gas disks ranging from 5 to 500 parsecs in radius. These simulations are designed to survey the range of surface densities between those typical of Milky Way GMCs (˜100 M⊙pc-2) and extreme ULIRG environments (˜104M⊙pc-2) so as to map out the scaling of star formation efficiency (SFE) between these two regimes. The simulations include prescriptions for supernova, stellar wind, and radiative feedback, which we find to be essential in determining both the instantaneous (ɛff) and integrated (ɛint) star formation efficiencies. In all simulations, the gas disks form stars until a critical stellar mass has been reached and the remaining gas is blown out by stellar feedback. We find that surface density is the best predictor of ɛint of all of the gas cloud's global properties, as suggested by analytic force balance arguments from previous works. Furthermore, SFE eventually saturates to ˜1 at high surface density, with very good agreement across different spatial scales. We also find a roughly proportional relationship between ɛff and ɛint. These results have implications for star formation in galactic disks, the nature and fate of nuclear starbursts, and the formation of bound star clusters. The scaling of ɛff also contradicts star formation models in which ɛff˜1% universally, including popular subgrid models for galaxy simulations.

Guanidine: A Highly Efficient Stabilizer in Atmospheric New-Particle Formation.

PubMed

Myllys, Nanna; Ponkkonen, Tuomo; Passananti, Monica; Elm, Jonas; Vehkamäki, Hanna; Olenius, Tinja

2018-05-24

The role of a strong organobase, guanidine, in sulfuric acid-driven new-particle formation is studied using state-of-the-art quantum chemical methods and molecular cluster formation simulations. Cluster formation mechanisms at the molecular level are resolved, and theoretical results on cluster stability are confirmed with mass spectrometer measurements. New-particle formation from guanidine and sulfuric acid molecules occurs without thermodynamic barriers under studied conditions, and clusters are growing close to a 1:1 composition of acid and base. Evaporation rates of the most stable clusters are extremely low, which can be explained by the proton transfers and symmetrical cluster structures. We compare the ability of guanidine and dimethylamine to enhance sulfuric acid-driven particle formation and show that more than 2000-fold concentration of dimethylamine is needed to yield as efficient particle formation as in the case of guanidine. At similar conditions, guanidine yields 8 orders of magnitude higher particle formation rates compared to dimethylamine. Highly basic compounds such as guanidine may explain experimentally observed particle formation events at low precursor vapor concentrations, whereas less basic and more abundant bases such as ammonia and amines are likely to explain measurements at high concentrations.

Formation, expansion, and interconversion of metallarings in a sulfur-bridged Au(I) Co(III) coordination system.

PubMed

Oji, Katsuya; Igashira-Kamiyama, Asako; Yoshinari, Nobuto; Konno, Takumi

2014-02-10

A novel Au(I) Co(III) coordination system that is derived from the newly prepared [Co(D-nmp)2 ](-) (1(-) ; D-nmp=N-methyl-D-penicillaminate) and a gold(I) precursor Au(I) is reported. Complex 1(-) acts as a sulfur-donating metallaligand and reacts with the gold(I) precursor to give [Au2 Co2 (D-nmp)4 ] (2), which has an eight-membered Au(I) 2 Co(III) 2 metallaring. Treatment of 2 with [Au2 (dppe)2 ](2+) (dppe=1,2-bis(diphenylphosphino)ethane) leads to the formation of [Au4 Co2 (dppe)2 (D-nmp)4 ](2+) (3(2+) ), which consists of an 18-membered Au(I) 4 Co(III) 2 metallaring that accommodates a tetrahedral anion (BF4 (-) , ClO4 (-) , ReO4 (-) ). In solution, the metallaring structure of 3(2+) is readily interconvertible with the nine-membered Au(I) 2 Co(III) metallaring structure of [Au2 Co(dppe)(D-nmp)2 ](+) (4(+) ); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the AuS and AuP bonds, which is essential for metallaring expansion and contraction. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Addendum I, BIOPLUME III Graphics Conversion to SURFER Format

EPA Pesticide Factsheets

This procedure can be used to create a SURFER® compatible grid file from Bioplume III input and output graphics. The input data and results from Bioplume III can be contoured and printed directly from SURFER.

Dark-ages reionization and galaxy formation simulation - III. Modelling galaxy formation and the epoch of reionization

NASA Astrophysics Data System (ADS)

Mutch, Simon J.; Geil, Paul M.; Poole, Gregory B.; Angel, Paul W.; Duffy, Alan R.; Mesinger, Andrei; Wyithe, J. Stuart B.

2016-10-01

We introduce MERAXES, a new, purpose-built semi-analytic galaxy formation model designed for studying galaxy growth during reionization. MERAXES is the first model of its type to include a temporally and spatially coupled treatment of reionization and is built upon a custom (100 Mpc)3 N-body simulation with high temporal and mass resolution, allowing us to resolve the galaxy and star formation physics relevant to early galaxy formation. Our fiducial model with supernova feedback reproduces the observed optical depth to electron scattering and evolution of the galaxy stellar mass function between z = 5 and 7, predicting that a broad range of halo masses contribute to reionization. Using a constant escape fraction and global recombination rate, our model is unable to simultaneously match the observed ionizing emissivity at z ≲ 6. However, the use of an evolving escape fraction of 0.05-0.1 at z ˜ 6, increasing towards higher redshift, is able to satisfy these three constraints. We also demonstrate that photoionization suppression of low-mass galaxy formation during reionization has only a small effect on the ionization history of the intergalactic medium. This lack of `self-regulation' arises due to the already efficient quenching of star formation by supernova feedback. It is only in models with gas supply-limited star formation that reionization feedback is effective at regulating galaxy growth. We similarly find that reionization has only a small effect on the stellar mass function, with no observationally detectable imprint at M* > 107.5 M⊙. However, patchy reionization has significant effects on individual galaxy masses, with variations of factors of 2-3 at z = 5 that correlate with environment.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

Dew and hoarfrost frequency, formation efficiency and chemistry in Wroclaw, Poland

NASA Astrophysics Data System (ADS)

Gałek, G.; Sobik, M.; Błaś, M.; Polkowska, Ż.; Cichała-Kamrowska, K.; Wałaszek, K.

2015-01-01

This article presents the results of a research study concerning a comparison of frequency, formation efficiency and basic physico-chemical properties of dew and hoarfrost in urban conditions. Longer than two-year series of measurements was carried out from 1 February 2008 to 10 March 2010 in Wroclaw, Poland. Sampling of atmospheric deposits was made by means of insulated plain passive radiative condensers, which allowed to collect 222 dew and 96 hoarfrost samples. The results indicate that the frequency of dew days was about threefold greater than hoarfrost days. The formation efficiency of both types of deposits was almost the same, and reached a mean value of about 100 mL·m- 2 per day. The conducted analysis of several meteorological parameters showed that dew and hoarfrost, despite seasonal weather changes, were formed in very similar meteorological conditions. Only water vapor pressure values were in average twice higher in the case of dew and the impact of this parameter on dew and hoarfrost formation efficiency seems to be more complex than expected. The role of night duration in counterbalancing of smaller amount of available moisture in hoarfrost days is not clear. The investigation showed also, that there was an expected clear positive dependence of dew and hoarfrost formation efficiency on relative humidity, and not so evident in the case of temperature inversion, and wind velocity. The physico-chemical analysis indicated that the pH of dew was only slightly lower than the hoarfrost ones, regardless of the deposit formation intensity. Simultaneously, the lower pH values were much more frequent in the case of dew, which resulted from more effective absorption of anthropogenic NO3- and SO42 - ions. For both types of deposits, the average pH was low (4.5-4.8) in relation to majority of studies reported in literature. In spite of seasonal changes of pollutant concentration, various weather conditions and different mechanisms of pollutant absorption of dew

Mn(2+)-mediated homogeneous Fenton-like reaction of Fe(III)-NTA complex for efficient degradation of organic contaminants under neutral conditions.

PubMed

Li, Yifan; Sun, Jianhui; Sun, Sheng-Peng

2016-08-05

In this work, we report a novel Mn(2+)-mediated Fenton-like process based on Fe(III)-NTA complex that is super-efficient at circumneutral pH range. Kinetics experiments showed that the presence of Mn(2+) significantly enhanced the effectiveness of Fe(III)-NTA complex catalyzed Fenton-like reaction. The degradation rate constant of crotamiton (CRMT), a model compound, by the Fe(III)- NTA_Mn(2+) Fenton-like process was at least 1.6 orders of magnitude larger than that in the absence of Mn(2+). Other metal ions such as Ca(2+), Mg(2+), Co(2+) and Cu(2+) had no impacts or little inhibitory effect on the Fe(III)-NTA complex catalyzed Fenton-like reaction. The generation of hydroxyl radical (HO) and superoxide radical anion (O2(-)) in the Fe(III)-NTA_Mn(2+) Fenton-like process were suggested by radicals scavenging experiments. The degradation efficiency of CRMT was inhibited significantly (approximately 92%) by the addition of HO scavenger 2-propanol, while the addition of O2(-) scavenger chloroform resulted in 68% inhibition. Moreover, the results showed that other chelating agents such as EDTA- and s,s-EDDS-Fe(III) catalyzed Fenton-like reactions were also enhanced significantly by the presence of Mn(2+). The mechanism involves an enhanced generation of O2(-) from the reactions of Mn(2+)-chelates with H2O2, indirectly promoting the generation of HO by accelerating the reduction rate of Fe(III)-chelates to Fe(II)- chelates. Copyright © 2016 Elsevier B.V. All rights reserved.

DNA Polymerase α Subunit Residues and Interactions Required for Efficient Initiation Complex Formation Identified by a Genetic Selection.

PubMed

Lindow, Janet C; Dohrmann, Paul R; McHenry, Charles S

2015-07-03

Biophysical and structural studies have defined many of the interactions that occur between individual components or subassemblies of the bacterial replicase, DNA polymerase III holoenzyme (Pol III HE). Here, we extended our knowledge of residues and interactions that are important for the first step of the replicase reaction: the ATP-dependent formation of an initiation complex between the Pol III HE and primed DNA. We exploited a genetic selection using a dominant negative variant of the polymerase catalytic subunit that can effectively compete with wild-type Pol III α and form initiation complexes, but cannot elongate. Suppression of the dominant negative phenotype was achieved by secondary mutations that were ineffective in initiation complex formation. The corresponding proteins were purified and characterized. One class of mutant mapped to the PHP domain of Pol III α, ablating interaction with the ϵ proofreading subunit and distorting the polymerase active site in the adjacent polymerase domain. Another class of mutation, found near the C terminus, interfered with τ binding. A third class mapped within the known β-binding domain, decreasing interaction with the β2 processivity factor. Surprisingly, mutations within the β binding domain also ablated interaction with τ, suggesting a larger τ binding site than previously recognized. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining.

PubMed

Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L; Tomkinson, Alan E; Tainer, John A; Ellenberger, Tom

2015-08-18

Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Role of an RNase III Binding Site in Transcription Termination at λ nutL by HK022 Nun Protein

PubMed Central

Washburn, Robert S.; Court, Donald L.; Gottesman, Max E.

2006-01-01

The phage HK022 Nun protein excludes phage λ by binding nascent λ pL and pR transcripts at nutL and nutR, respectively, and inducing transcription termination just downstream of these sites. Termination is more efficient at nutL than at nutR. One difference between nutL and nutR is the presence of RNase III processing sites (rIII) located immediately promoter distal to λ nutL. We found that deletion of rIII dramatically reduced Nun transcription arrest in vitro but had little effect on termination in vivo. However, consistent with the in vitro results, overexpression of a transcript carrying nutL and rIII efficiently titrated Nun, allowing λ to grow on a strain that expressed Nun, whereas a transcript carrying only nutL or nutL-rIII with nucleotides 97 to 141 deleted was ineffective. Rnc70, an RNase III mutant that binds but does not cleave rIII, also prevented Nun-mediated λ exclusion. We propose that rIII enhances the on-rate of Nun at nutL, stimulating Nun-mediated arrest in vitro. We have shown that a specific element in rIII, i.e., box C (G89GUGUGUG), strongly enhances arrest on rIII+ templates. Nun-rIII interactions do not stimulate Nun termination in vivo, presumably because formation of the Nun-nutL complex is normally not rate-limiting in the cell. In contrast to Nun, N is not occluded by Rnc70 and is not efficiently titrated by a nutL-rIII transcript. PMID:16980485

Reduction of aqueous chromate by Fe(II)/Fe(III) carbonate green rust: kinetic and mechanistic studies.

PubMed

Legrand, Ludovic; El Figuigui, Alaaeddine; Mercier, Florence; Chausse, Annie

2004-09-01

This work describes the heterogeneous reaction between FeII in carbonate green rust and aqueous chromate, in NaHCO3 solutions at 25 degrees C, and at pH values of 9.3-9.6. Evidence for reduction of CrVI to CrIII and concomitant solid-state oxidation of lattice FeII to FeIII was found from FeII titration and from structural analysis of the solids using FTIR, XRD, SEM, and XPS methods. Results indicate the formation of ferric oxyhydroxycarbonate and the concomitant precipitation of CrIII monolayers at the surface of the iron compound that induce passivation effects and progressive rate limitations. The number of CrIII monolayers formed at the completion of the reaction depends on [FeII]t=0, the molar concentration of FeII(solid) at t=0; on [n(o)]t=0, the molar concentration of reaction sites present at the surface of the solid phase at t=0; and on [CrVI]t=0, the molar concentration of CrVI at t=0. Kinetic data were modeled using a model based on the formation of successive CrIII monolayers, -(d[CrVI]/dt) = sigma(1)j k(i)[S] [CrVI]([n(i - 1)] - [n(i)]) with k(i)[S] (in s(-1) L mol(-1)), the rate coefficient of formation of CrIII monolayer i, and [n(i)] and [n(i - 1)], the molar concentration of CrIII precipitated in monolayer i and monolayer i - 1, respectively. Good matching curves were obtained with kinetic coefficients: k(1)[S] = 5-8 x 10(-4), k(2)[S] = 0.5-3 x 10(-5), and k(3)[S] about 1.7 x 10(-6) s(-1) m(-2) L. The CrVI removal efficiency progressively decreases along with the accumulation of CrIII monolayers at the surface of carbonate green rust particles. In the case of thick green rust particles resulting from the corrosion of iron in permeable reactive barriers, the quantity of FeII readily accessible for efficient CrVI removal should be rather low.

Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions.

PubMed

Mailhot, G; Sarakha, M; Lavedrine, B; Cáceres, J; Malato, S

2002-11-01

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

The influence of the cluster environment on the star formation efficiency of 12 Virgo spiral galaxies

NASA Astrophysics Data System (ADS)

Vollmer, B.; Wong, O. I.; Braine, J.; Chung, A.; Kenney, J. D. P.

2012-07-01

The influence of the environment on gas surface density and star formation efficiency of cluster spiral galaxies is investigated. We extend previous work on radial profiles by a pixel-to pixel analysis looking for asymmetries due to environmental interactions. The star formation rate is derived from GALEX UV and Spitzer total infrared data based on the 8, 24, 70, and 160 μm data. As in field galaxies, the star formation rate for most Virgo galaxies is approximately proportional to the molecular gas mass. Except for NGC 4438, the cluster environment does not affect the star formation efficiency with respect to the molecular gas. Gas truncation is not associated with major changes in the total gas surface density distribution of the inner disk of Virgo spiral galaxies. In three galaxies (NGC 4430, NGC 4501, and NGC 4522), possible increases in the molecular fraction and the star formation efficiency with respect to the total gas, of factors of 1.5 to 2, are observed on the windward side of the galactic disk. A significant increase of the star formation efficiency with respect to the molecular gas content on the windward side of ram pressure-stripped galaxies is not observed. The ram-pressure stripped extraplanar gas of 3 highly inclined spiral galaxies (NGC 4330, NGC 4438, and NGC 4522) shows a depressed star formation efficiency with respect to the total gas, and one of them (NGC 4438) shows a depressed rate even with respect to the molecular gas. The interpretation is that stripped gas loses the gravitational confinement and associated pressure of the galactic disk, and the gas flow is diverging, so the gas density decreases and the star formation rate drops. We found two such regions of low star formation efficiency in the more face-on galaxies NGC 4501 and NGC 4654 which are both undergoing ram pressure stripping. These regions show low radio continuum emission or unusually steep radio spectral index. However, the stripped extraplanar gas in one highly inclined

Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

PubMed

Chebeir, Michelle; Liu, Haizhou

2018-05-17

The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

Probing chromium(III) from chromium(VI) in cells by a fluorescent sensor

NASA Astrophysics Data System (ADS)

Hu, Xiangquan; Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2016-01-01

Cellular uptake of Cr(VI), followed by its reduction to Cr(III) with the formation of kinetically inert Cr(III) complexes, is a complex process. To better understand its physiological and pathological functions, efficient methods for the monitoring of Cr(VI) are desired. In this paper a selective fluorescent probe L, rhodamine hydrazide bearing a benzo[b]furan-2-carboxaldehyde group, was demonstrated as a red chemosensor for Cr(III) at about 586 nm. This probe has been used to probe Cr(III) which is reduced from Cr(VI) by reductants such as glutathione (GSH), vitamin C, cysteine (Cys), H2O2 and Dithiothreitol (DTT) by fluorescence spectra. Cr(VI) metabolism in vivo is primarily driven by Vc and GSH. Vc could reduce CrO42 - to Cr(III) in a faster rate than GSH. The indirectly detection limit for Cr(VI) by L + GSH system was determined to be 0.06 μM at pH = 6.2. Moreover, the confocal microscopy image experiments indicated that Cr(VI) can be reduced to Cr(III) inside cells rapidly and the resulted Cr(III) can be captured and imaged timely by L.

βIII Spectrin Is Necessary for Formation of the Constricted Neck of Dendritic Spines and Regulation of Synaptic Activity in Neurons

PubMed Central

Efimova, Nadia; Korobova, Farida; Moberly, Andrew H.; Stolz, Donna B.; Wang, Junling; Kashina, Anna; Ma, Minghong

2017-01-01

Dendritic spines are postsynaptic structures in neurons often having a mushroom-like shape. Physiological significance and cytoskeletal mechanisms that maintain this shape are poorly understood. The spectrin-based membrane skeleton maintains the biconcave shape of erythrocytes, but whether spectrins also determine the shape of nonerythroid cells is less clear. We show that βIII spectrin in hippocampal and cortical neurons from rodent embryos of both sexes is distributed throughout the somatodendritic compartment but is particularly enriched in the neck and base of dendritic spines and largely absent from spine heads. Electron microscopy revealed that βIII spectrin forms a detergent-resistant cytoskeletal network at these sites. Knockdown of βIII spectrin results in a significant decrease in the density of dendritic spines. Surprisingly, the density of presynaptic terminals is not affected by βIII spectrin knockdown. However, instead of making normal spiny synapses, the presynaptic structures in βIII spectrin-depleted neurons make shaft synapses that exhibit increased amplitudes of miniature EPSCs indicative of excessive postsynaptic excitation. Thus, βIII spectrin is necessary for formation of the constricted shape of the spine neck, which in turn controls communication between the synapse and the parent dendrite to prevent excessive excitation. Notably, mutations of SPTNB2 encoding βIII spectrin are associated with neurodegenerative syndromes, spinocerebellar ataxia Type 5, and spectrin-associated autosomal recessive cerebellar ataxia Type 1, but molecular mechanisms linking βIII spectrin functions to neuronal pathologies remain unresolved. Our data suggest that spinocerebellar ataxia Type 5 and spectrin-associated autosomal recessive cerebellar ataxia Type 1 pathology likely arises from poorly controlled synaptic activity that leads to excitotoxicity and neurodegeneration. SIGNIFICANCE STATEMENT Dendritic spines are small protrusions from neuronal

The formation efficiency of different generations of HMXBs in the low metallicity environment of the SMC

NASA Astrophysics Data System (ADS)

Antoniou, Vallia; Zezas, Andreas; Drake, Jeremy J.; Badenes, Carles; Hong, Jaesub; SMC XVP Collaboration

2018-01-01

Nearby star-forming galaxies offer a unique environment to study the populations of young (<100 Myr) X-ray binaries, which consist of a compact object - typically a neutron star or a black hole - powered by accretion from a companion star. These systems are tracers of past populations of massive stars that heavily affect their immediate environment and parent galaxies. The Small Magellanic Cloud (SMC) is the ideal environment for population studies of young X-ray binaries by providing us with what the Milky Way cannot: A complete sample of X-ray sources within a galaxy. Using a Chandra X-ray Visionary program, we investigate the young neutron-star binary population in this low-metallicity, nearby, star-forming galaxy by reaching quiescent X-ray luminosity levels (~few times 1032 erg/s). In this talk, I will present the first measurement of the formation efficiency of high-mass X-ray binaries (HMXBs) as a function of the age of their parent stellar populations. We use three indicators of the formation efficiency of young accreting binaries in the low SMC metallicity: the number ratio of the HMXBs, N(HMXBs), to the number of OB stars, to the star-formation rate (SFR), and to the stellar mass produced during the specific star-formation burst they are associated with, all as a function of the age of their parent stellar populations. In all cases, we find that the HMXB formation efficiency increases as a function of time up to ~40—60 Myr, and then gradually decreases. The peak formation efficiency N(HMXB)/SFR is in good agreement with previous estimates of the average formation efficiency in the broad ~20—60 Myr age range, and a factor of at least ~8 and ~4 higher than the formation efficiency in earlier (~10 Myr) and later (~260 Myr) epochs. I will also present the deepest luminosity function ever recorded for a galaxy, and discuss the X-ray properties of the largest sample of extragalactic accreting pulsars as well.

The effect of vortex formation on left ventricular filling and mitral valve efficiency.

PubMed

Pierrakos, Olga; Vlachos, Pavlos P

2006-08-01

A new mechanism for quantifying the filling energetics in the left ventricle (LV) and past mechanical heart valves (MHV) is identified and presented. This mechanism is attributed to vortex formation dynamics past MHV leaflets. Recent studies support the conjecture that the natural healthy left ventricle (LV) performs in an optimum, energy-preserving manner by redirecting the flow with high efficiency. Yet to date, no quantitative proof has been presented. The present work provides quantitative results and validation of a theory based on the dynamics of vortex ring formation, which is governed by a critical formation number (FN) that corresponds to the dimensionless time at which the vortex ring has reached its maximum circulation content, in support of this hypothesis. Herein, several parameters (vortex ring circulation, vortex ring energy, critical FN, hydrodynamic efficiencies, vortex ring propagation speed) have been quantified and presented as a means of bridging the physics of vortex formation in the LV. In fact, the diastolic hydrodynamic efficiencies were found to be 60, 41, and 29%, respectively, for the porcine, anti-anatomical, and anatomical valve configurations. This assessment provides quantitative proof of vortex formation, which is dependent of valve design and orientation, being an important flow characteristic and associated to LV energetics. Time resolved digital particle image velocimetry with kilohertz sampling rate was used to study the ejection of fluid into the LV and resolve the spatiotemporal evolution of the flow. The clinical significance of this study is quantifying vortex formation and the critical FN that can potentially serve as a parameter to quantify the LV filling process and the performance of heart valves.

When feedback fails: the scaling and saturation of star formation efficiency

NASA Astrophysics Data System (ADS)

Grudić, Michael Y.; Hopkins, Philip F.; Faucher-Giguère, Claude-André; Quataert, Eliot; Murray, Norman; Kereš, Dušan

2018-04-01

We present a suite of 3D multiphysics MHD simulations following star formation in isolated turbulent molecular gas discs ranging from 5 to 500 parsecs in radius. These simulations are designed to survey the range of surface densities between those typical of Milky Way giant molecular clouds (GMCs) ({˜ } 10^2 {M_{\\odot } pc^{-2}}) and extreme ultraluminous infrared galaxy environments ({˜ } 10^4 {M_{\\odot } pc^{-2}}) so as to map out the scaling of the cloud-scale star formation efficiency (SFE) between these two regimes. The simulations include prescriptions for supernova, stellar wind, and radiative feedback, which we find to be essential in determining both the instantaneous per-freefall (ɛff) and integrated (ɛint) star formation efficiencies. In all simulations, the gas discs form stars until a critical stellar surface density has been reached and the remaining gas is blown out by stellar feedback. We find that surface density is a good predictor of ɛint, as suggested by analytic force balance arguments from previous works. SFE eventually saturates to ˜1 at high surface density. We also find a proportional relationship between ɛff and ɛint, implying that star formation is feedback-moderated even over very short time-scales in isolated clouds. These results have implications for star formation in galactic discs, the nature and fate of nuclear starbursts, and the formation of bound star clusters. The scaling of ɛff with surface density is not consistent with the notion that ɛff is always ˜ 1 per cent on the scale of GMCs, but our predictions recover the ˜ 1 per cent value for GMC parameters similar to those found in spiral galaxies, including our own.

Cyclometalated Iridium(III) Carbene Phosphors for Highly Efficient Blue Organic Light-Emitting Diodes.

PubMed

Chen, Zhao; Wang, Liqi; Su, Sikai; Zheng, Xingyu; Zhu, Nianyong; Ho, Cheuk-Lam; Chen, Shuming; Wong, Wai-Yeung

2017-11-22

Five deep blue carbene-based iridium(III) phosphors were synthesized and characterized. Interestingly, one of them can be fabricated into deep blue, sky blue and white organic light-emitting diodes (OLEDs) through changing the host materials and exciton blocking layers. These deep and sky blue devices exhibit Commission Internationale de l'Éclairage (CIE) coordinates of (0.145, 0.186) and (0.152, 0.277) with external quantum efficiency (EQE) of 15.2% and 9.6%, respectively. The EQE of the deep blue device can be further improved up to 19.0% by choosing a host with suitable energy level of its lowest unoccupied molecular orbital (LUMO).

A binuclear Mn(III) complex of a scorpiand-like ligand displaying a single unsupported Mn(III)-O-Mn(III) bridge.

PubMed

Blasco, Salvador; Cano, Joan; Clares, M Paz; García-Granda, Santiago; Doménech, Antonio; Jiménez, Hermas R; Verdejo, Begoña; Lloret, Francesc; García-España, Enrique

2012-11-05

The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.

βIII Spectrin Is Necessary for Formation of the Constricted Neck of Dendritic Spines and Regulation of Synaptic Activity in Neurons.

PubMed

Efimova, Nadia; Korobova, Farida; Stankewich, Michael C; Moberly, Andrew H; Stolz, Donna B; Wang, Junling; Kashina, Anna; Ma, Minghong; Svitkina, Tatyana

2017-07-05

Dendritic spines are postsynaptic structures in neurons often having a mushroom-like shape. Physiological significance and cytoskeletal mechanisms that maintain this shape are poorly understood. The spectrin-based membrane skeleton maintains the biconcave shape of erythrocytes, but whether spectrins also determine the shape of nonerythroid cells is less clear. We show that βIII spectrin in hippocampal and cortical neurons from rodent embryos of both sexes is distributed throughout the somatodendritic compartment but is particularly enriched in the neck and base of dendritic spines and largely absent from spine heads. Electron microscopy revealed that βIII spectrin forms a detergent-resistant cytoskeletal network at these sites. Knockdown of βIII spectrin results in a significant decrease in the density of dendritic spines. Surprisingly, the density of presynaptic terminals is not affected by βIII spectrin knockdown. However, instead of making normal spiny synapses, the presynaptic structures in βIII spectrin-depleted neurons make shaft synapses that exhibit increased amplitudes of miniature EPSCs indicative of excessive postsynaptic excitation. Thus, βIII spectrin is necessary for formation of the constricted shape of the spine neck, which in turn controls communication between the synapse and the parent dendrite to prevent excessive excitation. Notably, mutations of SPTNB2 encoding βIII spectrin are associated with neurodegenerative syndromes, spinocerebellar ataxia Type 5, and spectrin-associated autosomal recessive cerebellar ataxia Type 1, but molecular mechanisms linking βIII spectrin functions to neuronal pathologies remain unresolved. Our data suggest that spinocerebellar ataxia Type 5 and spectrin-associated autosomal recessive cerebellar ataxia Type 1 pathology likely arises from poorly controlled synaptic activity that leads to excitotoxicity and neurodegeneration. SIGNIFICANCE STATEMENT Dendritic spines are small protrusions from neuronal

Silica, Alumina and Clay Catalyzed Peptide Bond Formation: Enhanced Efficiency of Alumina Catalyst

NASA Astrophysics Data System (ADS)

Bujdák, Juraj; Rode, Bernd M.

1999-10-01

Catalytic efficiencies of clay (hectorite), silica and alumina were tested in peptide bond formation reactions of glycine (Gly), alanine (Ala), proline (Pro), valine (Val) and leucine (Leu). The reactions were performed as drying/wetting (hectorite) and temperature fluctuation (silica and alumina) experiments at 85 °C. The reactivity of amino acids decreased in order Gly > Ala > Pro ~ Val ~ Leu. The highest catalytic efficiency was observed for alumina, the only catalyst producing oligopeptides in all investigated reaction systems. The peptide bond formation on alumina is probably catalyzed by the same sites and via similar reaction mechanisms as some alumina-catalyzed dehydration reactions used in industrial chemistry.

Low-Cost III-V Solar Cells | Photovoltaic Research | NREL

Science.gov Websites

Low-Cost III-V Solar Cells Low-Cost III-V Solar Cells At present, the cost of III-V solar cells is to drastically lower the cost of these devices, while maintaining their conversion efficiency, thus costs in the production of high-efficiency III-V devices: the cost of the epitaxy and the single-crystal

Uvf - Unified Volume Format: A General System for Efficient Handling of Large Volumetric Datasets.

PubMed

Krüger, Jens; Potter, Kristin; Macleod, Rob S; Johnson, Christopher

2008-01-01

With the continual increase in computing power, volumetric datasets with sizes ranging from only a few megabytes to petascale are generated thousands of times per day. Such data may come from an ordinary source such as simple everyday medical imaging procedures, while larger datasets may be generated from cluster-based scientific simulations or measurements of large scale experiments. In computer science an incredible amount of work worldwide is put into the efficient visualization of these datasets. As researchers in the field of scientific visualization, we often have to face the task of handling very large data from various sources. This data usually comes in many different data formats. In medical imaging, the DICOM standard is well established, however, most research labs use their own data formats to store and process data. To simplify the task of reading the many different formats used with all of the different visualization programs, we present a system for the efficient handling of many types of large scientific datasets (see Figure 1 for just a few examples). While primarily targeted at structured volumetric data, UVF can store just about any type of structured and unstructured data. The system is composed of a file format specification with a reference implementation of a reader. It is not only a common, easy to implement format but also allows for efficient rendering of most datasets without the need to convert the data in memory.

Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

PubMed

Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

2016-06-21

Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

Toward Efficient Team Formation for Crowdsourcing in Noncooperative Social Networks.

PubMed

Wang, Wanyuan; Jiang, Jiuchuan; An, Bo; Jiang, Yichuan; Chen, Bing

2017-12-01

Crowdsourcing has become a popular service computing paradigm for requesters to integrate the ubiquitous human-intelligence services for tasks that are difficult for computers but trivial for humans. This paper focuses on crowdsourcing complex tasks by team formation in social networks (SNs) where a requester connects to a large number of workers. A good indicator of efficient team collaboration is the social connection among workers. Most previous social team formation approaches, however, either assume that the requester can maintain information of all workers and can directly communicate with them to build teams, or assume that the workers are cooperative and be willing to join the specific team built by the requester, both of which are impractical in many real situations. To this end, this paper first models each worker as a selfish entity, where the requester prefers to hire inexpensive workers that require less payment and workers prefer to join the profitable teams where they can gain high revenue. Within the noncooperative SNs, a distributed negotiation-based team formation mechanism is designed for the requester to decide which worker to hire and for the worker to decide which team to join and how much should be paid for his skill service provision. The proposed social team formation approach can always build collaborative teams by allowing team members to form a connected graph such that they can work together efficiently. Finally, we conduct a set of experiments on real dataset of workers to evaluate the effectiveness of our approach. The experimental results show that our approach can: 1) preserve considerable social welfare by comparing the benchmark centralized approaches and 2) form the profitable teams within less negotiation time by comparing the traditional distributed approaches, making our approach a more economic option for real-world applications.

New anti-cancer chemicals Ertredin and its derivatives, regulate oxidative phosphorylation and glycolysis and suppress sphere formation in vitro and tumor growth in EGFRvIII-transformed cells.

PubMed

Atsumi, Sonoko; Nosaka, Chisato; Adachi, Hayamitsu; Kimura, Tomoyuki; Kobayashi, Yoshihiko; Takada, Hisashi; Watanabe, Takumi; Ohba, Shun-Ichi; Inoue, Hiroyuki; Kawada, Manabu; Shibasaki, Masakatsu; Shibuya, Masabumi

2016-07-19

EGFRvIII is a mutant form of the epidermal growth factor receptor gene (EGFR) that lacks exons 2-7. The resulting protein does not bind to ligands and is constitutively activated. The expression of EGFRvIII is likely confined to various types of cancer, particularly glioblastomas. Although an anti-EGFRvIII vaccine is of great interest, low-molecular-weight substances are needed to obtain better therapeutic efficacy. Thus, the purpose of this study is to identify low molecular weight substances that can suppress EGFRvIII-dependent transformation. We constructed a new throughput screening system and searched for substances that decreased cell survival of NIH3T3/EGFRvIII spheres under 3-dimensional (3D)-culture conditions, but retained normal NIH3T3 cell growth under 2D-culture conditions. In vivo activity was examined using a mouse transplantation model, and derivatives were chemically synthesized. Functional characterization of the candidate molecules was investigated using an EGFR kinase assay, immunoprecipitation, western blotting, microarray analysis, quantitative polymerase chain reaction analysis, and measurement of lactate and ATP synthesis. In the course of screening 30,000 substances, a reagent, "Ertredin" was found to inhibit anchorage-independent 3D growth of sphere-forming cells transfected with EGFRvIII cDNA. Ertredin also inhibited sphere formation in cells expressing wild-type EGFR in the presence of EGF. However, it did not affect anchorage-dependent 2D growth of parental NIH3T3 cells. The 3D-growth-inhibitory activity of some derivatives, including those with new structures, was similar to Ertredin. Furthermore, we demonstrated that Ertredin suppressed tumor growth in an allograft transplantation mouse model injected with EGFRvIII- or wild-type EGFR-expressing cells; a clear toxicity to host animals was not observed. Functional characterization of Ertredin in cells expressing EGFRvIII indicated that it stimulated EGFRvIII ubiquitination, suppressed

Silver Nanowire Transparent Conductive Electrodes for High-Efficiency III-Nitride Light-Emitting Diodes

PubMed Central

Oh, Munsik; Jin, Won-Yong; Jun Jeong, Hyeon; Jeong, Mun Seok; Kang, Jae-Wook; Kim, Hyunsoo

2015-01-01

Silver nanowires (AgNWs) have been successfully demonstrated to function as next-generation transparent conductive electrodes (TCEs) in organic semiconductor devices owing to their figures of merit, including high optical transmittance, low sheet resistance, flexibility, and low-cost processing. In this article, high-quality, solution-processed AgNWs with an excellent optical transmittance of 96.5% at 450 nm and a low sheet resistance of 11.7 Ω/sq were demonstrated as TCEs in inorganic III-nitride LEDs. The transmission line model applied to the AgNW contact to p-GaN showed that near ohmic contact with a specific contact resistance of ~10−3 Ωcm2 was obtained. The contact resistance had a strong bias-voltage (or current-density) dependence: namely, field-enhanced ohmic contact. LEDs fabricated with AgNW electrodes exhibited a 56% reduction in series resistance, 56.5% brighter output power, a 67.5% reduction in efficiency droop, and a approximately 30% longer current spreading length compared to LEDs fabricated with reference TCEs. In addition to the cost reduction, the observed improvements in device performance suggest that the AgNWs are promising for application as next-generation TCEs, to realise brighter, larger-area, cost-competitive inorganic III-nitride light emitters. PMID:26333768

Final Report: Vapor Transport Deposition for Thin Film III-V Photovoltaics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boettcher, Shannon; Greenaway, Ann; Boucher, Jason

2016-02-10

Silicon, the dominant photovoltaic (PV) technology, is reaching its fundamental performance limits as a single absorber/junction technology. Higher efficiency devices are needed to reduce cost further because the balance of systems account for about two-thirds of the overall cost of the solar electricity. III-V semiconductors such as GaAs are used to make the highest-efficiency photovoltaic devices, but the costs of manufacture are much too high for non-concentrated terrestrial applications. The cost of III-V’s is driven by two factors: (1) metal-organic chemical vapor deposition (MOCVD), the dominant growth technology, employs expensive, toxic and pyrophoric gas-phase precursors, and (2) the growth substratesmore » conventionally required for high-performance devices are monocrystalline III-V wafers. The primary goal of this project was to show that close-spaced vapor transport (CSVT), using water vapor as a transport agent, is a scalable deposition technology for growing low-cost epitaxial III-V photovoltaic devices. The secondary goal was to integrate those devices on Si substrates for high-efficiency tandem applications using interface nanopatterning to address the lattice mismatch. In the first task, we developed a CSVT process that used only safe solid-source powder precursors to grow epitaxial GaAs with controlled n and p doping and mobilities/lifetimes similar to that obtainable via MOCVD. Using photoelectrochemical characterization, we showed that the best material had near unity internal quantum efficiency for carrier collection and minority carrier diffusions lengths in of ~ 8 μm, suitable for PV devices with >25% efficiency. In the second task we developed the first pn junction photovoltaics using CSVT and showed unpassivated structures with open circuit photovoltages > 915 mV and internal quantum efficiencies >0.9. We also characterized morphological and electrical defects and identified routes to reduce those defects. In task three we grew

Magnetic bead-based enzyme-chromogenic substrate system for ultrasensitive colorimetric immunoassay accompanying cascade reaction for enzymatic formation of squaric acid-iron(III) chelate.

PubMed

Lai, Wenqiang; Tang, Dianping; Zhuang, Junyang; Chen, Guonan; Yang, Huanghao

2014-05-20

This work reports on a simple and feasible colorimetric immunoassay with signal amplification for sensitive determination of prostate-specific antigen (PSA, used as a model) at an ultralow concentration by using a new enzyme-chromogenic substrate system. We discovered that glucose oxidase (GOx), the enzyme broadly used in enzyme-linked immunosorbent assay (ELISA), has the ability to stimulate in situ formation of squaric acid (SQA)-iron(III) chelate. GOx-catalyzed oxidization of glucose leads to the formation of gluconic acid and hydrogen peroxide (H2O2). The latter can catalytically oxidize iron(II) to iron(III), which can rapidly (<1 min) coordinate with the SQA. Formation of the iron-squarate complex causes the color of the solution to change from bluish purple to bluish red accompanying the increasing absorbance with the increment of iron(III) concentration. On the basis of the SQA-iron(III) system, a new immunoassay protocol with GOx-labeled anti-PSA detection antibody can be designed for the detection of target PSA on capture antibody-functionalized magnetic immunosensing probe, monitored by recording the color or absorbance (λ = 468 nm) of the generated SQA-iron(III) chelate. The absorbance intensity shows to be dependent on the concentration of target PSA. A linear dependence between the absorbance and target PSA concentration is obtained under optimal conditions in the range from 1.0 pg mL(-1) to 30 ng mL(-1) with a detection limit (LOD) of 0.5 pg mL(-1) (0.5 ppt) estimated at the 3Sblank level. The sensitivity displays to be 3-5 orders of magnitude better than those of most commercialized human PSA ELISA kits. In addition, the developed colorimetric immunoassay was validated by assaying 12 human serum samples, receiving in good accordance with those obtained by the commercialized PSA ELISA kit. Importantly, the SQA-based immunosensing system can be further extended for the detection of other low-abundance proteins or biomarkers by controlling the target

Phase III Advanced Anodes and Cathodes Utilized in Energy Efficient Aluminum Production Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

R.A. Christini; R.K. Dawless; S.P. Ray

2001-11-05

During Phase I of the present program, Alcoa developed a commercial cell concept that has been estimated to save 30% of the energy required for aluminum smelting. Phase ii involved the construction of a pilot facility and operation of two pilots. Phase iii of the Advanced Anodes and Cathodes Program was aimed at bench experiments to permit the resolution of certain questions to be followed by three pilot cells. All of the milestones related to materials, in particular metal purity, were attained with distinct improvements over work in previous phases of the program. NiO additions to the ceramic phase andmore » Ag additions to the Cu metal phase of the cermet improved corrosion resistance sufficiently that the bench scale pencil anodes met the purity milestones. Some excellent metal purity results have been obtained with anodes of the following composition: Further improvements in anode material composition appear to be dependent on a better understanding of oxide solubilities in molten cryolite. For that reason, work was commissioned with an outside consultant to model the MeO - cryolite systems. That work has led to a better understanding of which oxides can be used to substitute into the NiO-Fe2O3 ceramic phase to stabilize the ferrites and reduce their solubility in molten cryolite. An extensive number of vertical plate bench electrolysis cells were run to try to find conditions where high current efficiencies could be attained. TiB2-G plates were very inconsistent and led to poor wetting and drainage. Pure TiB2 did produce good current efficiencies at small overlaps (shadowing) between the anodes and cathodes. This bench work with vertical plate anodes and cathodes reinforced the importance of good cathode wetting to attain high current efficiencies. Because of those conclusions, new wetting work was commissioned and became a major component of the research during the third year of Phase III. While significant progress was made in several areas, much work

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

PubMed

Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

2011-08-29

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of exoplanets from their formation. III. The statistics of planetary luminosities

NASA Astrophysics Data System (ADS)

Mordasini, C.; Marleau, G.-D.; Mollière, P.

2017-12-01

Context. This paper continues a series in which we predict the main observable characteristics of exoplanets based on their formation. In Paper I we described our global planet formation and evolution model that is based on the core accretion paradigm. In Paper II we studied the planetary mass-radius relationship with population syntheses. Aims: In this paper we present an extensive study of the statistics of planetary luminosities during both formation and evolution. Our results can be compared with individual directly imaged extrasolar (proto)planets and with statistical results from surveys. Methods: We calculated three populations of synthetic planets assuming different efficiencies of the accretional heating by gas and planetesimals during formation. We describe the temporal evolution of the planetary mass-luminosity relation. We investigate the relative importance of the shock and internal luminosity during formation, and predict a statistical version of the post-formation mass vs. entropy "tuning fork" diagram. Because the calculations now include deuterium burning we also update the planetary mass-radius relationship in time. Results: We find significant overlap between the high post-formation luminosities of planets forming with hot and cold gas accretion because of the core-mass effect. Variations in the individual formation histories of planets can still lead to a factor 5 to 20 spread in the post-formation luminosity at a given mass. However, if the gas accretional heating and planetesimal accretion rate during the runaway phase is unknown, the post-formation luminosity may exhibit a spread of as much as 2-3 orders of magnitude at a fixed mass. As a key result we predict a flat log-luminosity distribution for giant planets, and a steep increase towards lower luminosities due to the higher occurrence rate of low-mass (M ≲ 10-40 M⊕) planets. Future surveys may detect this upturn. Conclusions: Our results indicate that during formation an estimation of

Improving Efficiency of III-N Quantum Well Based Optoelectronic Devices through Active Region Design and Growth Techniques

NASA Astrophysics Data System (ADS)

Young, Nathan Garrett

The III-Nitride materials system provides a fascinating platform for developing optoelectronic devices, such as solar cells and LEDs, which have the power to dramatically improve the efficiency of our power consumption and reduce our environmental footprint. Finding ways to make these devices more efficient is key to driving their widespread adoption. This dissertation focuses on the intersection of challenges in physics and metalorganic chemical vapor deposition (MOCVD) growth at the nanoscale when designing for device efficiency. In order to create the best possible InGaN solar cell, a multiple quantum well (MQW) active region design had to be employed to prevent strain relaxation related degradation. There were two competing challenges for MQW active region design and growth. First, it was observed current collection efficiency improved with thinner quantum barriers, which promoted efficient tunneling transport instead of inefficiency thermally activated escape. Second, GaN barriers could planarize surface defects in the MQW region under the right conditions and when grown thick enough. A two-step growth method for thinner quantum barriers was developed that simultaneously allowed for tunneling transport and planarized V-defects. Barriers as thin as 4 nm were employed in MQW active regions with up to 30 periods without structural or electrical degradation, leading to record performance. Application of dielectric optical coatings greatly reduced surface reflections and allowed a second pass of light through the device. This both demonstrated the feasibility of multijunction solar integration and boosted conversion efficiency to record levels for an InGaN solar cell. III-N LEDs have achieved state-of-the-art performance for decades, but still suffer from the phenomena of efficiency droop, where device efficiency drops dramatically at high power operation. Droop is exacerbated by the polarization-induced electric fields in InGaN quantum wells, which originate from

Formation of Light Absorbing Soluble Secondary Organics and Insoluble Polymeric Particles from the Dark Reaction of Catechol and Guaiacol with Fe(III).

PubMed

Slikboer, Samantha; Grandy, Lindsay; Blair, Sandra L; Nizkorodov, Sergey A; Smith, Richard W; Al-Abadleh, Hind A

2015-07-07

Transition metals such as iron are reactive components of environmentally relevant surfaces. Here, dark reaction of Fe(III) with catechol and guaiacol was investigated in an aqueous solution at pH 3 under experimental conditions that mimic reactions in the adsorbed phase of water. Using UV-vis spectroscopy, liquid chromatography, mass spectrometry, elemental analysis, dynamic light scattering, and electron microscopy techniques, we characterized the reactants, intermediates, and products as a function of reaction time. The reactions of Fe(III) with catechol and guaiacol produced significant changes in the optical spectra of the solutions due to the formation of light absorbing secondary organics and colloidal organic particles. The primary steps in the reaction mechanism were shown to include oxidation of catechol and guaiacol to hydroxy- and methoxy-quinones. The particles formed within a few minutes of reaction and grew to micron-size aggregates after half an hour reaction. The mass-normalized absorption coefficients of the particles were comparable to those of strongly absorbing brown carbon compounds produced by biomass burning. These results could account for new pathways that lead to atmospheric secondary organic aerosol formation and abiotic polymer formation on environmental surfaces mediated by transition metals.

Revisiting The First Galaxies: The epoch of Population III stars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muratov, Alexander L.; Gnedin, Oleg Y.; Gnedin, Nickolay Y.

2013-07-19

We investigate the transition from primordial Population III (Pop III) star formation to normal Pop II star formation in the first galaxies using new cosmological hydrodynamic simulations. We find that while the first stars seed their host galaxies with metals, they cannot sustain significant outflows to enrich the intergalactic medium, even assuming a top-heavy initial mass function. This means that Pop III star formation could potentially continue until z 6 in different unenriched regions of the universe, before being ultimately shut off by cosmic reionization. Within an individual galaxy, the metal production and stellar feedback from Pop II stars overtake Pop III stars inmore » 20-200 Myr, depending on galaxy mass.« less

Efficient formation of benzylic quaternary centers via palladium catalysis.

PubMed

Gottumukkala, Aditya L; Suljagic, Jasmin; Matcha, Kiran; de Vries, Johannes G; Minnaard, Adriaan J

2013-09-01

Four's a crowd: An efficient protocol for the formation of benzylic quaternary centers via arylation of enones using a catalyst made from Pd(O2 CCF3 )2 and 2,2'-bipyridine is developed. For cyclic substrates, catalyst loadings as low as 1 mol % Pd are enough to afford excellent yields (>90%) using a variety of arylboronic acids. In case of acyclic substrates, the addition of KSbF6 was found to improve conversions and yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl-Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Fatalov, Alexey M; Yudanova, Evgenia I; Lyubovskaya, Rimma N

2018-04-14

Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K + )}{(cis-indigo-O,O) 2- Ti IV (Pc 2- )}(Cl - )⋅C 6 H 4 Cl 2 (1), {cryptand(K + )}{(cis-thioindigo-O,O) 2- In III (Pc 2- )} - ⋅C 6 H 4 Cl 2 (2), and {cryptand(K + )}{[(SQ) 2 -O,O] 2- In III (Pc 2- )} - ⋅3.5 C 6 H 4 Cl 2 (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti IV Pc or In III Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ - ) 2 dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In III Pc. Dianionic Pc 2- macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of anodic layers on InAs (111)III. Study of the chemical composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valisheva, N. A., E-mail: valisheva@thermo.isp.nsc.ru; Tereshchenko, O. E.; Prosvirin, I. P.

2012-04-15

The chemical composition of {approx}20-nm-thick anodic layers grown on InAs (111)III in alkaline and acid electrolytes containing or not containing NH{sub 4}F is studied by X-ray photoelectron spectroscopy. It is shown that the composition of fluorinated layers is controlled by the relation between the concentrations of fluorine and hydroxide ions in the electrolyte and by diffusion processes in the growing layer. Fluorine accumulates at the (anodic layer)/InAs interface. Oxidation of InAs in an acid electrolyte with a low oxygen content and a high NH{sub 4}F content brings about the formation of anodic layers with a high content of fluorine andmore » elemental arsenic and the formation of an oxygen-free InF{sub x}/InAs interface. Fluorinated layers grown in an alkaline electrolyte with a high content of O{sup 2-} and/or OH{sup -} groups contain approximately three times less fluorine and consist of indium and arsenic oxyfluorides. No distinction between the compositions of the layers grown in both types of fluorine-free electrolytes is established.« less

WHERE ARE THE LOW-MASS POPULATION III STARS?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishiyama, Tomoaki; Sudo, Kae; Yokoi, Shingo

2016-07-20

We study the number and the distribution of low-mass Population III (Pop III) stars in the Milky Way. In our numerical model, hierarchical formation of dark matter minihalos and Milky-Way-sized halos are followed by a high-resolution cosmological simulation. We model the Pop III formation in H{sub 2} cooling minihalos without metal under UV radiation of the Lyman–Werner bands. Assuming a Kroupa initial mass function (IMF) from 0.15 to 1.0 M {sub ⊙} for low-mass Pop III stars, as a working hypothesis, we try to constrain the theoretical models in reverse by current and future observations. We find that the survivorsmore » tend to concentrate on the center of halo and subhalos. We also evaluate the observability of Pop III survivors in the Milky Way and dwarf galaxies, and constraints on the number of Pop III survivors per minihalo. The higher latitude fields require lower sample sizes because of the high number density of stars in the galactic disk, the required sample sizes are comparable in the high- and middle-latitude fields by photometrically selecting low-metallicity stars with optimized narrow-band filters, and the required number of dwarf galaxies to find one Pop III survivor is less than 10 at <100 kpc for the tip of red giant stars. Provided that available observations have not detected any survivors, the formation models of low-mass Pop III stars with more than 10 stars per minihalo are already excluded. Furthermore, we discuss the way to constrain the IMF of Pop III stars at a high mass range of ≳10 M {sub ⊙}.« less

Efficient Sporulation of Saccharomyces cerevisiae in a 96 Multiwell Format.

PubMed

Paulissen, Scott M; Huang, Linda S

2016-09-17

During times of nutritional stress, Saccharomyces cerevisiae undergoes gametogenesis, known as sporulation. Diploid yeast cells that are starved for nitrogen and carbon will initiate the sporulation process. The process of sporulation includes meiosis followed by spore formation, where the haploid nuclei are packaged into environmentally resistant spores. We have developed methods for the efficient sporulation of budding yeast in 96 multiwell plates, to increase the throughput of screening yeast cells for sporulation phenotypes. These methods are compatible with screening with yeast containing plasmids requiring nutritional selection, when appropriate minimal media is used, or with screening yeast with genomic alterations, when a rich presporulation regimen is used. We find that for this method, aeration during sporulation is critical for spore formation, and have devised techniques to ensure sufficient aeration that are compatible with the 96 multiwell plate format. Although these methods do not achieve the typical ~80% level of sporulation that can be achieved in large-volume flask based experiments, these methods will reliably achieve about 50-60% level of sporulation in small-volume multiwell plates.

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Efficiently Visible-Light Driven Photoelectrocatalytic Oxidation of As(III) at Low Positive Biasing Using Pt/TiO2 Nanotube Electrode

NASA Astrophysics Data System (ADS)

Qin, Yanyan; Li, Yilian; Tian, Zhen; Wu, Yangling; Cui, Yanping

2016-01-01

A constant current deposition method was selected to load highly dispersed Pt nanoparticles on TiO2 nanotubes in this paper, to extend the excited spectrum range of TiO2-based photocatalysts to visible light. The morphology, elemental composition, and light absorption capability of as-obtained Pt/TiO2 nanotubes electrodes were characterized by FE-SEM, energy dispersive spectrometer (EDS), X-ray photoelectron spectrometer (XPS), and UV-vis spectrometer. The photocatalytic and photoelectrocatalytic oxidation of As(III) using a Pt/TiO2 nanotube arrays electrode under visible light ( λ > 420 nm) irradiation were investigated in a divided anode/cathode electrolytic tank. Compared with pure TiO2 which had no As(III) oxidation capacity under visible light, Pt/TiO2 nanotubes exhibited excellent visible-light photocatalytic performance toward As(III), even at dark condition. In anodic cell, As(III) could be oxidized with high efficiency by photoelectrochemical process with only 1.2 V positive biasing. Experimental results showed that photoelectrocatalytic oxidation process of As(III) could be well described by pseudo-first-order kinetic model. Rate constants depended on initial concentration of As(III), applied bias potential and solution pH. At the same time, it was interesting to find that in cathode cell, As(III) was also continuously oxidized to As(V). Furthermore, high-arsenic groundwater sample (25 m underground) with 0.32 mg/L As(III) and 0.35 mg/L As(V), which was collected from Daying Village, Datong basin, Northern China, could totally transform to As(V) after 200 min under visible light in this system.

Fab is the most efficient format to express functional antibodies by yeast surface display.

PubMed

Sivelle, Coline; Sierocki, Raphaël; Ferreira-Pinto, Kelly; Simon, Stéphanie; Maillere, Bernard; Nozach, Hervé

2018-04-30

Multiple formats are available for engineering of monoclonal antibodies (mAbs) by yeast surface display, but they do not all lead to efficient expression of functional molecules. We therefore expressed four anti-tumor necrosis factor and two anti-IpaD mAbs as single-chain variable fragment (scFv), antigen-binding fragment (Fab) or single-chain Fabs and compared their expression levels and antigen-binding efficiency. Although the scFv and scFab formats are widely used in the literature, 2 of 6 antibodies were either not or weakly expressed. In contrast, all 6 antibodies expressed as Fab revealed strong binding and high affinity, comparable to that of the soluble form. We also demonstrated that the variations in expression did not affect Fab functionality and were due to variations in light chain display and not to misfolded dimers. Our results suggest that Fab is the most versatile format for the engineering of mAbs.

Misbalance in type III collagen formation/degradation as a novel serological biomarker for penetrating (Montreal B3) Crohn's disease.

PubMed

van Haaften, W T; Mortensen, J H; Karsdal, M A; Bay-Jensen, A C; Dijkstra, G; Olinga, P

2017-07-01

Misbalances in extracellular matrix turnover are key factors in the development of stricturing (Montreal B2) and penetrating (Montreal B3) Crohn's disease. To determine whether serological markers for collagen formation and degradation could serve as biomarkers for complications of Crohn's disease. Serum biomarkers for type I, III, V and VI collagen formation (P1NP, Pro-C3, Pro-C5, Pro-C6) and matrix metalloproteinase mediated degradation (C1M, C3M, C5M and C6M) were measured in a retrospective, single centre cohort of 112 patients with Crohn's disease in the terminal ileum (nonstricturing/nonpenetrating: n=40, stricturing: n=55, penetrating: n=17) and 24 healthy controls. Active inflammation was defined as CRP >5 mg/L. C3M and Pro-C5 levels were higher in penetrating vs nonpenetrating/nonstricturing and stricturing disease (33.6±5 vs 25.8±2.2 [P=.004] and 27.2±2.3 [P=.018] nmol/L C3M, 1262.7±259.4 vs 902.9±109.9 [P=.005] and 953.0±106.4 [P=.015] nmol/L Pro-C5). C1M (71.2±26.1 vs 46.2±6.2 nmol/L [P<.001]), C3M (31.6±3.9 vs 26.1±1.6 nmol/L [P=.002] and Pro-C5 levels (1171.7±171.5 vs 909.6±80.4 nmol/L [P=.002]) were higher in patients with active inflammation vs without active inflammation. Pro-C3/C3M-ratios were best to differentiate between penetrating vs nonstricturing/nonpenetrating and stricturing disease with area under the curves of 0.815±0.109 (P<.001) and 0.746±0.114 (P=.002) respectively. Serological biomarkers show that penetrating Crohn's disease is characterised by increased matrix metalloproteinase-9 degraded type III collagen and formation of type V collagen. Active inflammation in Crohn's disease is characterised by increased formation of type V collagen and increased matrix metalloproteinase mediated breakdown of type I, III collagen. Pro-C3/C3M ratios are superior in differentiating between penetrating Crohn's disease vs inflammatory and stricturing Crohn's disease. © 2017 The Authors. Alimentary Pharmacology and Therapeutics

Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.; Jiang, J.; Lou, S.; Yarberry, F.

1999-01-01

Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.

Innovative design of composite structures: Use of curvilinear fiber format to improve structural efficiency

NASA Technical Reports Server (NTRS)

Hyer, M. W.; Charette, R. F.

1987-01-01

To increase the effectiveness and efficiency of fiber-reinforced materials, the use of fibers in a curvilinear rather than the traditional straightline format is explored. The capacity of a laminated square plate with a central circular hole loaded in tension is investigated. The orientation of the fibers is chosen so that the fibers in a particular layer are aligned with the principle stress directions in that layer. Finite elements and an iteration scheme are used to find the fiber orientation. A noninteracting maximum strain criterion is used to predict load capacity. The load capacities of several plates with different curvilinear fibers format are compared with the capacities of more conventional straightline format designs. It is found that the most practical curvilinear design sandwiches a group of fibers in a curvilinear format between a pair of +/-45 degree layers. This design has a 60% greater load capacity than a conventional quasi-isotropic design with the same number of layers. The +/-45 degree layers are necessary to prevent matrix cracking in the curvilinear layers due to stresses perpendicular to the fibers in those layers. Greater efficiencies are achievable with composite structures than now realized.

Polydopamine nanotube mediated fluorescent biosensor for Hg(ii) determination through exonuclease III-assisted signal amplification.

PubMed

A, Ravikumar; P, Panneerselvam

2018-05-29

We describe a highly sensitive fluorescence biosensor incorporating polydopamine nanotubes (PDNTs) based on the mechanism of exonuclease III (Exo III) assisted signal amplification for the determination of Hg2+ in aqueous solution. Fluorescent probes of FAM labeled ssDNA (FAM-ssDNA) adsorbed on the PDNTs act as an efficient quencher. In the presence of Hg2+, the FAM-ssDNA can bind to Hg2+ to form double stranded DNA (dsDNA) via the formation of T-Hg2+-T base pairs. Then, the dsDNA was removed from the surface of the PDNTs to restore the fluorescence. The release of the dsDNA was triggered by Exo III digestion. At the same time, the liberated Hg2+ mediates a new cycle of digestion. This assay is ultrasensitive for the selective recognition of Hg2+, and a detection limit as low as 10 pM was achieved. In addition, the fluorescent biosensing system also displays remarkable specificity to Hg2+ in the presence of other possible competing ions. This approach was applied to the determination of Hg2+ in real water samples with good recovery and high efficiency for practical analysis.

Evidence for a hyperglycaemia-dependent decrease of antithrombin III-thrombin complex formation in humans.

PubMed

Ceriello, A; Giugliano, D; Quatraro, A; Marchi, E; Barbanti, M; Lefèbvre, P

1990-03-01

In the presence of increased levels of fibrinopeptide A, decreased antithrombin III biological activity, and thrombin-antithrombin III complex levels are seen in diabetic patients. Induced-hyperglycaemia in diabetic and normal subjects decreased antithrombin III activity and thrombin-antithrombin III levels, and increased fibrinopeptide A plasma levels, while antithrombin III concentration did not change; heparin was shown to reduced these phenomena. In diabetic patients, euglycaemia induced by insulin infusion restored antithrombin III activity, thrombin-antithrombin III complex and fibrinopeptide A concentrations; heparin administration had the same effects. These data stress the role of a hyperglycaemia-dependent decrease of antithrombin III activity in precipitating thrombin hyperactivity in diabetes mellitus.

Novel red phosphorescent polymers bearing both ambipolar and functionalized Ir(III) phosphorescent moieties for highly efficient organic light-emitting diodes.

PubMed

Zhao, Jiang; Lian, Meng; Yu, Yue; Yan, Xiaogang; Xu, Xianbin; Yang, Xiaolong; Zhou, Guijiang; Wu, Zhaoxin

2015-01-01

A series of novel red phosphorescent polymers is successfully developed through Suzuki cross-coupling among ambipolar units, functionalized Ir(III) phosphorescent blocks, and fluorene-based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy-transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light-emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η L ) of 8.31 cd A(-1) , external quantum efficiency (η ext ) of 16.07%, and power efficiency (η P ) of 2.95 lm W(-1) , representing the state-of-the-art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

C III] Emission in Star-forming Galaxies Near and Far

NASA Astrophysics Data System (ADS)

Rigby, J. R.; Bayliss, M. B.; Gladders, M. D.; Sharon, K.; Wuyts, E.; Dahle, H.; Johnson, T.; Peña-Guerrero, M.

2015-11-01

We measure [C iii] 1907, C iii] 1909 Å emission lines in 11 gravitationally lensed star-forming galaxies at z ˜ 1.6-3, finding much lower equivalent widths than previously reported for fainter lensed galaxies. While it is not yet clear what causes some galaxies to be strong C iii] emitters, C iii] emission is not a universal property of distant star-forming galaxies. We also examine C iii] emission in 46 star-forming galaxies in the local universe, using archival spectra from GHRS, FOS, and STIS on HST and IUE. Twenty percent of these local galaxies show strong C iii] emission, with equivalent widths < -5 Å. Three nearby galaxies show C iii] emission equivalent widths as large as the most extreme emitters yet observed in the distant universe; all three are Wolf-Rayet galaxies. At all redshifts, strong C iii] emission may pick out low-metallicity galaxies experiencing intense bursts of star formation. Such local C iii] emitters may shed light on the conditions of star formation in certain extreme high-redshift galaxies.

Lanthanoplatins: emissive Eu(iii) and Tb(iii) complexes staining nucleoli targeted through Pt-DNA crosslinking.

PubMed

Singh, Khushbu; Singh, Swati; Srivastava, Payal; Sivakumar, Sri; Patra, Ashis K

2017-06-01

Two highly luminescent water-soluble heterometallic LnPt 2 complexes, [{cis-PtCl(NH 3 ) 2 } 2 Ln(L)(H 2 O)](NO 3 ) 2 (Ln = Eu (1), Tb (2)), have been designed for their selective nucleoli staining through formation of Pt-DNA crosslinks. The complexes showed significant cellular uptake and distinctive nucleoli localization through intrinsic emission from Eu III or Tb III observed through confocal fluorescence microscopy.

C III] Emission in Star-Forming Galaxies Near and Far

NASA Technical Reports Server (NTRS)

Rigby, J, R.; Bayliss, M. B.; Gladders, M. D.; Sharon, K.; Wuyts, E.; Dahle, H.; Johnson, T.; Pena-Guerrero, M.

2015-01-01

We measure C III Lambda Lambda 1907, 1909 Angstrom emission lines in eleven gravitationally-lensed star-forming galaxies at zeta at approximately 1.6-3, finding much lower equivalent widths than previously reported for fainter lensed galaxies (Stark et al. 2014). While it is not yet clear what causes some galaxies to be strong C III] emitters, C III] emission is not a universal property of distant star-forming galaxies. We also examine C III] emission in 46 star-forming galaxies in the local universe, using archival spectra from GHRS, FOS, and STIS on HST, and IUE. Twenty percent of these local galaxies show strong C III] emission, with equivalent widths less than -5 Angstrom. Three nearby galaxies show C III] emission equivalent widths as large as the most extreme emitters yet observed in the distant universe; all three are Wolf-Rayet galaxies. At all redshifts, strong C III] emission may pick out low-metallicity galaxies experiencing intense bursts of star formation. Such local C III] emitters may shed light on the conditions of star formation in certain extreme high-redshift galaxies.

The Relation between [O III]/Hβ and Specific Star Formation Rate in Galaxies at z ˜ 2

NASA Astrophysics Data System (ADS)

Dickey, Claire Mackay; van Dokkum, Pieter G.; Oesch, Pascal A.; Whitaker, Katherine E.; Momcheva, Ivelina G.; Nelson, Erica J.; Leja, Joel; Brammer, Gabriel B.; Franx, Marijn; Skelton, Rosalind E.

2016-09-01

Recent surveys have identified a seemingly ubiquitous population of galaxies with elevated [O III]/Hβ emission line ratios at z > 1, although the nature of this phenomenon continues to be debated. The [O III]/Hβ line ratio is of interest because it is a main component of the standard diagnostic tools used to differentiate between active galactic nuclei and star-forming galaxies as well as the gas-phase metallicity indicators O 23 and R 23. Here, we investigate the primary driver of increased [O III]/Hβ ratios by median-stacking rest-frame optical spectra for a sample of star-forming galaxies in the 3D-HST survey in the redshift range z ˜ 1.4-2.2. Using N = 4220 star-forming galaxies, we stack the data in bins of mass and specific star formation rates (sSFRs), respectively. After accounting for stellar Balmer absorption, we measure [O III]λ5007 Å/Hβ down to M ˜ 109.2 M ⊙ and sSFR ˜ 10-9.6 yr-1, greater than an order of magnitude lower than previous work at similar redshifts. We find an offset of 0.59 ± 0.05 dex between the median ratios at z ˜ 2 and z ˜ 0 at fixed stellar mass, in agreement with existing studies. However, with respect to sSFR, the z ˜ 2 stacks all lie within 1σ of the median SDSS ratios, with an average offset of only -0.06 ± 0.05. We find that the excitation properties of galaxies are tightly correlated with their sSFR at both z ˜ 2 and z ˜ 0, with a relation that appears to be roughly constant over the last 10 Gyr of cosmic time.

Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water - the Tooeleite Way

NASA Astrophysics Data System (ADS)

Malakar, Arindam; Das, Bidisa; Islam, Samirul; Meneghini, Carlo; de Giudici, Giovanni; Merlini, Marco; Kolen'Ko, Yury V.; Iadecola, Antonella; Aquilanti, Giuliana; Acharya, Somobrata; Ray, Sugata

2016-05-01

Increasing exposure to arsenic (As) contaminated ground water is a great threat to humanity. Suitable technology for As immobilization and removal from water, especially for As(III) than As(V), is not available yet. However, it is known that As(III) is more toxic than As(V) and most groundwater aquifers, particularly the Gangetic basin in India, is alarmingly contaminated with it. In search of a viable solution here, we took a cue from the natural mineralization of Tooeleite, a mineral containing Fe(III) and As(III)ions, grown under acidic condition, in presence of SO42- ions. Complying to this natural process, we could grow and separate Tooeleite-like templates from Fe(III) and As(III) containing water at overall circumneutral pH and in absence of SO42- ions by using highly polar Zn-only ends of wurtzite ZnS nanorods as insoluble nano-acidic-surfaces. The central idea here is to exploit these insoluble nano-acidic-surfaces (called as INAS in the manuscript) as nucleation centres for Tooeleite growth while keeping the overall pH of the aqueous media neutral. Therefore, we propose a novel method of artificial mineralization of As(III) by mimicking a natural process at nanoscale.

Reversal of Fortune: Increased Star Formation Efficiencies in the Early Histories of Dwarf Galaxies?

NASA Astrophysics Data System (ADS)

Madau, Piero; Weisz, Daniel R.; Conroy, Charlie

2014-08-01

On dwarf galaxy scales, the different shapes of the galaxy stellar mass function and the dark halo mass function require a star-formation efficiency (SFE) in these systems that is currently more than 1 dex lower than that of Milky Way-size halos. Here, we argue that this trend may actually be reversed at high redshift. Specifically, by combining the resolved star-formation histories of nearby isolated dwarfs with the simulated mass-growth rates of dark matter halos, we show that the assembly of these systems occurs in two phases: (1) an early, fast halo accretion phase with a rapidly deepening potential well, characterized by a high SFE; and (2) a late, slow halo accretion phase where, perhaps as a consequence of reionization, the SFE is low. Nearby dwarfs have more old stars than predicted by assuming a constant or decreasing SFE with redshift, a behavior that appears to deviate qualitatively from the trends seen among more massive systems. Taken at face value, the data suggest that at sufficiently early epochs, dwarf galaxy halos above the atomic cooling mass limit can be among the most efficient sites of star formation in the universe.

Effect of temperature on carrier formation efficiency in organic photovoltaic cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moritomo, Yutaka, E-mail: moritomo.yutaka.gf@u.tsukuba.ac.jp; Yonezawa, Kouhei; Yasuda, Takeshi

2014-08-18

The internal quantum efficiency (ϕ{sub IQ}) of an organic photovoltaic cell is governed by plural processes. Here, we propose that ϕ{sub IQ} can be experimentally decomposed into carrier formation (ϕ{sub CF}) and carrier transfer (ϕ{sub CT}) efficiencies. By combining femtosecond time-resolved and electrochemical spectroscopy, we clarified the effect of temperature on ϕ{sub CF} in a regioregular poly(3-hexylthiophene) (rr-P3HT)/[6,6]-phenyl C{sub 61}-butyric acid methyl ester blend film. We found that ϕ{sub CF} (=0.55) at 80 K is the same as that (=0.55) at 300 K. The temperature insensitivity of ϕ{sub CF} indicates that the electron-hole pairs at the D/A interface are seldom subjected to coulombicmore » binding energy.« less

Distinguishing crystallization stages and their influence on quantum efficiency during perovskite solar cell formation in real-time.

PubMed

Wagner, Lukas; Mundt, Laura E; Mathiazhagan, Gayathri; Mundus, Markus; Schubert, Martin C; Mastroianni, Simone; Würfel, Uli; Hinsch, Andreas; Glunz, Stefan W

2017-11-02

Relating crystallization of the absorber layer in a perovskite solar cell (PSC) to the device performance is a key challenge for the process development and in-depth understanding of these types of high efficient solar cells. A novel approach that enables real-time photo-physical and electrical characterization using a graphite-based PSC is introduced in this work. In our graphite-based PSC, the device architecture of porous monolithic contact layers creates the possibility to perform photovoltaic measurements while the perovskite crystallizes within this scaffold. The kinetics of crystallization in a solution based 2-step formation process has been analyzed by real-time measurement of the external photon to electron quantum efficiency as well as the photoluminescence emission spectra of the solar cell. With this method it was in particular possible to identify a previously overlooked crystallization stage during the formation of the perovskite absorber layer. This stage has significant influence on the development of the photocurrent, which is attributed to the formation of electrical pathways between the electron and hole contact, enabling efficient charge carrier extraction. We observe that in contrast to previously suggested models, the perovskite layer formation is indeed not complete with the end of crystal growth.

Effect of iron(III) ion on moso bamboo pyrolysis under microwave irradiation.

PubMed

Dong, Qing; Li, Xiangqian; Wang, Zhaoyu; Bi, Yanhong; Yang, Rongling; Zhang, Jinfeng; Luo, Hongzhen; Niu, Miaomiao; Qi, Bo; Lu, Chen

2017-11-01

The effect of iron(III) ion on microwave pyrolysis of moso bamboo was investigated. Hydrofluoric acid washing was used as a pilot process to demineralize moso bamboo in order to eliminate the influences of the other inorganics contained in moso bamboo itself. The results indicated that the addition of iron(III) ion increased the maximal reaction temperatures under microwave condition dependent on the amount of the added iron(III) ion. The production of the non-condensable gases was promoted by the addition of iron(III) ion mainly at the expense of liquid products. Iron(III) ion exhibited the positive effect for syngas production and inhibited the formation of CO 2 and CH 4 . The formation of Fe 2 O 3 and Fe 3 O 4 was found during microwave pyrolysis and the mechanism of the two metallic oxides formation was described in this work. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Stopped-Flow Kinetics Experiment for Advanced Undergraduate Laboratories: Formation of Iron(III) Thiocyannate

NASA Astrophysics Data System (ADS)

Clark, Charles R.

1997-10-01

A series of 15 stopped-flow kinetic experiments relating to the formation of iron(III)- thiocyanate at 25.0 °C and I = 1.0 M (NaClO4) is described. A methodology is given whereby solution preparation and data collection are able to be carried out within the time scale of a single laboratory period (3-4 h). Kinetic data are obtained using constant [SCN-], and at three H+ concentrations (0.10, 0.20, 0.30 M) for varying concentrations of Fe3+ (ca. 0.0025 - 0.020 M). Rate data (450 nm) are consistent with rate laws for the forward and reverse reactions: kf = (k1 + k2Ka1/[H+])[Fe3+] and kr = k-1 + k-2Ka2/[H+] respectively, with k1,k-1 corresponding to the rate constants for formation and decay of FeSCN2+, k2, k-2 to the rate constants for formation and decay of the FeSCN(OH)+ ion and Ka1,Ka2 to the acid dissociation constants (coordinated OH2 ionization) of Fe3+ and FeSCN2+. Using literature values for the latter two quantities ( Ka1 = 2.04 x 10-3 M, Ka2 = 6.5 x 10-5 M) allows values for the four rate constants to be obtained. A typical data set is analyzed to give k1 = 109(10) M-1s-1, k-1 = 0.79(0.10) s-1, k2= 8020(800) M-1s-1, k-2 = 2630(230) s-1. Absorbance change data for reaction (DeltaA) follow the expression: DeltaA = Alim.Kf.[Fe3+]/(1 + Kf.[Fe3+]), with Alim corresponding to the absorbance of fully formed FeSCN2+ (i.e. free SCN- absent) and Kf to the formation constant of this complex (value in the example 112(5) M-1, c.f. 138(29) M-1 from the kinetic data).

Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

PubMed Central

Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

2012-01-01

A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H2 mol−1 catalyst h−1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

DSM-III as a research tool.

PubMed

Treece, C

1982-05-01

The author describes the use of the DSM-III's diagnostic criteria and classification system as a research instrument and discusses some of the advantages and drawbacks of DMS-III for a specific type of study. A rearrangement of the hierarchical order of the DSM-III diagnostic classes is suggested. This rearrangement provides for levels of certainty in analyzing interrater reliability and offers a simplified framework for summarizing group data. When this approach is combined with a structured interview and response format, it provides a flexible way of managing a large classification system for a smaller study without sacrificing standardization.

Efficient generation of perfluoroalkyl radicals from sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent: mild, metal-free synthesis of perfluoroalkylated organic molecules.

PubMed

Sakamoto, Ryu; Kashiwagi, Hirotaka; Selvakumar, Sermadurai; Moteki, Shin A; Maruoka, Keiji

2016-07-06

This article describes an efficient method for the introduction of perfluoroalkyl groups into N-acrylamides, 2-isocyanides, olefins, and other heterocycles using perfluoroalkyl radicals that were generated from the reaction between sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent. This approach represents a simple, scalable perfluoroalkylation method under mild and metal-free conditions.

Th(As(III)4As(V)4O18): a mixed-valent oxoarsenic(III)/arsenic(V) actinide compound obtained under extreme conditions.

PubMed

Yu, Na; Klepov, Vladislav V; Kegler, Philip; Bosbach, Dirk; Albrecht-Schmitt, Thomas E; Alekseev, Evgeny V

2014-08-18

A high-temperature/high-pressure method was employed to investigate phase formation in the Th(NO3)4·5H2O-As2O3-CsNO3 system. It was observed that an excess of arsenic(III) in starting system leads to the formation of Th(As(III)4As(V)4O18), which is representative of a rare class of mixed-valent arsenic(III)/arsenic(V) compounds. This compound was studied with X-ray diffraction, energy-dispersive X-ray, and Raman spectroscopy methods. Crystallographic data show that Th(As(III)4As(V)4O18) is built from (As(III)4As(V)4O18)(4-) layers connected through Th atoms. The arsenic layers are found to be isoreticular to those in previously reported As2O3 and As3O5(OH), and the geometric differences between them are discussed. Bands in the Raman spectrum are assigned with respect to the presence of AsO3 and AsO4 groups.

Bis(μ-oxo) dicopper(III) species of the simplest peralkylated diamine: enhanced reactivity toward exogenous substrates.

PubMed

Kang, Peng; Bobyr, Elena; Dustman, John; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I; Stack, T Daniel P

2010-12-06

N,N,N',N'-tetramethylethylenediamine (TMED), the simplest and most extensively used peralkylated diamine ligand, is conspicuously absent from those known to form a bis(μ-oxo)dicopper(III) (O) species, [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+), upon oxygenation of its Cu(I) complex. Presented here is the characterization of this O species and its reactivity toward exogenous substrates. Its formation is complicated both by the instability of the [(TMED)Cu(I)](1+) precursor and by competitive formation of a presumed mixed-valent trinuclear [(TMED)(3)Cu(III)Cu(II)(2)(μ(3)-O)(2)](3+) (T) species. Under most reaction conditions, the T species dominates, yet, the O species can be formed preferentially (>80%) upon oxygenation of acetone solutions, if the copper concentration is low (<2 mM) and [(TMED)Cu(I)](1+) is prepared immediately before use. The experimental data of this simplest O species provide a benchmark by which to evaluate density functional theory (DFT) computational methods for geometry optimization and spectroscopic predictions. The enhanced thermal stability of [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+) and its limited steric demands compared to other O species allows more efficient oxidation of exogenous substrates, including benzyl alcohol to benzaldehyde (80% yield), highlighting the importance of ligand structure to not only enhance the oxidant stability but also maintain accessibility to the nascent metal/O(2) oxidant.

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Electrical properties of III-Nitride LEDs: Recombination-based injection model and theoretical limits to electrical efficiency and electroluminescent cooling

DOE Office of Scientific and Technical Information (OSTI.GOV)

David, Aurelien, E-mail: adavid@soraa.com; Hurni, Christophe A.; Young, Nathan G.

The current-voltage characteristic and ideality factor of III-Nitride quantum well light-emitting diodes (LEDs) grown on bulk GaN substrates are investigated. At operating temperature, these electrical properties exhibit a simple behavior. A model in which only active-region recombinations have a contribution to the LED current is found to account for experimental results. The limit of LED electrical efficiency is discussed based on the model and on thermodynamic arguments, and implications for electroluminescent cooling are examined.

New Sm(III) complexes as electronic-excitation donors of the Seta-632 squaraine dye

NASA Astrophysics Data System (ADS)

Egorova, A. V.; Leonenko, I. I.; Aleksandrova, D. I.; Skripinets, Yu. V.; Antonovich, V. P.; Obukhova, E. N.; Patsenker, L. D.

2015-07-01

We have found optimal formation conditions of new Sm(III) chelate complexes with derivatives of oxoquinolinecarboxylic acid ( L 1 and L 2) and determined their spectral-luminescent characteristics (the luminescence and luminescence excitation wavelength maxima and the luminescence lifetimes). We have revealed that the Seta-632 squaraine dye (a fluorescent label of proteins and other biological molecules) quenches the luminescence of complexes Sm(III)- L 1 and Sm(III)- L 2. The quenching of chelate complexes is caused by the Förster resonant electronic-excitation energy transfer (FRET) from the donor (Sm(III)- L 1 or Sm(III)- L 2) to the acceptor (Seta-632). In this case, the luminescence intensity of the Seta-632 dye in the presence of Sm(III)- L 1 and Sm(III)- L 2 increases by factors of 64 and 27, respectively. The values of the Förster radii ( R 0(Sm- L1) = 38 Å, R 0(Sm- L2) = 35 Å) and the overlap integrals of the luminescence spectra of the two energy donors with the absorption spectrum of the acceptor ( J Sm- L1 = 1.22 × 1012 M-1 cm-1 nm4 and J Sm- L2 = 1.06 × 1012 M-1 cm-1 nm4), which have been calculated from the luminescence quantum intensity of the donors and from the absorption spectrum of the acceptor and its molar absorption coefficient, have made it possible to characterize the Seta-632 dye as an efficient quencher of the luminescence of Sm(III) ions. We are the first to propose Sm(III)- L 1 and Sm(III)- L 2 chelate complexes as FRET donors.

The rate and efficiency of high-mass star formation along the Hubble sequence

NASA Technical Reports Server (NTRS)

Devereux, Nicholas A.; Young, Judith S.

1991-01-01

Data obtained with IRAS are used to compare and contrast the global star formation rates for a galactic sample which represents essentially all known noninteracting spiral and lenticular galaxies within 40 Mpc. The distribution of 60 micron luminosity is similar for spirals of types Sa-Scd inclusively, although the luminosities of the very early and very late types are, on average, one order of magnitude lower. High-mass star formation rates are similar for early, intermediate, and late type spirals, and the average high-mass star formation rate per unit molecular gas mass is independent of type for spiral galaxies. A remarkable homogeneity exists in the high-mass star-forming capabilities of spiral galaxies, particularly among the Sa-Scd types. The Hubble sequence is therefore not a sequence in the present-day rate or production efficiency of high-mass stars.

Insights from Synthetic Star-forming Regions. III. Calibration of Measurement and Techniques of Star Formation Rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koepferl, Christine M.; Robitaille, Thomas P.; Dale, James E., E-mail: koepferl@usm.lmu.de

Through an extensive set of realistic synthetic observations (produced in Paper I), we assess in this part of the paper series (Paper III) how the choice of observational techniques affects the measurement of star formation rates (SFRs) in star-forming regions. We test the accuracy of commonly used techniques and construct new methods to extract the SFR, so that these findings can be applied to measure the SFR in real regions throughout the Milky Way. We investigate diffuse infrared SFR tracers such as those using 24 μ m, 70 μ m and total infrared emission, which have been previously calibrated formore » global galaxy scales. We set up a toy model of a galaxy and show that the infrared emission is consistent with the intrinsic SFR using extra-galactic calibrated laws (although the consistency does not prove their reliability). For local scales, we show that these techniques produce completely unreliable results for single star-forming regions, which are governed by different characteristic timescales. We show how calibration of these techniques can be improved for single star-forming regions by adjusting the characteristic timescale and the scaling factor and give suggestions of new calibrations of the diffuse star formation tracers. We show that star-forming regions that are dominated by high-mass stellar feedback experience a rapid drop in infrared emission once high-mass stellar feedback is turned on, which implies different characteristic timescales. Moreover, we explore the measured SFRs calculated directly from the observed young stellar population. We find that the measured point sources follow the evolutionary pace of star formation more directly than diffuse star formation tracers.« less

Progress in efficient doping of high aluminum-containing group III-nitrides

NASA Astrophysics Data System (ADS)

Liang, Y.-H.; Towe, E.

2018-03-01

The group III-nitride (InN, GaN, and AlN) class of semiconductors has become one of two that are critical to a number of technologies in modern life—the other being silicon. Light-emitting diodes made from (In,Ga)N, for example, dominate recent innovations in general illumination and signaling. Even though the (In,Ga)N materials system is fairly well established and widely used in advanced devices, challenges continue to impede development of devices that include aluminum-containing nitride films such as (Al,Ga)N. The main difficulty is efficient doping of films with aluminum-rich compositions; the problem is particularly severe for p-type doping, which is essential for Ohmic contacts to bipolar device structures. This review briefly summarizes the fundamental issues related to p-type doping, and then discusses a number of approaches that are being pursued to resolve the doping problem or for circumventing the need for p-type doping. Finally, we discuss an approach to doping under liquid-metal-enabled growth by molecular beam epitaxy. Recent results from a number of groups appear to indicate that p-type doping of nitride films under liquid-metal-enabled growth conditions might offer a solution to the doping problem—at least for materials grown by molecular beam epitaxy.

Propionibacterium-Produced Coproporphyrin III Induces Staphylococcus aureus Aggregation and Biofilm Formation

PubMed Central

Wollenberg, Michael S.; Claesen, Jan; Escapa, Isabel F.; Aldridge, Kelly L.; Fischbach, Michael A.

2014-01-01

ABSTRACT The majority of bacteria detected in the nostril microbiota of most healthy adults belong to three genera: Propionibacterium, Corynebacterium, and Staphylococcus. Among these staphylococci is the medically important bacterium Staphylococcus aureus. Almost nothing is known about interspecies interactions among bacteria in the nostrils. We observed that crude extracts of cell-free conditioned medium from Propionibacterium spp. induce S. aureus aggregation in culture. Bioassay-guided fractionation implicated coproporphyrin III (CIII), the most abundant extracellular porphyrin produced by human-associated Propionibacterium spp., as a cause of S. aureus aggregation. This aggregation response depended on the CIII dose and occurred during early stationary-phase growth, and a low pH (~4 to 6) was necessary but was not sufficient for its induction. Additionally, CIII induced plasma-independent S. aureus biofilm development on an abiotic surface in multiple S. aureus strains. In strain UAMS-1, CIII stimulation of biofilm depended on sarA, a key biofilm regulator. This study is one of the first demonstrations of a small-molecule-mediated interaction among medically relevant members of the nostril microbiota and the first description of a role for CIII in bacterial interspecies interactions. Our results indicate that CIII may be an important mediator of S. aureus aggregation and/or biofilm formation in the nostril or other sites inhabited by Propionibacterium spp. and S. aureus. PMID:25053784

Rapid and highly efficient preconcentration of Eu(III) by core-shell structured Fe3O4@humic acid magnetic nanoparticles.

PubMed

Yang, Shitong; Zong, Pengfei; Ren, Xuemei; Wang, Qi; Wang, Xiangke

2012-12-01

In this study, humic acid-coated Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)@HA MNPs) were synthesized using a chemical coprecipitation method and characterized in detail. The XRD analysis results showed that HA coating did not change the phase of Fe(3)O(4) cores. The TEM image suggested that Fe(3)O(4)@HA MNPs had nearly uniform size without the observation of aggregation. The Fe(3)O(4)@HA MNPs were stable in solution and could be easily separated from aqueous solution using a magnetic separation method. A batch technique was adopted to investigate the removal efficiency of Fe(3)O(4)@HA MNPs toward Eu(III) under various environmental conditions. The kinetic process of Eu(III) sorption on Fe(3)O(4)@HA MNPs reached equilibrium within <30 min. The fast sorption kinetics and high sorption amount were attributed to the plentiful surface sites provided by the surface-coated HA macromolecules. The Fe(3)O(4)@HA MNPs was able to remove ~99% of Eu(III) in aqueous solution at pH 8.5. Except for SO(4)(2-) anions, the coexisting electrolyte ions had no significant competition effects on the removal of Eu(III) by Fe(3)O(4)@HA MNPs. The obvious sorption-desorption hysteresis suggested that the removal of Eu(III) was dominated by inner-sphere surface complexation. The sorption isotherm agreed well with the Langmuir model, having a maximum sorption capacity of 6.95 × 10(-5) mol g(-1). The leaching test showed that the Eu(III)-loaded Fe(3)O(4)@HA colloids were capable to maintain high thermodynamic stability for long aging times. The findings herein suggested that Fe(3)O(4)@HA MNPs could be potentially used as a highly effective material for the enrichment and preconcentration of radionuclide Eu(III) or other trivalent lanthanides/actinides in geological repositories or in nuclear waste management.

PANCHROMATIC HUBBLE ANDROMEDA TREASURY. XVI. STAR CLUSTER FORMATION EFFICIENCY AND THE CLUSTERED FRACTION OF YOUNG STARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, L. Clifton; Sandstrom, Karin; Seth, Anil C.

We use the Panchromatic Hubble Andromeda Treasury survey data set to perform spatially resolved measurements of star cluster formation efficiency (Γ), the fraction of stellar mass formed in long-lived star clusters. We use robust star formation history and cluster parameter constraints, obtained through color–magnitude diagram analysis of resolved stellar populations, to study Andromeda’s cluster and field populations over the last ∼300 Myr. We measure Γ of 4%–8% for young, 10–100 Myr-old populations in M31. We find that cluster formation efficiency varies systematically across the M31 disk, consistent with variations in mid-plane pressure. These Γ measurements expand the range of well-studiedmore » galactic environments, providing precise constraints in an H i-dominated, low-intensity star formation environment. Spatially resolved results from M31 are broadly consistent with previous trends observed on galaxy-integrated scales, where Γ increases with increasing star formation rate surface density (Σ{sub SFR}). However, we can explain observed scatter in the relation and attain better agreement between observations and theoretical models if we account for environmental variations in gas depletion time ( τ {sub dep}) when modeling Γ, accounting for the qualitative shift in star formation behavior when transitioning from a H{sub 2}-dominated to a H i-dominated interstellar medium. We also demonstrate that Γ measurements in high Σ{sub SFR} starburst systems are well-explained by τ {sub dep}-dependent fiducial Γ models.« less

Efficient CO2-Reducing Activity of NAD-Dependent Formate Dehydrogenase from Thiobacillus sp. KNK65MA for Formate Production from CO2 Gas

PubMed Central

Cho, Dae Haeng; Kim, Min Hoo; Lee, Sang Hyun; Jung, Kwang Deog; Kim, Yong Hwan

2014-01-01

NAD-dependent formate dehydrogenase (FDH) from Candida boidinii (CbFDH) has been widely used in various CO2-reduction systems but its practical applications are often impeded due to low CO2-reducing activity. In this study, we demonstrated superior CO2-reducing properties of FDH from Thiobacillus sp. KNK65MA (TsFDH) for production of formate from CO2 gas. To discover more efficient CO2-reducing FDHs than a reference enzyme, i.e. CbFDH, five FDHs were selected with biochemical properties and then, their CO2-reducing activities were evaluated. All FDHs including CbFDH showed better CO2-reducing activities at acidic pHs than at neutral pHs and four FDHs were more active than CbFDH in the CO2 reduction reaction. In particular, the FDH from Thiobacillus sp. KNK65MA (TsFDH) exhibited the highest CO2-reducing activity and had a dramatic preference for the reduction reaction, i.e., a 84.2-fold higher ratio of CO2 reduction to formate oxidation in catalytic efficiency (k cat/K B) compared to CbFDH. Formate was produced from CO2 gas using TsFDH and CbFDH, and TsFDH showed a 5.8-fold higher formate production rate than CbFDH. A sequence and structural comparison showed that FDHs with relatively high CO2-reducing activities had elongated N- and C-terminal loops. The experimental results demonstrate that TsFDH can be an alternative to CbFDH as a biocatalyst in CO2 reduction systems. PMID:25061666

III-V/Ge MOS device technologies for low power integrated systems

NASA Astrophysics Data System (ADS)

Takagi, S.; Noguchi, M.; Kim, M.; Kim, S.-H.; Chang, C.-Y.; Yokoyama, M.; Nishi, K.; Zhang, R.; Ke, M.; Takenaka, M.

2016-11-01

CMOS utilizing high mobility III-V/Ge channels on Si substrates is expected to be one of the promising devices for high performance and low power integrated systems in the future technology nodes, because of the enhanced carrier transport properties. In addition, Tunneling-FETs (TFETs) using Ge/III-V materials are regarded as one of the most important steep slope devices for the ultra-low power applications. In this paper, we address the device and process technologies of Ge/III-V MOSFETs and TFETs on the Si CMOS platform. The channel formation, source/drain (S/D) formation and gate stack engineering are introduced for satisfying the device requirements. The plasma post oxidation to form GeOx interfacial layers is a key gate stack technology for Ge CMOS. Also, direct wafer bonding of ultrathin body quantum well III-V-OI channels, combined with Tri-gate structures, realizes high performance III-V n-MOSFETs on Si. We also demonstrate planar-type InGaAs and Ge/strained SOI TFETs. The defect-less p+-n source junction formation with steep impurity profiles is a key for high performance TFET operation.

Preparation of manganese(II), chromium(III) and ferric(III) oxides nanoparticles in situ metal citraconate complexes frameworks

NASA Astrophysics Data System (ADS)

Refat, Moamen S.

2014-12-01

The new reactions of some divalent and trivalent transition metal ions (Mn(II), Cr(III), and Fe(III)) with citraconic acid has been studied. The obtained results indicate the formation of citraconic acid compounds with molar ratio of metal to citraconic acid of 2:2 or 2:3 with general formulas Mn2(C5H4O4)2 or M2(C5H4O4)3ṡnH2O where n = 6 for Cr, and Fe(III). The thermal decomposition of the crystalline solid complexes was investigated. The IR spectra of citraconate suggested that the carboxylic groups are bidentatically bridging and chelating. In the course of decomposition the complexes are dehydrated and then decompose either directly to oxides in only one step or with intermediate formation of oxocarbonates. This proposal dealing the preparation of MnO2, Fe2O3 and Cr2O3 nanoparticles. The crystalline structure of oxide products were checked by X-ray powder diffraction (XRD), and the morphology of particles by scanning electron microscopy (SEM).

Cytotoxic and genotoxic potential of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA complex in human hepatoma (HepG2) cells.

PubMed

Novotnik, Breda; Ščančar, Janez; Milačič, Radmila; Filipič, Metka; Žegura, Bojana

2016-07-01

Chromium (Cr) and ethylenediaminetetraacetate (EDTA) are common environmental pollutants and can be present in high concentrations in surface waters at the same time. Therefore, chelation of Cr with EDTA can occur and thereby stable Cr(III)-EDTA complex is formed. Since there are no literature data on Cr(III)-EDTA toxicity, the aim of our work was to evaluate and compare Cr(III)-EDTA cytotoxic and genotoxic activity with those of Cr(VI) and Cr(III)-nitrate in human hepatoma (HepG2) cell line. First the effect of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on cell viability was studied in the concentration range from 0.04 μg mL(-1) to 25 μg mL(-1) after 24 h exposure. Further the influence of non-cytotoxic concentrations of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on DNA damage and genomic stability was determined with the comet assay and cytokinesis block micronucleus cytome assay, respectively. Cell viability was decreased only by Cr(VI) at concentrations above 1.0 μg mL(-1). Cr(VI) at ≥0.2 μg mL(-1) and Cr(III) at ≥1.0 μg mL(-1) induced DNA damage, while after Cr(III)-EDTA exposure no formation DNA strand breaks was determined. Statistically significant formation of micronuclei was induced only by Cr(VI) at ≥0.2 μg mL(-1), while no influence on the frequency of nuclear buds nor nucleoplasmic bridges was observed at any exposure. This study provides the first evidence that Cr(III)-EDTA did not induce DNA damage and had no influence on the genomic stability of HepG2 cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of ribonuclease III from Brucella.

PubMed

Wu, Chang-Xian; Xu, Xian-Jin; Zheng, Ke; Liu, Fang; Yang, Xu-Dong; Chen, Chuang-Fu; Chen, Huan-Chun; Liu, Zheng-Fei

2016-04-01

Bacterial ribonuclease III (RNase III) is a highly conserved endonuclease, which plays pivotal roles in RNA maturation and decay pathways by cleaving double-stranded structure of RNAs. Here we cloned rncS gene from the genomic DNA of Brucella melitensis, and analyzed the cleavage properties of RNase III from Brucella. We identified Brucella-encoding small RNA (sRNA) by high-throughput sequencing and northern blot, and found that sRNA of Brucella and Homo miRNA precursor (pre-miRNA) can be bound and cleaved by B.melitensis ribonuclease III (Bm-RNase III). Cleavage activity of Bm-RNase III is bivalent metal cations- and alkaline buffer-dependent. We constructed several point mutations in Bm-RNase III, whose cleavage activity indicated that the 133th Glutamic acid residue was required for catalytic activity. Western blot revealed that Bm-RNase III was differently expressed in Brucella virulence strain 027 and vaccine strain M5-90. Collectively, our data suggest that Brucella RNase III can efficiently bind and cleave stem-loop structure of small RNA, and might participate in regulation of virulence in Brucella. Copyright © 2016 Elsevier B.V. All rights reserved.

Structure and magnetic properties of an unprecedented syn-anti μ-nitrito-1κO:2κO' bridged Mn(III)-salen complex and its isoelectronic and isostructural formate analogue.

PubMed

Kar, Paramita; Biswas, Rituparna; Drew, Michael G B; Ida, Yumi; Ishida, Takayuki; Ghosh, Ashutosh

2011-04-07

The preparation, crystal structures and magnetic properties of two new isoelectronic and isomorphous formate- and nitrite-bridged 1D chains of Mn(III)-salen complexes, [Mn(salen)(HCOO)](n) (1) and [Mn(salen)(NO(2))](n) (2), where salen is the dianion of N,N'-bis(salicylidene)-1,2-diaminoethane, are presented. The structures show that the salen ligand coordinates to the four equatorial sites of the metal ion and the formate or nitrite ions coordinate to the axial positions to bridge the Mn(III)-salen units through a syn-antiμ-1κO:2κO' coordination mode. Such a bridging mode is unprecedented in Mn(III) for formate and in any transition metal ion for nitrite. Variable-temperature magnetic susceptibility measurements of complexes 1 and 2 indicate the presence of ferromagnetic exchange interactions with J values of 0.0607 cm(-1) (for 1) and 0.0883 cm(-1) (for 2). The ac measurements indicate negligible frequency dependence for 1 whereas compound 2 exhibits a decrease of χ(ac)' and a concomitant increase of χ(ac)'' on elevating frequency around 2 K. This finding is an indication of slow magnetization reversal characteristic of single-chain magnets or spin-glasses. The μ-nitrito-1κO:2κO' bridge seems to be a potentially superior magnetic coupler to the formate bridge for the construction of single-molecule/-chain magnets as its coupling constant is greater and the χ(ac)' and χ(ac)'' show frequency dependence. © The Royal Society of Chemistry 2011

Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

PubMed

Ivanov, Mikhail V; Babikov, Dmitri

2012-05-14

Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

Photofunctional triplet excited states of cyclometalated Ir(III) complexes: beyond electroluminescence.

PubMed

You, Youngmin; Nam, Wonwoo

2012-11-07

The development of cyclometalated Ir(III) complexes has enabled important breakthroughs in electroluminescence because such complexes permit the efficient population of triplet excited states that give rise to luminescent transitions. The triplet states of Ir(III) complexes are advantageous over those of other transition metal complexes in that their electronic transitions and charge-transfer characteristics are tunable over wide ranges. These favorable properties suggest that Ir(III) complexes have significant potential in a variety of photofunctions other than electroluminescence. In this critical review, we describe recent photonic applications of novel Ir(III) complexes. Ir(III) complexes have been shown to affect the exciton statistics in the active layers of organic photovoltaic cells, thereby improving the photon-to-current conversion efficiencies. Nonlinear optical applications that take advantage of the strong charge-transfer properties of triplet transitions are also discussed. The tunability of the electrochemical potentials facilitates the development of efficient photocatalysis in the context of water photolysis or organic syntheses. The photoredox reactivities of Ir(III) complexes have been employed in studies of charge migration along DNA chains. The photoinduced cytotoxicity of Ir(III) complexes on live cells suggests that the complexes may be useful in photodynamic therapy. Potential biological applications of the complexes include phosphorescence labeling and sensing. Intriguing platforms based on cyclometalated Ir(III) complexes potentially provide novel protein tagging and ratiometric detection. We envision that future research into the photofunctionality of Ir(III) complexes will provide important breakthroughs in a variety of photonic applications.

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

PubMed

Adam, Christian; Beele, Björn B; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J

2015-02-01

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15 N labeling and characterized by NMR and LIFDI-MS methods. 15 N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15 N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP) 3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP) 3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

PubMed

Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

2015-03-01

A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical constraints on the contribution of population III stars to cosmic reionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Girish; Hennawi, Joseph F.; Rollinde, Emmanuel

2014-05-20

Recent studies have highlighted that galaxies at z = 6-8 fall short of producing enough ionizing photons to reionize the intergalactic medium, and suggest that Population III stars could resolve this tension, because their harder spectra can produce ∼10 × more ionizing photons than Population II. We use a semi-analytic model of galaxy formation, which tracks galactic chemical evolution, to gauge the impact of Population III stars on reionization. Population III supernovae produce distinct metal abundances, and we argue that the duration of the Population III era can be constrained by precise relative abundance measurements in high-z damped Lyα absorbersmore » (DLAs), which provide a chemical record of past star formation. We find that a single generation of Population III stars can self-enrich galaxies above the critical metallicity Z {sub crit} = 10{sup –4} Z {sub ☉} for the Population III-to-II transition, on a very short timescale t {sub self-enrich} ∼ 10{sup 6} yr, owing to the large metal yields and short lifetimes of Population III stars. This subsequently terminates the Population III era, so they contribute ≳ 50% of the ionizing photons only for z ≳ 30, and at z = 10 contribute <1%. The Population III contribution can be increased by delaying metal mixing into the interstellar medium. However, comparing the resulting metal abundance pattern to existing measurements in z ≲ 6 DLAs, we show that the observed [O/Si] ratios of absorbers rule out Population III stars being a major contributor to reionization. Future abundance measurements of z ∼ 7-8 QSOs and gamma-ray bursts should probe the era when the chemical vestiges of Population III star formation become detectable.« less

CARE3MENU- A CARE III USER FRIENDLY INTERFACE

NASA Technical Reports Server (NTRS)

Pierce, J. L.

1994-01-01

CARE3MENU generates an input file for the CARE III program. CARE III is used for reliability prediction of complex, redundant, fault-tolerant systems including digital computers, aircraft, nuclear and chemical control systems. The CARE III input file often becomes complicated and is not easily formatted with a text editor. CARE3MENU provides an easy, interactive method of creating an input file by automatically formatting a set of user-supplied inputs for the CARE III system. CARE3MENU provides detailed on-line help for most of its screen formats. The reliability model input process is divided into sections using menu-driven screen displays. Each stage, or set of identical modules comprising the model, must be identified and described in terms of number of modules, minimum number of modules for stage operation, and critical fault threshold. The fault handling and fault occurence models are detailed in several screens by parameters such as transition rates, propagation and detection densities, Weibull or exponential characteristics, and model accuracy. The system fault tree and critical pairs fault tree screens are used to define the governing logic and to identify modules affected by component failures. Additional CARE3MENU screens prompt the user for output options and run time control values such as mission time and truncation values. There are fourteen major screens, many with default values and HELP options. The documentation includes: 1) a users guide with several examples of CARE III models, the dialog required to input them to CARE3MENU, and the output files created; and 2) a maintenance manual for assistance in changing the HELP files and modifying any of the menu formats or contents. CARE3MENU is written in FORTRAN 77 for interactive execution and has been implemented on a DEC VAX series computer operating under VMS. This program was developed in 1985.

Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

PubMed

Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

2017-06-01

Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn 2 Al-Met-LDHs, identified with the formula of Zn 0.7 Al 0.3 (OH) 2 (Met) 0.3 ·0.32H 2 O, has good thermal stability. Adsorption experiments with Zn 2 Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn 2 Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn 2 Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Neutrino Background from Population III Stars

NASA Astrophysics Data System (ADS)

Iocco, Fabio

2011-12-01

Population III Stars (PopIII) are the first generation of stars formed from the collapse of the very first structures in the Universe. Their peculiar chemical composition (metal-free, resembling the Primordial Nucleosynthesis yields) affects their formation and evolution and makes them unusually big and hot stars. They are good candidates for the engines of Reionization of the Universe although their direct observation is extremely difficult. Here we summarize a study of their expected diffuse low-energy neutrino background flux at Earth.

Redox Conversion of Chromium(VI) and Arsenic(III) with the Intermediates of Chromium(V) and Arsenic(IV) via AuPd/CNTs Electrocatalysis in Acid Aqueous Solution.

PubMed

Sun, Meng; Zhang, Gong; Qin, Yinghua; Cao, Meijuan; Liu, Yang; Li, Jinghong; Qu, Jiuhui; Liu, Huijuan

2015-08-04

Simultaneous reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) is a promising pretreatment process for the removal of chromium and arsenic from acid aqueous solution. In this work, the synergistic redox conversion of Cr(VI) and As(III) was efficiently achieved in a three-dimensional electrocatalytic reactor with synthesized AuPd/CNTs particles as electrocatalysts. The AuPd/CNTs facilitated the exposure of active Pd{111} facets and possessed an approximate two-electron-transfer pathway of oxygen reduction with the highly efficient formation of H2O2 as end product, resulting in the electrocatalytic reduction of 97.2 ± 2.4% of Cr(VI) and oxidation of 95.7 ± 4% of As(III). The electrocatalytic reduction of Cr(VI) was significantly accelerated prior to the electrocatalytic oxidation of As(III), and the effectiveness of Cr(VI)/As(III) conversion was favored at increased currents from 20 to 150 mA, decreased initial pH from 7 to 1 and concentrations of Cr(VI) and As(III) ranging from 50 to 1 mg/L. The crucial intermediates of Cr(V) and As(IV) and active free radicals HO(•) and O2(•-) were found for the first time, whose roles in the control of Cr(VI)/As(III) redox conversion were proposed. Finally, the potential applicability of AuPd/CNTs was revealed by their stability in electrocatalytic conversion over 10 cycles.

N,B-Bidentate Boryl Ligand-Supported Iridium Catalyst for Efficient Functional-Group-Directed C-H Borylation.

PubMed

Wang, Guanghui; Liu, Li; Wang, Hong; Ding, You-Song; Zhou, Jing; Mao, Shuai; Li, Pengfei

2017-01-11

Convenient silylborane precursors for introducing N,B-bidentate boryl ligands onto transition metals were designed, prepared, and employed in ready formation of irdium(III) complexes via Si-B oxidative addition. A practical, efficient catalytic ortho-borylation reaction of arenes with a broad range of directing groups was developed using an in situ generated catalyst from the silylborane preligand 3c and [IrCl(COD)] 2 .

How can macromolecular crowding inhibit biological reactions? The enhanced formation of DNA nanoparticles

PubMed Central

Hou, Sen; Trochimczyk, Piotr; Sun, Lili; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Zhang, Xuzhu; Wielgus-Kutrowska, Beata; Bzowska, Agnieszka; Holyst, Robert

2016-01-01

In contrast to the already known effect that macromolecular crowding usually promotes biological reactions, solutions of PEG 6k at high concentrations stop the cleavage of DNA by HindIII enzyme, due to the formation of DNA nanoparticles. We characterized the DNA nanoparticles and probed the prerequisites for their formation using multiple techniques such as fluorescence correlation spectroscopy, dynamic light scattering, fluorescence analytical ultracentrifugation etc. In >25% PEG 6k solution, macromolecular crowding promotes the formation of DNA nanoparticles with dimensions of several hundreds of nanometers. The formation of DNA nanoparticles is a fast and reversible process. Both plasmid DNA (2686 bp) and double-stranded/single-stranded DNA fragment (66bp/nt) can form nanoparticles. We attribute the enhanced nanoparticle formation to the depletion effect of macromolecular crowding. This study presents our idea to enhance the formation of DNA nanoparticles by macromolecular crowding, providing the first step towards a final solution to efficient gene therapy. PMID:26903405

How can macromolecular crowding inhibit biological reactions? The enhanced formation of DNA nanoparticles.

PubMed

Hou, Sen; Trochimczyk, Piotr; Sun, Lili; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Zhang, Xuzhu; Wielgus-Kutrowska, Beata; Bzowska, Agnieszka; Holyst, Robert

2016-02-23

In contrast to the already known effect that macromolecular crowding usually promotes biological reactions, solutions of PEG 6k at high concentrations stop the cleavage of DNA by HindIII enzyme, due to the formation of DNA nanoparticles. We characterized the DNA nanoparticles and probed the prerequisites for their formation using multiple techniques such as fluorescence correlation spectroscopy, dynamic light scattering, fluorescence analytical ultracentrifugation etc. In >25% PEG 6k solution, macromolecular crowding promotes the formation of DNA nanoparticles with dimensions of several hundreds of nanometers. The formation of DNA nanoparticles is a fast and reversible process. Both plasmid DNA (2686 bp) and double-stranded/single-stranded DNA fragment (66 bp/nt) can form nanoparticles. We attribute the enhanced nanoparticle formation to the depletion effect of macromolecular crowding. This study presents our idea to enhance the formation of DNA nanoparticles by macromolecular crowding, providing the first step towards a final solution to efficient gene therapy.

Computed tomographic analysis of temporal maxillary stability and pterygomaxillary generate formation following pediatric Le Fort III distraction advancement.

PubMed

Hopper, Richard A; Sandercoe, Gavin; Woo, Albert; Watts, Robyn; Kelley, Patrick; Ettinger, Russell E; Saltzman, Babette

2010-11-01

Le Fort III distraction requires generation of bone in the pterygomaxillary region. The authors performed retrospective digital analysis on temporal fine-cut computed tomographic images to quantify both radiographic evidence of pterygomaxillary region bone formation and relative maxillary stability. Fifteen patients with syndromic midface hypoplasia were included in the study. The average age of the patients was 8.7 years; 11 had either Crouzon or Apert syndrome. The average displacement of the maxilla during distraction was 16.2 mm (range, 7 to 31 mm). Digital analysis was performed on fine-cut computed tomographic scans before surgery, at device removal, and at annual follow-up. Seven patients also had mid-consolidation computed tomographic scans. Relative maxillary stability and density of radiographic bone in the pterygomaxillary region were calculated between each scan. There was no evidence of clinically significant maxillary relapse, rotation, or growth between the end of consolidation and 1-year follow-up, other than a relatively small 2-mm subnasal maxillary vertical growth. There was an average radiographic ossification of 0.5 mm/mm advancement at the time of device removal, with a 25th percentile value of 0.3 mm/mm. The time during consolidation that each patient reached the 25th percentile of pterygomaxillary region bone density observed in this series of clinically stable advancements ranged from 1.3 to 9.8 weeks (average, 3.7 weeks). There was high variability in the amount of bone formed in the pterygomaxillary region associated with clinical stability of the advanced Le Fort III segment. These data suggest that a subsection of patients generate the minimal amount of pterygomaxillary region bone formation associated with advancement stability as early as 4 weeks into consolidation.

Universal description of III-V/Si epitaxial growth processes

NASA Astrophysics Data System (ADS)

Lucci, I.; Charbonnier, S.; Pedesseau, L.; Vallet, M.; Cerutti, L.; Rodriguez, J.-B.; Tournié, E.; Bernard, R.; Létoublon, A.; Bertru, N.; Le Corre, A.; Rennesson, S.; Semond, F.; Patriarche, G.; Largeau, L.; Turban, P.; Ponchet, A.; Cornet, C.

2018-06-01

Here, we experimentally and theoretically clarify III-V/Si crystal growth processes. Atomically resolved microscopy shows that monodomain three-dimensional islands are observed at the early stages of AlSb, AlN, and GaP epitaxy on Si, independently of misfit. It is also shown that complete III-V/Si wetting cannot be achieved in most III-V/Si systems. Surface/interface contributions to the free-energy variations are found to be prominent over strain relief processes. We finally propose a general and unified description of III-V/Si growth processes, including a description of the formation of antiphase boundaries.

Trifluoromethyl-Substituted Iridium(III) Complexes: From Photophysics to Photooxidation of a Biological Target.

PubMed

Bevernaegie, Robin; Marcélis, Lionel; Laramée-Milette, Baptiste; De Winter, Julien; Robeyns, Koen; Gerbaux, Pascal; Hanan, Garry S; Elias, Benjamin

2018-02-05

Photodynamic therapeutic agents are of key interest in developing new strategies to develop more specific and efficient anticancer treatments. In comparison to classical chemotherapeutic agents, the activity of photodynamic therapeutic compounds can be finely controlled thanks to the light triggering of their photoreactivity. The development of type I photosensitizing agents, which do not rely on the production of ROS, is highly desirable. In this context, we developed new iridium(III) complexes which are able to photoreact with biomolecules; namely, our Ir(III) complexes can oxidize guanine residues under visible light irradiation. We report the synthesis and extensive photophysical characterization of four new Ir(III) complexes, [Ir(ppyCF 3 ) 2 (N^N)] + [ppyCF 3 = 2-(3,5-bis(trifluoromethyl)phenyl)pyridine) and N^N = 2,2'-dipyridyl (bpy); 2-(pyridin-2-yl)pyrazine (pzpy); 2,2'-bipyrazine (bpz); 1,4,5,8-tetraazaphenanthrene (TAP)]. In addition to an extensive experimental and theoretical study of the photophysics of these complexes, we characterize their photoreactivity toward model redox-active targets and the relevant biological target, the guanine base. We demonstrate that photoinduced electron transfer takes place between the excited Ir(III) complex and guanine which leads to the formation of stable photoproducts, indicating that the targeted guanine is irreversibly damaged. These results pave the way to the elaboration of new type I photosensitizers for targeting cancerous cells.

Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium.

PubMed

Pathak, P N; Mohapatra, M; Godbole, S V

2013-11-01

UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1×10(-3)M Eu(III) and AHA complex system decreased with increased AHA concentration from 116±0.2μs (no AHA) to 1.6±0.1μs (0.1M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu(3+)-AHA complex as 1.42±0.64 under the conditions of this study. By contrast, the Tb(III)-AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364±9μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)-AHA system showed the formation of 1:1 complex (log K: 1.72±0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium

NASA Astrophysics Data System (ADS)

Pathak, P. N.; Mohapatra, M.; Godbole, S. V.

2013-11-01

UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1 M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1 × 10-3 M Eu(III) and AHA complex system decreased with increased AHA concentration from 116 ± 0.2 μs (no AHA) to 1.6 ± 0.1 μs (0.1 M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu3+-AHA complex as 1.42 ± 0.64 under the conditions of this study. By contrast, the Tb(III)-AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364 ± 9 μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)-AHA system showed the formation of 1:1 complex (log K: 1.72 ± 0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions.

Composition, formation, and regulation of the cytosolic c-ring, a dynamic component of the type III secretion injectisome.

PubMed

Diepold, Andreas; Kudryashev, Mikhail; Delalez, Nicolas J; Berry, Richard M; Armitage, Judith P

2015-01-01

Many gram-negative pathogens employ a type III secretion injectisome to translocate effector proteins into eukaryotic host cells. While the structure of the distal "needle complex" is well documented, the composition and role of the functionally important cytosolic complex remain less well understood. Using functional fluorescent fusions, we found that the C-ring, an essential and conserved cytosolic component of the system, is composed of ~22 copies of SctQ (YscQ in Yersinia enterocolitica), which require the presence of YscQC, the product of an internal translation initiation site in yscQ, for their cooperative assembly. Photoactivated localization microscopy (PALM) reveals that in vivo, YscQ is present in both a free-moving cytosolic and a stable injectisome-bound state. Notably, fluorescence recovery after photobleaching (FRAP) shows that YscQ exchanges between the injectisome and the cytosol, with a t½ of 68 ± 8 seconds when injectisomes are secreting. In contrast, the secretin SctC (YscC) and the major export apparatus component SctV (YscV) display minimal exchange. Under non-secreting conditions, the exchange rate of YscQ is reduced to t½ = 134 ± 16 seconds, revealing a correlation between C-ring exchange and injectisome activity, which indicates a possible role for C-ring stability in regulation of type III secretion. The stabilization of the C-ring depends on the presence of the functional ATPase SctN (YscN). These data provide new insights into the formation and composition of the injectisome and present a novel aspect of type III secretion, the exchange of C-ring subunits, which is regulated with respect to secretion.

Impact of a star formation efficiency profile on the evolution of open clusters

NASA Astrophysics Data System (ADS)

Shukirgaliyev, B.; Parmentier, G.; Berczik, P.; Just, A.

2017-09-01

Aims: We study the effect of the instantaneous expulsion of residual star-forming gas on star clusters in which the residual gas has a density profile that is shallower than that of the embedded cluster. This configuration is expected if star formation proceeds with a given star-formation efficiency per free-fall time in a centrally concentrated molecular gas clump. Methods: We performed direct N-body simulations whose initial conditions were generated by the program "mkhalo" from the package "falcON", adapted for our models. Our model clusters initially had a Plummer profile and are in virial equilibrium with the gravitational potential of the cluster-forming clump. The residual gas contribution was computed based on a local-density driven clustered star formation model. Our simulations included mass loss by stellar evolution and the tidal field of a host galaxy. Results: We find that a star cluster with a minimum global star formation efficiency (SFE) of 15 percent is able to survive instantaneous gas expulsion and to produce a bound cluster. Its violent relaxation lasts no longer than 20 Myr, independently of its global SFE and initial stellar mass. At the end of violent relaxation, the bound fractions of the surviving clusters with the same global SFEs are similar, regardless of their initial stellar mass. Their subsequent lifetime in the gravitational field of the Galaxy depends on their bound stellar masses. Conclusions: We therefore conclude that the critical SFE needed to produce a bound cluster is 15 percent, which is roughly half the earlier estimates of 33 percent. Thus we have improved the survival likelihood of young clusters after instantaneous gas expulsion. Young clusters can now survive instantaneous gas expulsion with a global SFEs as low as the SFEs observed for embedded clusters in the solar neighborhood (15-30 percent). The reason is that the star cluster density profile is steeper than that of the residual gas. However, in terms of the

Sensitizing Tb(III) and Eu(III) emission with triarylboron functionalized 1,3-diketonato ligands.

PubMed

Smith, Larissa F; Blight, Barry A; Park, Hee-Jun; Wang, Suning

2014-08-04

Four BMes2Ar (Mes = mesityl, Ar = phenyl or duryl) functionalized 1,3-diketonato ligands have been investigated for use in selective sensitization of Tb(III) and Eu(III) emission. These ligands have the general formula of [R1C(O)CR2C(O)R3](-) (R1 = Ph, R2 = H, R3 = p-Ph-BMes2, L1; R1 = R3 = p-Ph-BMes2, R2 = H, L2; R1 = R3 = Me, R2 = p-Ph-BMes2, L3; R1 = R3 = Me, R2 = p-duryl-BMes2, L4) and belong to class I (L1 and L2) and class II (L3 and L4), respectively. In class I, the boron unit is conjugated with the phenyl linker and the diketone backbone, while in class II, the boron unit, the linker unit, and the diketone unit are nonconjugated with a mutually orthogonal arrangement. To understand the impact of the location of the BMes2Ar unit on the electronic properties of the 1,3-diketone molecules and their ability in activating lanthanide emission, the difluoroboron chelate compounds (1-BF2 to 4-BF2) of ligands L1-L4 were synthesized and examined. The class I ligands were effective in activating Eu(III) emission, while the class II ligands were effective in activating Tb(III) emission. Four Ln(III) complexes, 1Eu, 2Eu, 3Tb, and 4Tb, based on the L1-L4 ligands, respectively, were prepared and examined. The emission quantum efficiency of 1Eu and 2Eu is low (Φ(Eu) ≤ 0.01 in THF, 0.07-0.13 in the solid state), but can be greatly enhanced by the addition of fluoride ions. In contrast, the complex 4Tb has a moderate emission efficiency (Φ(Tb) = 0.14 in THF, 0.47 in the solid state) and experiences a distinct emission quenching upon the addition of fluoride. The selective sensitization of Eu(III) and Tb(III) by L1-L4 and the distinct luminescent response of their Ln(III) complexes toward fluoride ions are caused by the distinct intraligand charge transfer transitions of the two different classes of ligands involving the BMes2 unit.

Three-step effluent chlorination increases disinfection efficiency and reduces DBP formation and toxicity.

PubMed

Li, Yu; Zhang, Xiangru; Yang, Mengting; Liu, Jiaqi; Li, Wanxin; Graham, Nigel J D; Li, Xiaoyan; Yang, Bo

2017-02-01

Chlorination is extensively applied for disinfecting sewage effluents, but it unintentionally generates disinfection byproducts (DBPs). Using seawater for toilet flushing introduces a high level of bromide into domestic sewage. Chlorination of sewage effluent rich in bromide causes the formation of brominated DBPs. The objectives of achieving a disinfection goal, reducing disinfectant consumption and operational costs, as well as diminishing adverse effects to aquatic organisms in receiving water body remain a challenge in sewage treatment. In this study, we have demonstrated that, with the same total chlorine dosage, a three-step chlorination (dosing chlorine by splitting it into three equal portions with a 5-min time interval for each portion) was significantly more efficient in disinfecting a primary saline sewage effluent than a one-step chlorination (dosing chlorine at one time). Compared to one-step chlorination, three-step chlorination enhanced the disinfection efficiency by up to 0.73-log reduction of Escherichia coli. The overall DBP formation resulting from one-step and three-step chlorination was quantified by total organic halogen measurement. Compared to one-step chlorination, the DBP formation in three-step chlorination was decreased by up to 23.4%. The comparative toxicity of one-step and three-step chlorination was evaluated in terms of the development of embryo-larva of a marine polychaete Platynereis dumerilii. The results revealed that the primary sewage effluent with three-step chlorination was less toxic than that with one-step chlorination, indicating that three-step chlorination could reduce the potential adverse effects of disinfected sewage effluents to aquatic organisms in the receiving marine water. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Yellow-Emitting Homoleptic Iridium(III) Complex Constructed from a Multifunctional Spiro Ligand for Highly Efficient Phosphorescent Organic Light-Emitting Diodes.

PubMed

Ren, Bao-Yi; Guo, Run-Da; Zhong, Dao-Kun; Ou, Chang-Jin; Xiong, Gang; Zhao, Xiang-Hua; Sun, Ya-Guang; Jurow, Matthew; Kang, Jun; Zhao, Yi; Li, Sheng-Biao; You, Li-Xin; Wang, Lin-Wang; Liu, Yi; Huang, Wei

2017-07-17

To suppress concentration quenching and to improve charge-carrier injection/transport in the emission layer (EML) of phosphorescent organic light-emitting diodes (PhOLEDs), a facial homoleptic iridium(III) complex emitter with amorphous characteristics was designed and prepared in one step from a multifunctional spiro ligand containing spiro[fluorene-9,9'-xanthene] (SFX) unit. Single-crystal X-ray analysis of the resulting fac-Ir(SFXpy) 3 complex revealed an enlarged Ir···Ir distance and negligible intermolecular π-π interactions between the spiro ligands. The emitter exhibits yellow emission and almost equal energy levels compared to the commercial phosphor iridium(III) bis(4-phenylthieno[3,2-c]pyridinato-N,C 2 ')acetylacetonate (PO-01). Dry-processed devices using a common host, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl, and the fac-Ir(SFXpy) 3 emitter at a doping concentration of 15 wt % exhibited a peak performance of 46.2 cd A -1 , 36.3 lm W -1 , and 12.1% for the current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE), respectively. Compared to control devices using PO-01 as the dopant, the fac-Ir(SFXpy) 3 -based devices remained superior in the doping range between 8 and 15 wt %. The current densities went up with increasing doping concentration at the same driving voltage, while the roll-offs remain relatively low even at high doping levels. The superior performance of the new emitter-based devices was ascribed to key roles of the spiro ligand for suppressing aggregation and assisting charge-carrier injection/transport. Benefiting from the amorphous stability of the emitter, the wet-processed device also exhibited respectful CE, PE, and EQE of 32.2 cd A -1 , 22.1 lm W -1 , and 11.3%, respectively, while the EQE roll-off was as low as 1.7% at the luminance of 1000 cd m -2 . The three-dimensional geometry and binary-conjugation features render SFX the ideal multifunctional module for suppressing concentration quenching

Efficient automatic OCR word validation using word partial format derivation and language model

NASA Astrophysics Data System (ADS)

Chen, Siyuan; Misra, Dharitri; Thoma, George R.

2010-01-01

In this paper we present an OCR validation module, implemented for the System for Preservation of Electronic Resources (SPER) developed at the U.S. National Library of Medicine.1 The module detects and corrects suspicious words in the OCR output of scanned textual documents through a procedure of deriving partial formats for each suspicious word, retrieving candidate words by partial-match search from lexicons, and comparing the joint probabilities of N-gram and OCR edit transformation corresponding to the candidates. The partial format derivation, based on OCR error analysis, efficiently and accurately generates candidate words from lexicons represented by ternary search trees. In our test case comprising a historic medico-legal document collection, this OCR validation module yielded the correct words with 87% accuracy and reduced the overall OCR word errors by around 60%.

Me-3,2-HOPO Complexes of Near Infra-Red (NIR) Emitting Lanthanides: Efficient Sensitization of Yb(III) and Nd(III) in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Evan G.; Xu, Jide; Dodani, Sheel

2009-11-10

The synthesis, X-ray structure, solution stability, and photophysical properties of several trivalent lanthanide complexes of Yb(III) and Nd(III) using both tetradentate and octadentate ligand design strategies and incorporating the 1-methyl-3-hydroxy-pyridin-2-one (Me-3,2-HOPO) chelate group are reported. Both the Yb(III) and Nd(III) complexes have emission bands in the Near Infra-Red (NIR) region, and this luminescence is retained in aqueous solution ({Phi}{sub tot}{sup Yb} {approx} 0.09-0.22%). Furthermore, the complexes demonstrate very high stability (pYb {approx} 18.8-21.9) in aqueous solution, making them good candidates for further development as probes for NIR imaging. Analysis of the low temperature (77 K) photophysical measurements for a modelmore » Gd(III) complex were used to gain an insight into the electronic structure, and were found to agree well with corresponding TD-DFT calculations at the B3LYP/6-311G{sup ++}(d,p) level of theory for a simplified model monovalent sodium complex.« less

Comparative study on Ce (III) and La (III) solvent extraction and separation from a nitric acid medium by D2EHPA and Cyanex272

NASA Astrophysics Data System (ADS)

Habibpour, R.; Dargahi, M.; Kashi, E.; Bagherpour, M.

2018-01-01

The solvent extraction of Cerium(III) and Lanthanum(III) from nitric acid solution using the organophosphorous extractants Di-(2-ethyl hexyl) phosphate (D2EHPA) and di-2,4,4- trimethylpentyl phosphoric acid (Cyanex272) in kerosene was investigated. In this study, the magnitude of the extraction of Ce(III) was found to be more significant with Cyanex272 than D2EHPA. D2EHPA was found to be a better extractant for La(III). Among the two extractants, Cyanex272 was used for the separation of Ce from La in three stages with an extraction efficiency of 90.2% for Ce. A 556 mg/L Ce solution was used for the scrubbing of La with an efficiency of ≈34%, which required multi stage scrubbing. The study of thermodynamic parameters such as enthalpy, entropy, and Gibbs free energy impart the exothermic and non-spontaneous process. The chemical speciation curves for lanthanum and cerium in the aqueous phase as a function of pH showed that the free La(III) and Ce(III) metal ion species were largely predominate between a pH = 0 and pH = 7.

Opposite effects of dissolved oxygen on the removal of As(III) and As(V) by carbonate structural Fe(II).

PubMed

Tian, Zeyuan; Feng, Yong; Guan, Yiyi; Shao, Binbin; Zhang, Yalei; Wu, Deli

2017-12-05

Freshly prepared carbonate structural Fe(II) (CSF) was used to immobilize As(III) and As(V) in wastewater under oxic and anoxic conditions. Dissolved oxygen was found to exert opposite effects on these two arsenic species. The sorption density of As(III) was higher under oxic conditions, whereas that of As(V) was higher under anoxic conditions. X-ray diffraction and infrared spectroscopic analyses indicated that crystalline parasymplesite (Fe(II) 3 (AsO 4 ) 2 ·8H 2 O) was formed when As(V) was removed under anoxic conditions, while an amorphous Fe-As-containing precipitate was formed when As(III) was removed under oxic conditions. The distribution of arsenic and iron between the solution and sediments suggested that the oxidation of structural Fe(II) promoted coprecipitation process and inhibited surface complexation. X-ray photoelectron spectroscopic analyses revealed that more As(III) was oxidized under oxic condition, which contributed to a higher sorption capacity for As(III). The formation of parasymplesite through surface complexation/precipitation was proposed to be more effective for the removal of As(V) by CSF, while As(III) was more efficiently removed through coprecipitation. Together, the results suggest that CSF may be an effective material for sequestering both As(III) and As(V). In addition, attention should be paid to the dissolved oxygen content when remediating different arsenic species.

Crystallization efficiencies of inorganic polyphosphate oligomers reacted with magnesium and calcium cations using anion-exchange chromatography with particulate formation-laser scattering detector.

PubMed

Ando, Masaki; Imadzu, Sakiyo; Kitagawa, Shinya; Ohtani, Hajime

2010-08-06

A particulate formation-laser scattering detector (PFLSD) was developed and used for evaluating the crystallization efficiency of inorganic polyphosphates (PPs) that reacted with either magnesium or calcium cations. As the solutions for reactive crystallization, 0.5 M ammonium buffer (pH 9.6) containing either 0.15 M MgCl(2) or 0.15 M CaCl(2) (MAP: magnesium ammonium phosphate and HAP: hydroxyapatite solution) were used. In the case of mono- and diphosphate (P1 and P2), the significant dependences of the particulate formation efficiency on various types of both P1/P2 and MAP/HAP reaction solutions were observed with the direct sample injection mode. The PFLSD was hyphenated with the anion-exchange chromatography and the dependence of the particulate formation efficiency on the polymerization degree (n(p)) of PP oligomers, separated chromatographically, was evaluated sequentially. The significant suppression of the particulate formation for PP oligomers was clearly confirmed, i.e., the MAP and HAP reaction solutions did not produce the particulates of the PP oligomers having an n(p) value of more than 3 and 5, respectively. As the overall tendency, the particulate formation efficiency in the case of the HAP solution was superior to that in the case of the MAP solution. Copyright 2010 Elsevier B.V. All rights reserved.

Synthesis and characterization of carbazolide-based iridium PNP pincer complexes. Mechanistic and computational investigation of alkene hydrogenation: evidence for an Ir(III)/Ir(V)/Ir(III) catalytic cycle.

PubMed

Cheng, Chen; Kim, Bong Gon; Guironnet, Damien; Brookhart, Maurice; Guan, Changjian; Wang, David Y; Krogh-Jespersen, Karsten; Goldman, Alan S

2014-05-07

New carbazolide-based iridium pincer complexes ((carb)PNP)Ir(C2H4), 3a, and ((carb)PNP)Ir(H)2, 3b, have been prepared and characterized. The dihydride, 3b, reacts with ethylene to yield the cis-dihydride ethylene complex cis-((carb)PNP)Ir(C2H4)(H)2. Under ethylene this complex reacts slowly at 70 °C to yield ethane and the ethylene complex, 3a. Kinetic analysis establishes that the reaction rate is dependent on ethylene concentration and labeling studies show reversible migratory insertion to form an ethyl hydride complex prior to formation of 3a. Exposure of cis-((carb)PNP)Ir(C2H4)(H)2 to hydrogen results in very rapid formation of ethane and dihydride, 3b. DFT analysis suggests that ethane elimination from the ethyl hydride complex is assisted by ethylene through formation of ((carb)PNP)Ir(H)(Et)(C2H4) and by H2 through formation of ((carb)PNP)Ir(H)(Et)(H2). Elimination of ethane from Ir(III) complex ((carb)PNP)Ir(H)(Et)(H2) is calculated to proceed through an Ir(V) complex ((carb)PNP)Ir(H)3(Et) which reductively eliminates ethane with a very low barrier to return to the Ir(III) dihydride, 3b. Under catalytic hydrogenation conditions (C2H4/H2), cis-((carb)PNP)Ir(C2H4)(H)2 is the catalyst resting state, and the catalysis proceeds via an Ir(III)/Ir(V)/Ir(III) cycle. This is in sharp contrast to isoelectronic (PCP)Ir systems in which hydrogenation proceeds through an Ir(III)/Ir(I)/Ir(III) cycle. The basis for this remarkable difference is discussed.

The eighth fibronectin type III domain of protein tyrosine phosphatase receptor J influences the formation of protein complexes and cell localization.

PubMed

Iuliano, Rodolfo; Raso, Cinzia; Quintiero, Alfina; Pera, Ilaria Le; Pichiorri, Flavia; Palumbo, Tiziana; Palmieri, Dario; Pattarozzi, Alessandra; Florio, Tullio; Viglietto, Giuseppe; Trapasso, Francesco; Croce, Carlo Maria; Fusco, Alfredo

2009-03-01

Regulation of receptor-type phosphatases can involve the formation of higher-order structures, but the exact role played in this process by protein domains is not well understood. In this study we show the formation of different higher-order structures of the receptor-type phosphatase PTPRJ, detected in HEK293A cells transfected with different PTPRJ expression constructs. In the plasma membrane PTPRJ forms dimers detectable by treatment with the cross-linking reagent BS(3) (bis[sulfosuccinimidyl]suberate). However, other PTPRJ complexes, dependent on the formation of disulfide bonds, are detected by treatment with the oxidant agent H(2)O(2) or by a mutation Asp872Cys, located in the eighth fibronectin type III domain of PTPRJ. A deletion in the eighth fibronectin domain of PTPRJ impairs its dimerization in the plasma membrane and increases the formation of PTPRJ complexes dependent on disulfide bonds that remain trapped in the cytoplasm. The deletion mutant maintains the catalytic activity but is unable to carry out inhibition of proliferation on HeLa cells, achieved by the wild type form, since it does not reach the plasma membrane. Therefore, the intact structure of the eighth fibronectin domain of PTPRJ is critical for its localization in plasma membrane and biological function.

A Novel Role for Cytochrome c: Efficient Catalysis of S-Nitrosothiol Formation

PubMed Central

Basu, Swati; Keszler, Agnes; Azarova, Natalia A.; Nwanze, Nneka; Perlegas, Andreas; Shiva, Sruti; Broniowska, Katarzyna A.; Hogg, Neil; Kim-Shapiro, Daniel B.

2009-01-01

While S-nitrosothiols are regarded as important elements of many NO-dependent signal transduction pathways, the physiological mechanism of their formation remains elusive. Here, we demonstrate a novel mechanism by which cytochrome c may represent an efficient catalyst of S-nitrosation in vivo. In this mechanism, initial binding of GSH to ferric cytochrome c is followed by reaction of NO with this complex, yielding ferrous cytochrome c and GSNO. We show that when submitochondrial particles or cell lysates are exposed to NO in the presence of cytochrome c, there is a robust formation of protein S-nitrosothiols. In the case of submitochondrial particles protein S-nitrosation is paralleled with an inhibition of mitochondrial complex I. These observations raise the possibility that cytochrome c is a mediator of S-nitrosation in biological systems, particularly during hypoxia, and that release of cytochrome c in to the cytosol during apoptosis potentially releases a GSNO synthase activity which could modulate apoptotic signaling. PMID:19879353

Transition to the vgosDb Format

NASA Astrophysics Data System (ADS)

Bolotin, Sergei; Baver, Karen; Gipson, John; Gordon, David; MacMillan, Daniel

2016-12-01

The IVS Working Group 4 developed a new format to store and exchange data obtained from geodetic VLBI observations. The new data format, vgosDb, will replace existing Mark III databases this year. At GSFC we developed utilities that implement the vgosDb format and will be used routinely to convert correlator output to the new data storage format.

Efficient generation of volatile cadmium species using Ti(III) and Ti(IV) and application to determination of cadmium by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)†

PubMed Central

Arslan, Zikri; Yilmaz, Vedat; Rose, LaKeysha

2015-01-01

In this study, a highly efficient chemical vapor generation (CVG) approach is reported for determination of cadmium (Cd). Titanium (III) and titanium (IV) were investigated for the first time as catalytic additives along with thiourea, L-cysteine and potassium cyanide (KCN) for generation of volatile Cd species. Both Ti(III) and Ti(IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine enhanced signal slightly only with Ti(III) in H2SO4. Optimum CVG conditions were 4% (v/v) HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% (v/v) HNO3 + 0.03 M Ti(IV) + 0.16 M KCN with a 3% (m/v) NaBH4 solution. The sensitivity was improved about 40-fold with Ti(III) and 35-fold with Ti(IV). A limit of detection (LOD) of 3.2 ng L−1 was achieved with Ti(III) by CVG-ICP-MS. The LOD with Ti(IV) was 6.4 ng L−1 which was limited by the blank signals in Ti(IV) solution. Experimental evidence indicated that Ti(III) and Ti(IV) enhanced Cd vapor generation catalytically; for best efficiency mixing prior to reaction with NaBH4 was critical. The method was highly robust against the effects of transition metal ions. No significant suppression was observed in the presence of Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) up to 1.0 μg mL−1. Among the hydride forming elements, no interference was observed from As(III) and Se(IV) at 0.5 μg mL−1 level. The depressive effects from Pb(II) and Sb(III) were not significant at 0.1 μg mL−1 while those from Bi(III) and Sn(II) were marginal. The procedures were validated with determination of Cd by CVG-ICP-MS in a number certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781). PMID:26251554

PROTOSTELLAR OUTFLOWS AND RADIATIVE FEEDBACK FROM MASSIVE STARS. II. FEEDBACK, STAR-FORMATION EFFICIENCY, AND OUTFLOW BROADENING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuiper, Rolf; Turner, Neal J.; Yorke, Harold W., E-mail: rolf.kuiper@uni-tuebingen.de, E-mail: Neal.J.Turner@jpl.nasa.gov, E-mail: Harold.W.Yorke@jpl.nasa.gov

2016-11-20

We perform two-dimensional axially symmetric radiation hydrodynamic simulations to assess the impact of outflows and radiative force feedback from massive protostars by varying when the protostellar outflow starts, and to determine the ratio of ejection to accretion rates and the strength of the wide-angle disk wind component. The star-formation efficiency, i.e., the ratio of final stellar mass to initial core mass, is dominated by radiative forces and the ratio of outflow to accretion rates. Increasing this ratio has three effects. First, the protostar grows slower with a lower luminosity at any given time, lowering radiative feedback. Second, bipolar cavities clearedmore » by the outflow become larger, further diminishing radiative feedback on disk and core scales. Third, the higher momentum outflow sweeps up more material from the collapsing envelope, decreasing the protostar's potential mass reservoir via entrainment. The star-formation efficiency varies with the ratio of ejection to accretion rates from 50% in the case of very weak outflows to as low as 20% for very strong outflows. At latitudes between the low-density bipolar cavity and the high-density accretion disk, wide-angle disk winds remove some of the gas, which otherwise would be part of the accretion flow onto the disk; varying the strength of these wide-angle disk winds, however, alters the final star-formation efficiency by only ±6%. For all cases, the opening angle of the bipolar outflow cavity remains below 20° during early protostellar accretion phases, increasing rapidly up to 65° at the onset of radiation pressure feedback.« less

Thermometric studies on the Fe(III)-EDTA chelate.

PubMed

Dot, K

1978-02-01

A DeltaH of -11.5 +/- 0.5 kJ/mole has been determined for the formation of the Fe(III)-EDTA chelate at 25.0 degrees and mu = 0.1(= [HClO(4)] + [NaClO(4)]) by a direct thermometric titration procedure. The entropy change, DeltaS, has been calculated to be 440 J.mole(-1) .deg(-1) by combining the result of the heat measurements with the free energy change obtained from the stability constant previously determined. A relationship between the DeltaS values and the standard partial molal entropies of the tervalent metal ions is discussed. In addition, conditions for the thermometric titration of Fe(III) with NA(4)EDTA at room temperature have been investigated. Iron(III) can be determined in the presence of fairly large amounts of phosphate, Cr(III), Mn(II) and Al(III).

2D lateral heterostructures of group-III monochalcogenide: Potential photovoltaic applications

NASA Astrophysics Data System (ADS)

Cheng, Kai; Guo, Yu; Han, Nannan; Jiang, Xue; Zhang, Junfeng; Ahuja, Rajeev; Su, Yan; Zhao, Jijun

2018-04-01

Solar photovoltaics provides a practical and sustainable solution to the increasing global energy demand. Using first-principles calculations, we investigate the energetics and electronic properties of two-dimensional lateral heterostructures by group-III monochalcogenides and explore their potential applications in photovoltaics. The band structures and formation energies from supercell calculations demonstrate that these heterostructures retain semiconducting behavior and might be synthesized in laboratory using the chemical vapor deposition technique. According to the computed band offsets, most of the heterojunctions belong to type II band alignment, which can prevent the recombination of electron-hole pairs. Besides, the electronic properties of these lateral heterostructures can be effectively tailored by the number of layers, leading to a high theoretical power conversion efficiency over 20%.

High-Concentration III-V Multijunction Solar Cells | Photovoltaic Research

Science.gov Websites

| NREL High-Concentration III-V Multijunction Solar Cells High-Concentration III-V transfer to the high-efficiency cell industry, and the invention and development of the inverted metamorphic multijunction (IMM) cell technology. PV Research Other Materials & Devices pages: High

Constraints on superoxide mediated formation of manganese oxides

PubMed Central

Learman, Deric R.; Voelker, Bettina M.; Madden, Andrew S.; Hansel, Colleen M.

2013-01-01

Manganese (Mn) oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide (O2−) both of biogenic and abiogenic origin as an effective oxidant of Mn(II) leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III) and Mn(III/IV) oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide (H2O2), a product of the reaction of O2− with Mn(II), inhibits the oxidation process presumably through the reduction of Mn(III). Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III)-ligand complexes. While complexing ligands played a role in stabilizing Mn(III), they did not eliminate the inhibition of net Mn(III) formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II) by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II) by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation. PMID:24027565

A novel role for the integrin-binding III-10 module in fibronectin matrix assembly.

PubMed

Hocking, D C; Smith, R K; McKeown-Longo, P J

1996-04-01

Fibronectin matrix assembly is a cell-dependent process which is upregulated in tissues at various times during development and wound repair to support the functions of cell adhesion, migration, and differentiation. Previous studies have demonstrated that the alpha 5 beta 1 integrin and fibronectin's amino terminus and III-1 module are important in fibronectin polymerization. We have recently shown that fibronectin's III-1 module contains a conformationally sensitive binding site for fibronectin's amino terminus (Hocking, D.C., J. Sottile, and P.J. McKeown-Longo. 1994. J. Biol. Chem. 269: 19183-19191). The present study was undertaken to define the relationship between the alpha 5 beta 1 integrin and fibronectin polymerization. Solid phase binding assays using recombinant III-10 and III-1 modules of human plasma fibronectin indicated that the III-10 module contains a conformation-dependent binding site for the III-1 module of fibronectin. Unfolded III-10 could support the formation of a ternary complex containing both III-1 and the amino-terminal 70-kD fragment, suggesting that the III-1 module can support the simultaneous binding of III-10 and 70 kD. Both unfolded III-10 and unfolded III-1 could support fibronectin binding, but only III-10 could promote the formation of disulfide-bonded multimers of fibronectin in the absence of cells. III-10-dependent multimer formation was inhibited by both the anti-III-1 monoclonal antibody, 9D2, and amino-terminal fragments of fibronectin. A fragment of III-10, termed III-10/A, was able to block matrix assembly in fibroblast monolayers. Similar results were obtained using the III-10A/RGE fragment, in which the RGD site had been mutated to RGE, indicating that III-I0/A was blocking matrix assembly by a mechanism distinct from disruption of integrin binding. Texas red-conjugated recombinant III-1,2 localized to beta 1-containing sites of focal adhesions on cells plated on fibronectin or the III-9,10 modules of fibronectin

Mixing of phosphorescent and exciplex emission in efficient organic electroluminescent devices.

PubMed

Cherpak, Vladyslav; Stakhira, Pavlo; Minaev, Boris; Baryshnikov, Gleb; Stromylo, Evgeniy; Helzhynskyy, Igor; Chapran, Marian; Volyniuk, Dmytro; Hotra, Zenon; Dabuliene, Asta; Tomkeviciene, Ausra; Voznyak, Lesya; Grazulevicius, Juozas Vidas

2015-01-21

We fabricated a yellow organic light-emitting diode (OLED) based on the star-shaped donor compound tri(9-hexylcarbazol-3-yl)amine, which provides formation of the interface exciplexes with the iridium(III) bis[4,6-difluorophenyl]-pyridinato-N,C2']picolinate (FIrpic). The exciplex emission is characterized by a broad band and provides a condition to realize the highly effective white OLED. It consists of a combination of the blue phosphorescent emission from the FIrpic complex and a broad efficient delayed fluorescence induced by thermal activation with additional direct phosphorescence from the triplet exciplex formed at the interface. The fabricated exciplex-type device exhibits a high brightness of 38 000 cd/m(2) and a high external quantum efficiency.

Uptake Mechanisms of Eu(III) on Hydroxyapatite: A Potential Permeable Reactive Barrier Backfill Material for Trapping Trivalent Minor Actinides.

PubMed

Xu, Lin; Zheng, Tao; Yang, Shitong; Zhang, Linjuan; Wang, Jianqiang; Liu, Wei; Chen, Lanhua; Diwu, Juan; Chai, Zhifang; Wang, Shuao

2016-04-05

The permeable reactive barrier (PRB) technique has attracted an increasing level of attention for the in situ remediation of contaminated groundwater. In this study, the macroscopic uptake behaviors and microscopic speciation of Eu(III) on hydroxyapatite (HAP) were investigated by a combination of theoretical modeling, batch experiments, powder X-ray diffraction (PXRD) fitting, and X-ray absorption spectroscopy (XAS). The underlying removal mechanisms were identified to further assess the application potential of HAP as an effective PRB backfill material. The macroscopic analysis revealed that nearly all dissolved Eu(III) in solution was removed at pH 6.5 within an extremely short reaction time of 5 min. In addition, the thermodynamic calculations, desorption experiments, and PXRD and XAS analyses definitely confirmed the formation of the EuPO4·H2O(s) phase during the process of uptake of dissolved Eu(III) by HAP via the dissolution-precipitation mechanism. A detailed comparison of the present experimental findings and related HAP-metal systems suggests that the relative contribution of precipitation to the total Eu(III) removal increases as the P:Eu ratio decreases. The dosage of HAP-based PRB for the remediation of groundwater polluted by Eu(III) and analogous trivalent actinides [e.g., Am(III) and Cm(III)] should be strictly controlled depending on the dissolved Eu(III) concentration to obtain an optimal P:M (M represents Eu, Am, or Cm) ratio and treatment efficiency.

Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study.

PubMed

Kong, Xiang-He; Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Chai, Zhi-Fang; Nie, Chang-Ming; Shi, Wei-Qun

2018-05-10

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is one of the most important steps in spent nuclear fuel reprocessing. However, it is very difficult and challenging to separate them due to their similar chemical properties. Recently the pyridylpyrazole ligand (PypzH) has been identified to show good separation ability toward Am(III) over Eu(III). In this work, to explore the Am(III)/Eu(III) separation mechanism of PypzH at the molecular level, the geometrical structures, bonding nature, and thermodynamic behaviors of the Am(III) and Eu(III) complexes with PypzH ligands modified by alkyl chains (Cn-PypzH, n = 2, 4, 8) have been systematically investigated using scalar relativistic density functional theory (DFT). According to the NBO (natural bonding orbital) and QTAIM (quantum theory of atoms in molecules) analyses, the M-N bonds exhibit a certain degree of covalent character, and more covalency appears in Am-N bonds compared to Eu-N bonds. Thermodynamic analyses suggest that the 1:1 extraction reaction, [M(NO 3 )(H 2 O) 6 ] 2+ + PypzH + 2NO 3 - → M(PypzH)(NO 3 ) 3 (H 2 O) + 5H 2 O, is the most suitable for Am(III)/Eu(III) separation. Furthermore, the extraction ability and the Am(III)/Eu(III) selectivity of the ligand PypzH is indeed enhanced by adding alkyl-substituted chains in agreement with experimental observations. Besides this, the nitrogen atom of pyrazole ring plays a more significant role in the extraction reactions related to Am(III)/Eu(III) separation compared to that of pyridine ring. This work could identify the mechanism of the Am(III)/Eu(III) selectivity of the ligand PypzH and provide valuable theoretical information for achieving an efficient Am(III)/Eu(III) separation process for spent nuclear fuel reprocessing.

Galaxy Formation Efficiency and the Multiverse Explanation of the Cosmological Constant with EAGLE Simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-04-01

Models of the very early universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Galaxy formation efficiency and the multiverse explanation of the cosmological constant with EAGLE simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-07-01

Models of the very early Universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Human Metapneumovirus Induces Formation of Inclusion Bodies for Efficient Genome Replication and Transcription

PubMed Central

Cifuentes-Muñoz, Nicolás; Branttie, Jean; Slaughter, Kerri Beth

2017-01-01

ABSTRACT Human metapneumovirus (HMPV) causes significant upper and lower respiratory disease in all age groups worldwide. The virus possesses a negative-sense single-stranded RNA genome of approximately 13.3 kb encapsidated by multiple copies of the nucleoprotein (N), giving rise to helical nucleocapsids. In addition, copies of the phosphoprotein (P) and the large RNA polymerase (L) decorate the viral nucleocapsids. After viral attachment, endocytosis, and fusion mediated by the viral glycoproteins, HMPV nucleocapsids are released into the cell cytoplasm. To visualize the subsequent steps of genome transcription and replication, a fluorescence in situ hybridization (FISH) protocol was established to detect different viral RNA subpopulations in infected cells. The FISH probes were specific for detection of HMPV positive-sense RNA (+RNA) and viral genomic RNA (vRNA). Time course analysis of human bronchial epithelial BEAS-2B cells infected with HMPV revealed the formation of inclusion bodies (IBs) from early times postinfection. HMPV IBs were shown to be cytoplasmic sites of active transcription and replication, with the translation of viral proteins being closely associated. Inclusion body formation was consistent with an actin-dependent coalescence of multiple early replicative sites. Time course quantitative reverse transcription-PCR analysis suggested that the coalescence of inclusion bodies is a strategy to efficiently replicate and transcribe the viral genome. These results provide a better understanding of the steps following HMPV entry and have important clinical implications. IMPORTANCE Human metapneumovirus (HMPV) is a recently discovered pathogen that affects human populations of all ages worldwide. Reinfections are common throughout life, but no vaccines or antiviral treatments are currently available. In this work, a spatiotemporal analysis of HMPV replication and transcription in bronchial epithelial cell-derived immortal cells was performed. HMPV was

Human Metapneumovirus Induces Formation of Inclusion Bodies for Efficient Genome Replication and Transcription.

PubMed

Cifuentes-Muñoz, Nicolás; Branttie, Jean; Slaughter, Kerri Beth; Dutch, Rebecca Ellis

2017-12-15

Human metapneumovirus (HMPV) causes significant upper and lower respiratory disease in all age groups worldwide. The virus possesses a negative-sense single-stranded RNA genome of approximately 13.3 kb encapsidated by multiple copies of the nucleoprotein (N), giving rise to helical nucleocapsids. In addition, copies of the phosphoprotein (P) and the large RNA polymerase (L) decorate the viral nucleocapsids. After viral attachment, endocytosis, and fusion mediated by the viral glycoproteins, HMPV nucleocapsids are released into the cell cytoplasm. To visualize the subsequent steps of genome transcription and replication, a fluorescence in situ hybridization (FISH) protocol was established to detect different viral RNA subpopulations in infected cells. The FISH probes were specific for detection of HMPV positive-sense RNA (+RNA) and viral genomic RNA (vRNA). Time course analysis of human bronchial epithelial BEAS-2B cells infected with HMPV revealed the formation of inclusion bodies (IBs) from early times postinfection. HMPV IBs were shown to be cytoplasmic sites of active transcription and replication, with the translation of viral proteins being closely associated. Inclusion body formation was consistent with an actin-dependent coalescence of multiple early replicative sites. Time course quantitative reverse transcription-PCR analysis suggested that the coalescence of inclusion bodies is a strategy to efficiently replicate and transcribe the viral genome. These results provide a better understanding of the steps following HMPV entry and have important clinical implications. IMPORTANCE Human metapneumovirus (HMPV) is a recently discovered pathogen that affects human populations of all ages worldwide. Reinfections are common throughout life, but no vaccines or antiviral treatments are currently available. In this work, a spatiotemporal analysis of HMPV replication and transcription in bronchial epithelial cell-derived immortal cells was performed. HMPV was shown to

Influence of dihydroxybenzenes on paracetamol and ciprofloxacin degradation and iron(III) reduction in Fenton processes.

PubMed

Costa E Silva, Beatriz; de Lima Perini, João Angelo; Nogueira, Raquel F Pupo

2017-03-01

The degradation of paracetamol (PCT) and ciprofloxacin (CIP) was compared in relation to the generation of dihydroxylated products, Fe(III) reduction and reaction rate in the presence of dihydroxybenzene (DHB) compounds, or under irradiation with free iron (Fe 3+ ) or citrate complex (Fecit) in Fenton or photo-Fenton process. The formation of hydroquinone (HQ) was observed only during PCT degradation in the dark, which increased drastically the rate of PCT degradation, since HQ formed was able to reduce Fe 3+ and contributed to PCT degradation efficiency. When HQ was initially added, PCT and CIP degradation rate in the dark was much higher in comparison to the absence of HQ, due to the higher and faster formation of Fe 2+ at the beginning of reaction. In the absence of HQ, no CIP degradation was observed; however, when HQ was added after 30 min, the degradation rate increased drastically. Ten PCT hydroxylated intermediates were identified in the absence of HQ, which could contribute for Fe(III) reduction and consequently to the degradation in a similar way as HQ. During CIP degradation, only one product of hydroxyl radical attack on benzene ring and substitution of the fluorine atom was identified when HQ was added to the reaction medium.

How the First Stars Regulated Star Formation. II. Enrichment by Nearby Supernovae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ke-Jung; Whalen, Daniel J.; Wollenberg, Katharina M. J.

Metals from Population III (Pop III) supernovae led to the formation of less massive Pop II stars in the early universe, altering the course of evolution of primeval galaxies and cosmological reionization. There are a variety of scenarios in which heavy elements from the first supernovae were taken up into second-generation stars, but cosmological simulations only model them on the largest scales. We present small-scale, high-resolution simulations of the chemical enrichment of a primordial halo by a nearby supernova after partial evaporation by the progenitor star. We find that ejecta from the explosion crash into and mix violently with ablativemore » flows driven off the halo by the star, creating dense, enriched clumps capable of collapsing into Pop II stars. Metals may mix less efficiently with the partially exposed core of the halo, so it might form either Pop III or Pop II stars. Both Pop II and III stars may thus form after the collision if the ejecta do not strip all the gas from the halo. The partial evaporation of the halo prior to the explosion is crucial to its later enrichment by the supernova.« less

How the First Stars Regulated Star Formation. II. Enrichment by Nearby Supernovae

NASA Astrophysics Data System (ADS)

Chen, Ke-Jung; Whalen, Daniel J.; Wollenberg, Katharina M. J.; Glover, Simon C. O.; Klessen, Ralf S.

2017-08-01

Metals from Population III (Pop III) supernovae led to the formation of less massive Pop II stars in the early universe, altering the course of evolution of primeval galaxies and cosmological reionization. There are a variety of scenarios in which heavy elements from the first supernovae were taken up into second-generation stars, but cosmological simulations only model them on the largest scales. We present small-scale, high-resolution simulations of the chemical enrichment of a primordial halo by a nearby supernova after partial evaporation by the progenitor star. We find that ejecta from the explosion crash into and mix violently with ablative flows driven off the halo by the star, creating dense, enriched clumps capable of collapsing into Pop II stars. Metals may mix less efficiently with the partially exposed core of the halo, so it might form either Pop III or Pop II stars. Both Pop II and III stars may thus form after the collision if the ejecta do not strip all the gas from the halo. The partial evaporation of the halo prior to the explosion is crucial to its later enrichment by the supernova.

H2-based star formation laws in hierarchical models of galaxy formation

NASA Astrophysics Data System (ADS)

Xie, Lizhi; De Lucia, Gabriella; Hirschmann, Michaela; Fontanot, Fabio; Zoldan, Anna

2017-07-01

We update our recently published model for GAlaxy Evolution and Assembly (GAEA), to include a self-consistent treatment of the partition of cold gas in atomic and molecular hydrogen. Our model provides significant improvements with respect to previous ones used for similar studies. In particular, GAEA (I) includes a sophisticated chemical enrichment scheme accounting for non-instantaneous recycling of gas, metals and energy; (II) reproduces the measured evolution of the galaxy stellar mass function; (III) reasonably reproduces the observed correlation between galaxy stellar mass and gas metallicity at different redshifts. These are important prerequisites for models considering a metallicity-dependent efficiency of molecular gas formation. We also update our model for disc sizes and show that model predictions are in nice agreement with observational estimates for the gas, stellar and star-forming discs at different cosmic epochs. We analyse the influence of different star formation laws including empirical relations based on the hydrostatic pressure of the disc, analytic models and prescriptions derived from detailed hydrodynamical simulations. We find that modifying the star formation law does not affect significantly the global properties of model galaxies, neither their distributions. The only quantity showing significant deviations in different models is the cosmic molecular-to-atomic hydrogen ratio, particularly at high redshift. Unfortunately, however, this quantity also depends strongly on the modelling adopted for additional physical processes. Useful constraints on the physical processes regulating star formation can be obtained focusing on low-mass galaxies and/or at higher redshift. In this case, self-regulation has not yet washed out differences imprinted at early time.

Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): a comparative solution equilibrium study†

PubMed Central

Enyedy, Éva A.; Primik, Michael F.; Kowol, Christian R.; Arion, Vladimir B.; Kiss, Tamás; Keppler, Bernhard K.

2012-01-01

Stoichiometry and stability of GaIII, FeIII, FeII complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, 1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Formation of high stability bis-ligand complexes was found in all cases, which are predominant at physiological pH with FeIII/FeII, whilst only at the acidic pH range with GaIII. The results show that among the thiosemicarbazones with various substituents the N-terminal dimethylation does not exert a measurable effect on the redox potential, but has the highest impact on the stability of the complexes as well as the cytotoxicity, especially in the absence of a pyridine-NH2 group in the molecule. In addition the fluorescence properties of the ligands in aqueous solution and their changes caused by GaIII were studied. PMID:21523301

Oligomeric states of the Shigella translocator protein IpaB provide structural insights into formation of the type III secretion translocon

PubMed Central

Dickenson, Nicholas E; Choudhari, Shyamal P; Adam, Philip R; Kramer, Ryan M; Joshi, Sangeeta B; Middaugh, C Russell; Picking, Wendy L; Picking, William D

2013-01-01

The Shigella flexneri Type III secretion system (T3SS) senses contact with human intestinal cells and injects effector proteins that promote pathogen entry as the first step in causing life threatening bacillary dysentery (shigellosis). The Shigella Type III secretion apparatus (T3SA) consists of an anchoring basal body, an exposed needle, and a temporally assembled tip complex. Exposure to environmental small molecules recruits IpaB, the first hydrophobic translocator protein, to the maturing tip complex. IpaB then senses contact with a host cell membrane, forming the translocon pore through which effectors are delivered to the host cytoplasm. Within the bacterium, IpaB exists as a heterodimer with its chaperone IpgC; however, IpaB's structural state following secretion is unknown due to difficulties isolating stable protein. We have overcome this by coexpressing the IpaB/IpgC heterodimer and isolating IpaB by incubating the complex in mild detergents. Interestingly, preparation of IpaB with n-octyl-oligo-oxyethylene (OPOE) results in the assembly of discrete oligomers while purification in N,N-dimethyldodecylamine N-oxide (LDAO) maintains IpaB as a monomer. In this study, we demonstrate that IpaB tetramers penetrate phospholipid membranes to allow a size-dependent release of small molecules, suggesting the formation of discrete pores. Monomeric IpaB also interacts with liposomes but fails to disrupt them. From these and additional findings, we propose that IpaB can exist as a tetramer having inherent flexibility, which allows it to cooperatively interact with and insert into host cell membranes. This event may then lay the foundation for formation of the Shigella T3SS translocon pore. PMID:23456854

Sparkle/AM1 Parameters for the Modeling of Samarium(III) and Promethium(III) Complexes.

PubMed

Freire, Ricardo O; da Costa, Nivan B; Rocha, Gerd B; Simas, Alfredo M

2006-01-01

The Sparkle/AM1 model is extended to samarium(III) and promethium(III) complexes. A set of 15 structures of high crystallographic quality (R factor < 0.05 Å), with ligands chosen to be representative of all samarium complexes in the Cambridge Crystallographic Database 2004, CSD, with nitrogen or oxygen directly bonded to the samarium ion, was used as a training set. In the validation procedure, we used a set of 42 other complexes, also of high crystallographic quality. The results show that this parametrization for the Sm(III) ion is similar in accuracy to the previous parametrizations for Eu(III), Gd(III), and Tb(III). On the other hand, promethium is an artificial radioactive element with no stable isotope. So far, there are no promethium complex crystallographic structures in CSD. To circumvent this, we confirmed our previous result that RHF/STO-3G/ECP, with the MWB effective core potential (ECP), appears to be the most efficient ab initio model chemistry in terms of coordination polyhedron crystallographic geometry predictions from isolated lanthanide complex ion calculations. We thus generated a set of 15 RHF/STO-3G/ECP promethium complex structures with ligands chosen to be representative of complexes available in the CSD for all other trivalent lanthanide cations, with nitrogen or oxygen directly bonded to the lanthanide ion. For the 42 samarium(III) complexes and 15 promethium(III) complexes considered, the Sparkle/AM1 unsigned mean error, for all interatomic distances between the Ln(III) ion and the ligand atoms of the first sphere of coordination, is 0.07 and 0.06 Å, respectively, a level of accuracy comparable to present day ab initio/ECP geometries, while being hundreds of times faster.

CO observations of nearby galaxies and the efficiency of star formation

NASA Technical Reports Server (NTRS)

Young, Judith S.

1987-01-01

The CO distributions and total molecular content of 160 galaxies were observed using the 14 meter millimeter telescope of the FCRAO. For the luminous, relatively face-on Sc galaxies, the azimuthally averaged CO distributions are centrally peaked, while for the Sb and Sa galaxies the Co distributions often exhibit central CO holes up to 5 kpc across. None of the Sc galaxies have CO distributions which resemble the Milky Way. A general correlation was found between total CO and IR luminosities in galaxies. The scatter in this relation is highly correlated with dust temperature. No strong correlation of IR luminosities was found with HI masses, and it was thereby concluded that the infrared emission is more directly tied to the molecular content of galaxies. It is suggested that galaxies which have high Star Formation Effiencies (SFEs) produce more stars per unit molecular mass, thereby increasing the average temperature of the dust in the star forming regions. Irregular galaxies and galaxies previously identified as mergers have the highest observed star formation efficiencies. For the mergers, evidence was found that the IR/CO luminosity ratio increases with the merger age estimated by Joseph and Wright (1985).

Methods for fabricating thin film III-V compound solar cell

DOEpatents

Pan, Noren; Hillier, Glen; Vu, Duy Phach; Tatavarti, Rao; Youtsey, Christopher; McCallum, David; Martin, Genevieve

2011-08-09

The present invention utilizes epitaxial lift-off in which a sacrificial layer is included in the epitaxial growth between the substrate and a thin film III-V compound solar cell. To provide support for the thin film III-V compound solar cell in absence of the substrate, a backing layer is applied to a surface of the thin film III-V compound solar cell before it is separated from the substrate. To separate the thin film III-V compound solar cell from the substrate, the sacrificial layer is removed as part of the epitaxial lift-off. Once the substrate is separated from the thin film III-V compound solar cell, the substrate may then be reused in the formation of another thin film III-V compound solar cell.

[CrIII(NCMe)6]3+--a labile CrIII source enabling formation of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue-type magnetic materials.

PubMed

Nelson, Kendric J; Daniels, Matthew C; Reiff, William M; Troff, Shayla A; Miller, Joel S

2007-11-26

The kinetic inertness of the hexaaquachromium(III) (kH2O=2.4x10(-6) s(-1)) has led to challenges with respect to incorporating CrIII ions into Prussian blue-type materials; however, hexakis(acetonitrile)chromium(III) was shown to be substantially more labile (approximately 10(4) times) and enables a new synthetic route for the synthesis of these materials via nonaqueous solvents. The synthesis, spectroscopic, and physical properties of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue analogues synthesized from [CrIII(NCMe)6]3+ and the corresponding [MIII(CN)6]3- are described. All these compounds {(NEt4)0.02CrIII[VIII(CN)6]0.98(BF4)(0.08).0.10MeCN (1), CrIII[CrIII(CN)6].0.16MeCN (2), CrIII[MnIII(CN)6].0.10MeCN (3), and (NEt4)0.04CrIII0.64CrIV0.40[FeII(CN)6]0.40[FeIII(CN)6]0.60(BF4)(0.16).1.02MeCN (4)} are ferrimagnets exhibiting cluster-glass behavior. Strong antiferromagnetic coupling was observed for M=V, Cr, and Mn with Weiss constants (theta) ranging from -132 to -524 K; and in 2, where the strongest coupling is observed (theta=-524 K), the highest Tc (110 K) value was observed. Weak antiferromagnetic coupling was observed for M=Fe (theta=-12 K) leading to the lowest Tc (3 K) value in this series. Weak coupling and the low Tc value observed in 4 were additionally contributed by the presence of both [FeII(CN)6]4- and [FeIII(CN)6]3- as confirmed by 57Fe-Mössbauer spectroscopy.

Anti-freezing-protein type III strongly influences the expression of relevant genes in cryopreserved potato shoot tips.

PubMed

Seo, Ji Hyang; Naing, Aung Htay; Jeon, Su Min; Kim, Chang Kil

2018-06-04

AFP improved cryopreservation efficiency of potato (Solanum tuberosum cv. Superior) by regulating transcript levels of CBF1 and DHN1. However, the optimal AFP concentration required for strong induction of the genes was dependent on the type of vitrification solution to which the AFP was added: This finding suggests that AFP increased cryopreservation efficiency by transcriptional regulation of these genes, which might protect plant cell membranes from cold stress during cryopreservation. Despite the availability of many studies reporting the benefits of anti-freeze protein III (AFP III) as a cryoprotectant, the role of AFP III in this process has not been well demonstrated using molecular analysis. In addition, AFP III has not been exploited in the cryopreservation of potato thus far. Therefore, we studied the effects of AFP III on the cryopreservation of potato (Solanum tuberosum cv. Superior). We found that CBF1 and DHN1 genes are low temperature-inducible in potato leaves (S. tuberosum cv. Superior). Transcript levels of these genes expressed in shoot tips cryopreserved with AFP III were higher than those of the controls. However, the optimal AFP III concentration required for strong induction of the genes was dependent on the type of cryoprotection solution to which the AFP III was added: 500 ng/mL worked best for PVS2, while 1500 ng/mL was optimal for LS. Interestingly, the involvement of AFP III in the cryoprotection solutions improved cryopreservation efficiency as compared to the control, and expression levels of the detected genes were associated with cryopreservation efficiency. This finding suggests that AFP III increased cryopreservation efficiency by transcriptional regulation of these genes, which might protect plant cell membranes from cold stress during cryopreservation. Therefore, we expect that our findings will lead to the successful application of AFP III as a potent cryoprotectant in the cryopreservation of rare and commercially important

Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

PubMed

Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

2015-11-01

Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

Tailored Gallium(III) chelator NOPO: synthesis, characterization, bioconjugation, and application in preclinical Ga-68-PET imaging.

PubMed

Simeček, Jakub; Zemek, Ondřej; Hermann, Petr; Notni, Johannes; Wester, Hans-Jürgen

2014-11-03

The bifunctional chelator NOPO (1,4,7-triazacyclononane-1,4-bis[methylene(hydroxymethyl)phosphinic acid]-7-[methylene(2-carboxyethyl)phosphinic acid]) shows remarkably high Ga(III) complexation efficiency and comprises one carboxylic acid moiety which is not involved into metal ion coordination. An improved synthetic protocol affords NOPO with 45% overall yield. Stepwise protonation constants (log Ka), determined by potentiometry, are 11.96, 5.22, 3.77, and 1.54; the stability constant of the Ga(III) complex is log KGaL = 25.0. Within 5 min, (68)Ga(III) incorporation by NOPO is virtually quantitative at room temperature between pH 3 and 4, and at 95 °C at pH ranging from 0.5 to 7, at NOPO concentrations of 30 μM and 10 μM, respectively. During amide bond formation at the distant carboxylate using the HATU coupling reagent, an intramolecular phosphinic acid ester (phosphilactone) is formed, which is cleaved during (68)Ga complexation or in acidic media, such as trifluoroacetic acid (TFA). Phosphilactone formation can also be suppressed by complexation of Zn(2+) prior to conjugation, the resulting zinc-containing conjugates nevertheless being suitable for direct (68)Ga-labeling. In AR42J (rat pancreatic carcinoma) xenografted CD-1 nude mice, (68)Ga-labeled NOPO-NaI(3)-octreotide conjugate ((68)Ga-NOPO-NOC) showed high and fully blockable tumor uptake (13.9 ± 5% ID/g, 120 min p.i., compared to 0.9 ± 0.4% ID/g with 5 mg/kg of nonlabeled peptide). Uptake in other tissues was generally below 3% ID/g, except appearance of excretion-related activity accumulation in kidneys. NOPO-functionalized compounds tend to be more hydrophilic than the corresponding DOTA- and NODAGA-conjugates, thus promoting fast and extensive renal excretion of (68)Ga-NOPO-radiopharmaceuticals. NOPO-functionalized peptides provide suitable pharmacokinetics in vivo and meet all requirements for efficient (68)Ga-labeling even at room temperature in a kit-like manner.

What is the maximum mass of a Population III galaxy?

NASA Astrophysics Data System (ADS)

Visbal, Eli; Bryan, Greg L.; Haiman, Zoltán

2017-08-01

We utilize cosmological hydrodynamic simulations to study the formation of Population III (Pop III) stars in dark matter haloes exposed to strong ionizing radiation. We simulate the formation of three haloes subjected to a wide range of ionizing fluxes, and find that for high flux, ionization and photoheating can delay gas collapse and star formation up to halo masses significantly larger than the atomic cooling threshold. The threshold halo mass at which gas first collapses and cools increases with ionizing flux for intermediate values, and saturates at a value approximately an order of magnitude above the atomic cooling threshold for extremely high flux (e.g. ≈5 × 108 M⊙ at z ≈ 6). This behaviour can be understood in terms of photoheating, ionization/recombination and Ly α cooling in the pressure-supported, self-shielded gas core at the centre of the growing dark matter halo. We examine the spherically averaged radial velocity profiles of collapsing gas and find that a gas mass of up to ≈106 M⊙ can reach the central regions within 3 Myr, providing an upper limit on the amount of massive Pop III stars that can form. The ionizing radiation increases this limit by a factor of a few compared to strong Lyman-Werner radiation alone. We conclude that the bright He II 1640 Å emission recently observed from the high-redshift galaxy CR7 cannot be explained by Pop III stars alone. However, in some haloes, a sufficient number of Pop III stars may form to be detectable with future telescopes such as the James Webb Space Telescope.

Hybrid III-V/silicon lasers

NASA Astrophysics Data System (ADS)

Kaspar, P.; Jany, C.; Le Liepvre, A.; Accard, A.; Lamponi, M.; Make, D.; Levaufre, G.; Girard, N.; Lelarge, F.; Shen, A.; Charbonnier, P.; Mallecot, F.; Duan, G.-H.; Gentner, J.-.; Fedeli, J.-M.; Olivier, S.; Descos, A.; Ben Bakir, B.; Messaoudene, S.; Bordel, D.; Malhouitre, S.; Kopp, C.; Menezo, S.

2014-05-01

The lack of potent integrated light emitters is one of the bottlenecks that have so far hindered the silicon photonics platform from revolutionizing the communication market. Photonic circuits with integrated light sources have the potential to address a wide range of applications from short-distance data communication to long-haul optical transmission. Notably, the integration of lasers would allow saving large assembly costs and reduce the footprint of optoelectronic products by combining photonic and microelectronic functionalities on a single chip. Since silicon and germanium-based sources are still in their infancy, hybrid approaches using III-V semiconductor materials are currently pursued by several research laboratories in academia as well as in industry. In this paper we review recent developments of hybrid III-V/silicon lasers and discuss the advantages and drawbacks of several integration schemes. The integration approach followed in our laboratory makes use of wafer-bonded III-V material on structured silicon-on-insulator substrates and is based on adiabatic mode transfers between silicon and III-V waveguides. We will highlight some of the most interesting results from devices such as wavelength-tunable lasers and AWG lasers. The good performance demonstrates that an efficient mode transfer can be achieved between III-V and silicon waveguides and encourages further research efforts in this direction.

MMTF-An efficient file format for the transmission, visualization, and analysis of macromolecular structures.

PubMed

Bradley, Anthony R; Rose, Alexander S; Pavelka, Antonín; Valasatava, Yana; Duarte, Jose M; Prlić, Andreas; Rose, Peter W

2017-06-01

Recent advances in experimental techniques have led to a rapid growth in complexity, size, and number of macromolecular structures that are made available through the Protein Data Bank. This creates a challenge for macromolecular visualization and analysis. Macromolecular structure files, such as PDB or PDBx/mmCIF files can be slow to transfer, parse, and hard to incorporate into third-party software tools. Here, we present a new binary and compressed data representation, the MacroMolecular Transmission Format, MMTF, as well as software implementations in several languages that have been developed around it, which address these issues. We describe the new format and its APIs and demonstrate that it is several times faster to parse, and about a quarter of the file size of the current standard format, PDBx/mmCIF. As a consequence of the new data representation, it is now possible to visualize structures with millions of atoms in a web browser, keep the whole PDB archive in memory or parse it within few minutes on average computers, which opens up a new way of thinking how to design and implement efficient algorithms in structural bioinformatics. The PDB archive is available in MMTF file format through web services and data that are updated on a weekly basis.

MMTF—An efficient file format for the transmission, visualization, and analysis of macromolecular structures

PubMed Central

Pavelka, Antonín; Valasatava, Yana; Prlić, Andreas

2017-01-01

Recent advances in experimental techniques have led to a rapid growth in complexity, size, and number of macromolecular structures that are made available through the Protein Data Bank. This creates a challenge for macromolecular visualization and analysis. Macromolecular structure files, such as PDB or PDBx/mmCIF files can be slow to transfer, parse, and hard to incorporate into third-party software tools. Here, we present a new binary and compressed data representation, the MacroMolecular Transmission Format, MMTF, as well as software implementations in several languages that have been developed around it, which address these issues. We describe the new format and its APIs and demonstrate that it is several times faster to parse, and about a quarter of the file size of the current standard format, PDBx/mmCIF. As a consequence of the new data representation, it is now possible to visualize structures with millions of atoms in a web browser, keep the whole PDB archive in memory or parse it within few minutes on average computers, which opens up a new way of thinking how to design and implement efficient algorithms in structural bioinformatics. The PDB archive is available in MMTF file format through web services and data that are updated on a weekly basis. PMID:28574982

The effect of butterfly scales on flight efficiency and leading edge vortex formation

NASA Astrophysics Data System (ADS)

Lang, Amy; Wilroy, Jacob; Wahidi, Redha; Slegers, Nathan; Heilman, Micahel; Cranford, Jacob

2016-11-01

It is hypothesized that the scales on a butterfly wing lead to increased flight efficiency. Recent testing of live butterflies tracked their motion over 246 flights for 11 different specimens. Results show a 37.8 percent mean decrease in flight efficiency and a flapping amplitude reduction of 6.7 percent once the scales were removed. This change could be largely a result of how the leading edge vortex (LEV) interacts with the wing. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied, as well as the subsequent effect on the LEV's growth rate and peak circulation. For this experiment butterfly inspired grooves were created using additive manufacturing and were attached to a flat plate with a chordwise orientation, thus increasing plate surface area. The vortex generated by the grooved plate was then compared to a smooth case as the plate translated vertically through a tow tank at Re = 1500, 3000, and 6000. Using DPIV, the vortex formation was documented and a maximum vortex formation time of 4.22 was found based on the flat plate travel distance and chord length. Results indicate that the patterned surface slows down the growth of the vortex which corroborates the flight test results. Funding from NSF CBET Fluid Dynamcis is gratefully acknowledged.

Decoupling degradation in exciton formation and recombination during lifetime testing of organic light-emitting devices

NASA Astrophysics Data System (ADS)

Hershey, Kyle W.; Suddard-Bangsund, John; Qian, Gang; Holmes, Russell J.

2017-09-01

The analysis of organic light-emitting device degradation is typically restricted to fitting the overall luminance loss as a function of time or the characterization of fully degraded devices. To develop a more complete understanding of degradation, additional specific data are needed as a function of luminance loss. The overall degradation in luminance during testing can be decoupled into a loss in emitter photoluminescence efficiency and a reduction in the exciton formation efficiency. Here, we demonstrate a method that permits separation of these component efficiencies, yielding the time evolution of two additional specific device parameters that can be used in interpreting and modeling degradation without modification to the device architecture or introduction of any additional post-degradation characterization steps. Here, devices based on the phosphor tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy)3) are characterized as a function of initial luminance and emissive layer thickness. The overall loss in device luminance is found to originate primarily from a reduction in the exciton formation efficiency which is exacerbated in devices with thinner emissive layers. Interestingly, the contribution to overall degradation from a reduction in the efficiency of exciton recombination (i.e., photoluminescence) is unaffected by thickness, suggesting a fixed exciton recombination zone width and degradation at an interface.

Microbial reduction of Fe(III) in acidic sediments: isolation of Acidiphilium cryptum JF-5 capable of coupling the reduction of Fe(III) to the oxidation of glucose.

PubMed

Küsel, K; Dorsch, T; Acker, G; Stackebrandt, E

1999-08-01

To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12 degrees C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H(2) was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4', 6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2. 3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H(2). Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic

Synthesis, structure, and magnetic characterization of a C3-symmetric Mn(III)3Cr(III) assembly: molecular recognition between a trinuclear Mn(III) triplesalen complex and a fac-triscyano Cr(III) complex.

PubMed

Freiherr von Richthofen, Carl-Georg; Stammler, Anja; Bögge, Hartmut; DeGroot, Marty W; Long, Jeffrey R; Glaser, Thorsten

2009-11-02

properties to those of the heptanuclear analogue [{(talen(t-Bu(2)))Mn(III)(3)}(2){Cr(III)(CN)(6)}](3+) ([Mn(III)(6)Cr(III)](3+)) formed by the reaction of 2 equiv of [(talen(t-Bu(2))){Mn(III)(solv)(n)}(3)](3+) with 1 equiv of [Cr(CN)(6)](3-) [Glaser, T.; Heidemeier, M.; Weyhermüller, T.; Hoffmann, R.-D.; Rupp, H.; Müller, P. Angew. Chem. Int. Ed., 2006, 45, 6033-6037] demonstrates a lower driving force for formation, a strongly reduced J(Mn-Cr) exchange, a slightly reduced J(Mn-Mn) exchange, and a significantly longer Mn-N(N[triple bond]C) bond length in [Mn(III)(3)Cr(III)](3+). Taking into account magneto-structural correlations establishes a supramolecular interaction between the two [(talen(t-Bu(2)))Mn(III)(3)](3+) subunits in [Mn(III)(6)Cr(III)](3+) responsible for the structural distortion and the short Mn-N(N[triple bond]C) distance which results in a strong J(Mn-Cr) exchange and thus [Mn(III)(6)Cr(III)](3+) being a single-molecule magnet with a relatively high effective anisotropy barrier of 25.4 K.

As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent.

PubMed

Hu, Chengzhi; Liu, Huijuan; Chen, Guixia; Jefferson, William A; Qu, Jiuhui

2012-06-19

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.

Short- and long-term efficiency of carboxymethylcellulose (CMC) to prevent crystal formation in South African wine.

PubMed

Greeff, A E; Robillard, B; du Toit, W J

2012-01-01

Crystal formation in bottled wine occurs due to the over-saturation of wine with potassium bitartrate (KHT) salt when exposed to low temperatures. In this study, special focus was given to the efficiency of a crystallisation-inhibiting additive, carboxymethylcellulose (CMC), which is widely used in the food industry. In 2008, CMC was authorised by the International Organisation of Vine and Wine (OIV) for use in white and sparkling wines, but is not yet officially permitted in all wine-producing countries. The use of CMC could be of economical importance to the wine industry because energy costs due to cooling can be reduced. Unlike traditional cooling methods, the use of CMC theoretically prevents the loss of acidity. In this study, the short- and long-term efficiencies of CMC were investigated in South African white, rosé and red wines. Efficiency was determined primarily by measuring changes in potassium (K(+)) and tartaric acid (H(2)T) concentrations and visual crystal formation. As part of this study CMC's efficiency was compared with several other crystal inhibition treatments, and was also evaluated for its temperature stability over a year. CMC's effect on colour and total phenols was also assessed. The results reveal a high efficiency in preventing losses in K(+) and H(2)T concentrations in white wines, even with an ageing period of up to 12 months. The addition of CMC to rosé wines also delivered certain positive results, but less so for red wine. Three different commercial CMCs were also compared with mannoproteins to prevent changes in K(+) and H(2)T concentrations in three different wines. Furthermore, sensory evaluation was performed to determine certain organoleptic changes as a result of CMC treatments.

Chracterization of class III peroxidases from switchgrass

USDA-ARS?s Scientific Manuscript database

Class III peroxidases (CIIIPRX) catalyze the oxidation of monolignols, generate radicals, and ultimately lead to the formation of lignin. In general, CIIIPRX genes encode a large number of isozymes with ranges of in vitro substrate specificities. In order to elucidate the mode of substrate specifici...

Theoretical characterization and design of highly efficient iridium (III) complexes bearing guanidinate ancillary ligand.

PubMed

Ren, Xin-Yao; Wu, Yong; Wang, Li; Zhao, Liang; Zhang, Min; Geng, Yun; Su, Zhong-Min

2014-06-01

A density functional theory/time-depended density functional theory was used to investigate the synthesized guanidinate-based iridium(III) complex [(ppy)2Ir{(N(i)Pr)2C(NPh2)}] (1) and two designed derivatives (2 and 3) to determine the influences of different cyclometalated ligands on photophysical properties. Except the conventional discussions on geometric relaxations, absorption and emission properties, many relevant parameters, including spin-orbital coupling (SOC) matrix elements, zero-field-splitting parameters, radiative rate constants (kr) and so on were quantitatively evaluated. The results reveal that the replacement of the pyridine ring in the 2-phenylpyridine ligand with different diazole rings cannot only enlarge the frontier molecular orbital energy gaps, resulting in a blue-shift of the absorption spectra for 2 and 3, but also enhance the absorption intensity of 3 in the lower-energy region. Furthermore, it is intriguing to note that the photoluminescence quantum efficiency (ΦPL) of 3 is significantly higher than that of 1. This can be explained by its large SOC value(n=3-4) and large transition electric dipole moment (μS3), which could significantly contribute to a larger kr. Besides, compared with 1, the higher emitting energy (ET1) and smaller (2) value for 3 may lead to a smaller non-radiative decay rate. Additionally, the detailed results also indicate that compared to 1 with pyridine ring, 3 with imidazole ring performs a better hole injection ability. Therefore, the designed complex 3 can be expected as a promising candidate for highly efficient guanidinate-based phosphorescence emitter for OLEDs applications. Copyright © 2014 Elsevier Inc. All rights reserved.

Low-metallicity Star Formation (IAU S255)

NASA Astrophysics Data System (ADS)

Hunt, Leslie K.; Madden, Suzanne C.; Schneider, Raffaella

2009-01-01

Preface; SOC and LOC; Participants; Life at the conference; Conference photo; Session I. Population III and Metal-Free Star Formation: 1. Open questions in the study of population III star formation S. C. O. Glover, P. C. Clark, T. H. Greif, J. L. Johnson, V. Bromm, R. S. Klessen and A. Stacy; 2. Protostar formation in the early universe Naoki Yoshida; 3. Population III.1 stars: formation, feedback and evolution of the IMF Jonathan C. Tan; 4. The formation of the first galaxies and the transition to low-mass star formation T. H. Greif, D. R. G. Schleicher, J. L. Johnson, A.-K. Jappsen, R. S. Klessen, P. C. Clark, S. C. O. Glover, A. Stacy and V. Bromm; 5. Low-metallicity star formation: the characteristic mass and upper mass limit Kazuyuki Omukai; 6. Dark stars: dark matter in the first stars leads to a new phase of stellar evolution Katherine Freese, Douglas Spolyar, Anthony Aguirre, Peter Bodenheimer, Paolo Gondolo, J. A. Sellwood and Naoki Yoshida; 7. Effects of dark matter annihilation on the first stars F. Iocco, A. Bressan, E. Ripamonti, R. Schneider, A. Ferrara and P. Marigo; 8. Searching for Pop III stars and galaxies at high redshift Daniel Schaerer; 9. The search for population III stars Sperello di Serego Alighieri, Jaron Kurk, Benedetta Ciardi, Andrea Cimatti, Emanuele Daddi and Andrea Ferrara; 10. Observational search for population III stars in high-redshift galaxies Tohru Nagao; Session II. Metal Enrichment, Chemical Evolution, and Feedback: 11. Cosmic metal enrichment Andrea Ferrara; 12. Insights into the origin of the galaxy mass-metallicity relation Henry Lee, Eric F. Bell and Rachel S. Somerville; 13. LSD and AMAZE: the mass-metallicity relation at z > 3 F. Mannucci and R. Maiolino; 14. Three modes of metal-enriched star formation at high redshift Britton D. Smith, Matthew J. Turk, Steinn Sigurdsson, Brian W. O'Shea and Michael L. Norman; 15. Primordial supernovae and the assembly of the first galaxies Daniel Whalen, Bob Van Veelen, Brian W. O

Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jiumeng; D’Ambro, Emma L.; Lee, Ben H.

2016-09-20

With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are a subject of intense research because particles affect Earth’s climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2, or more, higher than those typically used in coupled chemistry-climate models.more » SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 10 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the pre-industrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest a more complex representation of NOx dependent SOA yields may be important in models.« less

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

NASA Astrophysics Data System (ADS)

Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.; Broch, Katharina; Bayliss, Sam L.; Chen, Kai; Tabachnyk, Maxim; Thorley, Karl; Greenham, Neil; Hodgkiss, Justin M.; Anthony, John; Head-Gordon, Martin; Musser, Andrew J.; Rao, Akshay; Friend, Richard H.

2017-12-01

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature, even when the energy of S1 is as much as 200 meV less than that of 2T1. Here we study films of triisopropylsilyltetracene using transient optical spectroscopy and show that the triplet pair state (TT), which has been proposed to mediate singlet fission, forms on ultrafast timescales (in 300 fs) and that its formation is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower loss of singlet character as the excitation evolves to become only TT. We observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for 'temperature-independent' efficient TT formation and thermally activated TT separation.

An analytical method to compute comet cloud formation efficiency and its application

NASA Astrophysics Data System (ADS)

Brasser, Ramon; Duncan, Martin J.

2008-01-01

A quick analytical method is presented for calculating comet cloud formation efficiency in the case of a single planet or multiple-planet system for planets that are not too eccentric ( e p ≲ 0.3). A method to calculate the fraction of comets that stay under the control of each planet is also presented, as well as a way to determine the efficiency in different star cluster environments. The location of the planet(s) in mass-semi-major axis space to form a comet cloud is constrained based on the conditions developed by Tremaine (1993) together with estimates of the likelyhood of passing comets between planets; and, in the case of a single, eccentric planet, the additional constraint that it is, by itself, able to accelerate material to relative encounter velocity U ~ 0.4 within the age of the stellar system without sweeping up the majority of the material beforehand. For a single planet, it turns out the efficiency is mainly a function of planetary mass and semi-major axis of the planet and density of the stellar environment. The theory has been applied to some extrasolar systems and compared to numerical simulations for both these systems and the Solar System, as well as a diffusion scheme based on the energy kick distribution of Everhart (Astron J 73:1039 1052, 1968). The analytic results are in good agreement with the simulations.

Protonation of a peroxodiiron(III) complex and conversion to a diiron(III/IV) intermediate: implications for proton-assisted O-O bond cleavage in nonheme diiron enzymes.

PubMed

Cranswick, Matthew A; Meier, Katlyn K; Shan, Xiaopeng; Stubna, Audria; Kaizer, Jószef; Mehn, Mark P; Münck, Eckard; Que, Lawrence

2012-10-01

Oxygenation of a diiron(II) complex, [Fe(II)(2)(μ-OH)(2)(BnBQA)(2)(NCMe)(2)](2+) [2, where BnBQA is N-benzyl-N,N-bis(2-quinolinylmethyl)amine], results in the formation of a metastable peroxodiferric intermediate, 3. The treatment of 3 with strong acid affords its conjugate acid, 4, in which the (μ-oxo)(μ-1,2-peroxo)diiron(III) core of 3 is protonated at the oxo bridge. The core structures of 3 and 4 are characterized in detail by UV-vis, Mössbauer, resonance Raman, and X-ray absorption spectroscopies. Complex 4 is shorter-lived than 3 and decays to generate in ~20% yield of a diiron(III/IV) species 5, which can be identified by electron paramagnetic resonance and Mössbauer spectroscopies. This reaction sequence demonstrates for the first time that protonation of the oxo bridge of a (μ-oxo)(μ-1,2-peroxo)diiron(III) complex leads to cleavage of the peroxo O-O bond and formation of a high-valent diiron complex, thereby mimicking the steps involved in the formation of intermediate X in the activation cycle of ribonucleotide reductase.

Carbon disulfide-modified magnetic ion-imprinted chitosan-Fe(III): A novel adsorbent for simultaneous removal of tetracycline and cadmium.

PubMed

Chen, Anwei; Shang, Cui; Shao, Jihai; Lin, Yiqing; Luo, Si; Zhang, Jiachao; Huang, Hongli; Lei, Ming; Zeng, Qingru

2017-01-02

A novel composite of carbon disulfide-modified magnetic ion-imprinted chitosan-Fe(III), i.e., MMIC-Fe(III) composite, was prepared as an efficient adsorbent for the simultaneous removal of tetracycline (TC) and Cd(II). This adsorbent showed excellent performance in removing TC and Cd(II) due to its rapid kinetics, high adsorption capacity, good reusability, and was well suited for use with real water samples. Kinetics studies demonstrated that the adsorption proceeded according to a pseudo-second order model. The adsorption isotherms were well described by the Langmuir model, with maximum adsorption capacity for TC and Cd(II) being 516.29 and 194.31mg/g, respectively. The synergistic effect of TC and Cd(II) adsorption might be due to the formation of TC-Cd(II) complex bridging the adsorbate and adsorbent. These properties demonstrate the potential application of MMIC-Fe(III) for the simultaneous removal of TC and Cd(II), and may provide some information for the synergistic removal of antibiotics and heavy metals from aquatic environments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of Fe (III)-reducing enrichment culture and isolation of Fe (III)-reducing bacterium Enterobacter sp. L6 from marine sediment.

PubMed

Liu, Hongyan; Wang, Hongyu

2016-07-01

To enrich the Fe (III)-reducing bacteria, sludge from marine sediment was inoculated into the medium using Fe (OH)3 as the sole electron acceptor. Efficiency of Fe (III) reduction and composition of Fe (III)-reducing enrichment culture were analyzed. The results indicated that the Fe (III)-reducing enrichment culture with the dominant bacteria relating to Clostridium and Enterobacter sp. had high Fe (III) reduction of (2.73 ± 0.13) mmol/L-Fe (II). A new Fe (III)-reducing bacterium was isolated from the Fe (III)-reducing enrichment culture and identified as Enterobacter sp. L6 by 16S rRNA gene sequence analysis. The Fe (III)-reducing ability of strain L6 under different culture conditions was investigated. The results indicated that strain L6 had high Fe (III)-reducing activity using glucose and pyruvate as carbon sources. Strain L6 could reduce Fe (III) at the range of NaCl concentrations tested and had the highest Fe (III) reduction of (4.63 ± 0.27) mmol/L Fe (II) at the NaCl concentration of 4 g/L. This strain L6 could reduce Fe (III) with unique properties in adaptability to salt variation, which indicated that it can be used as a model organism to study Fe (III)-reducing activity isolated from marine environment. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

C III] Emission in Star-forming Galaxies at z ∼ 1

NASA Astrophysics Data System (ADS)

Du, Xinnan; Shapley, Alice E.; Martin, Crystal L.; Coil, Alison L.

2017-03-01

The C III]λλ1907, 1909 rest-frame UV emission doublet has recently been detected in galaxies during the epoch of reionization (z > 6), with a high equivalent width (EW; 10 Å, rest frame). Currently, it is possible to obtain much more detailed information for star-forming galaxies at significantly lower redshift. Accordingly, studies of their far-UV spectra are useful for understanding the factors modulating the strength of C III] emission. We present the first statistical sample of C III] emission measurements in star-forming galaxies at z ∼ 1. Our sample is drawn from the DEEP2 survey and spans the redshifts 0.64 ≤slant z ≤slant 1.35 (< z> =1.08). We find that the median EW of individual C III] detections in our sample (1.30 Å) is much smaller than the typical value observed thus far at z > 6. Furthermore, out of 184 galaxies with coverage of C III], only 40 have significant detections. Galaxies with individual C III] detections have bluer colors and lower luminosities on average than those without, implying that strong C III] emitters are in general young and low-mass galaxies without significant dust extinction. Using stacked spectra, we further investigate how C III] strength correlates with multiple galaxy properties (M B , U ‑ B, M *, star formation rate, specific star formation rate) and rest-frame near-UV (Fe II* and Mg II) and optical ([O III] and Hβ) emission line strengths. These results provide a detailed picture of the physical environment in star-forming galaxies at z ∼ 1, and motivate future observations of strong C III] emitters at similar redshifts.

Binuclear ruthenium(III) bis(thiosemicarbazone) complexes: Synthesis, spectral, electrochemical studies and catalytic oxidation of alcohol

NASA Astrophysics Data System (ADS)

Mohamed Subarkhan, M.; Ramesh, R.

2015-03-01

A new series of binuclear ruthenium(III) thiosemicarbazone complexes of general formula [(EPh3)2(X)2Ru-L-Ru(X)2(EPh3)2] (where E = P or As; X = Cl or Br; L = NS chelating bis(thiosemicarbazone ligands) has been synthesized and characterized by analytical and spectral (FT-IR, UV-Vis and EPR). IR spectra show that the thiosemicarbazones behave as monoanionic bidentate ligands coordinating through the azomethine nitrogen and thiolate sulphur. The electronic spectra of the complexes indicate that the presence of d-d and intense LMCT transitions in the visible region. The complexes are paramagnetic (low spin d5) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx ≠ gy ≠ gz) at 77 K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (RuIII-RuIII/RuIV-RuIV; RuIII-RuIII/RuII-RuII) within the potential range of 0.38-0.86 V and -0.39 to -0.66 V respectively, versus Ag/AgCl. Further, the catalytic efficiency of one of the complexes [Ru2Cl2(AsPh3)4(L1)] (4) has been investigated in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide(NMO) as co-oxidant. The formation of high valent RuVdbnd O species is proposed as catalytic intermediate for the catalytic cycle.

Batch sorption-desorption of As(III) from waste water by magnetic palm kernel shell activated carbon using optimized Box-Behnken design

NASA Astrophysics Data System (ADS)

Anyika, Chinedum; Asri, Nur Asilayana Mohd; Majid, Zaiton Abdul; Jaafar, Jafariah; Yahya, Adibah

2017-12-01

In this study, we converted activated carbon (AC) into magnetic activated carbon (MAC), which was established to have removed arsenic (III) from wastewater. Arsenic (III) is a toxic heavy metal which is readily soluble in water and can be detrimental to human health. The MAC was prepared by incorporating Fe3O4 into the AC by using Fe3O4 extracted from a ferrous sulfate solution, designated: magnetic palm kernel shell from iron suspension (MPKSF). Batch experiments were conducted using two methods: (1) one-factor-at-a-time and (2) Box-Behnken statistical analysis. Results showed that the optimum conditions resulted in 95% of As(III) removal in the wastewater sample. The adsorption data were best fitted to the Langmuir isotherm. The adsorption of As(III) onto the MPKSF was confirmed by energy dispersive X-ray spectrometry analysis which detected the presence of As(III) of 0.52% on the surface of the MPKSF. The Fourier transform infrared spectroscopy analysis of the MPKSF-As presented a peak at 573 cm-1, which was assigned to M-O (metal-oxygen) bending, indicating the coordination of As(III) with oxygen through the formation of inner-sphere complexation, thereby indicating a covalent bonding between the MPKSF functional groups and As(III). The findings suggested that the MPKSF exhibited a strong capacity to efficiently remove As(III) from wastewater, while the desorption studies showed that the As(III) was rigidly bound to the MPKSF thereby eliminating the possibility of secondary pollution.

Effect of alkaline precipitation on Cr species of Cr(III)-bearing complexes typically used in the tannery industry.

PubMed

Wang, Dandan; Ye, Yuxuan; Liu, Hui; Ma, Hongrui; Zhang, Weiming

2018-02-01

Various organic compounds extensively used in the leather industry could influence the performance of alkaline precipitation with Cr(III). This study focused on two typical Cr(III)-bearing complexes (Cr(III)-collagen and Cr(III)-citrate) ubiquitous in tannery effluent yet with distinct treatment efficiencies, as Cr(III) was much more difficult to remove in the Cr(III)-citrate solution. Comprehensive analytical methods were employed to explore the intrinsic mechanism. It was found that a lower removal efficiency towards Cr(III) was significantly associated with higher oligomers. The molecular size of the Cr(III)-citrate complex continued to increase with rising pH, making it larger overall than Cr(III)-collagen species. The growing oligomer moiety of dissolved Cr(III)-complex species could persist in the stronger basic pH range, leading to the large amount of residual Cr(III) in the Cr(III)-citrate system. Combining this result with potentiometric titration and X-ray photoelectron spectroscopy data, it was believed that the polymeric species other than monomers facilitated resisting the attack from hydroxide ions, and the postulated Cr(III)-citrate species towards higher oligomers were discovered. Beyond that, both charge neutralization and sweeping effects were presented among the gradually emerging flocs in the Cr(III)-collagen system together with the electric double layer compression effect derived from salinity, thus resulting in a larger floc size and higher Cr(III) removal efficiency in saline solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnetic Nature of the CrIII-LnIII Interactions in [CrIII2LnIII3] Clusters with Slow Magnetic Relaxation.

PubMed

Zhao, Xiao-Qing; Xiang, Shuo; Wang, Jin; Bao, Dong-Xu; Li, Yun-Chun

2018-02-01

Two 3 d -4 f hetero-metal pentanuclear complexes with the formula {[Cr III 2 Ln III 3 L 10 (OH) 6 (H 2 O) 2 ]Et 3 NH} [Ln=Tb ( 1 ), Dy ( 2 ); HL=pivalic acid, Et 3 N=triethylamine] have been produced. The metal core of each cluster is made up of a trigonal bipyramid with three Ln III ions (plane) and two Cr III ions (above and below) held together by six μ 3 -OH bridges. Also reported with this series is the diamagnetic Cr III -Y III analogue ( 3 ). Fortunately, we successfully prepared Al III -Ln III analogues with the formula {[Al III 2 Ln III 3 L 10 (OH) 6 (H 2 O) 2 ]Et 3 NH⋅H 2 O} [Ln=Tb ( 4 ), Dy ( 5 )], containing diamagnetic Al III ions, which can be used to evaluate the Cr III -Ln III magnetic nature through a diamagnetic substitution method. Subsequently, static (dc) magnetic susceptibility studies reveal dominant ferromagnetic interactions between Cr III and Ln III ions. Dynamic (ac) magnetic susceptibility studies show frequency-dependent out-of-phase ( χ '') signals for [Cr III 2 Tb III 3 ] ( 1 ), [Cr III 2 Dy III 3 ] ( 2 ), and [Al III 2 Dy III 3 ] ( 5 ), which are derived from the single-ion behavior of Ln III ions and/or the Cr III -Ln III ferromagnetic interactions.

DENSE GAS FRACTION AND STAR FORMATION EFFICIENCY VARIATIONS IN THE ANTENNAE GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bigiel, F.; Leroy, A. K.; Blitz, L.

2015-12-20

We use the Combined Array for Research in Millimeter-wave Astronomy (CARMA) millimeter interferometer to map the Antennae Galaxies (NGC 4038/39), tracing the bulk of the molecular gas via the {sup 12}CO(1–0) line and denser molecular gas via the high density transitions HCN(1–0), HCO{sup +}(1–0), CS(2–1), and HNC(1–0). We detect bright emission from all tracers in both the two nuclei and three locales in the overlap region between the two nuclei. These three overlap region peaks correspond to previously identified “supergiant molecular clouds.” We combine the CARMA data with Herschel infrared (IR) data to compare observational indicators of the star formationmore » efficiency (star formation rate/H{sub 2} ∝ IR/CO), dense gas fraction (HCN/CO), and dense gas star formation efficiency (IR/HCN). Regions within the Antennae show ratios consistent with those seen for entire galaxies, but these ratios vary by up to a factor of six within the galaxy. The five detected regions vary strongly in both their integrated intensities and these ratios. The northern nucleus is the brightest region in millimeter-wave line emission, while the overlap region is the brightest part of the system in the IR. We combine the CARMA and Herschel data with ALMA CO data to report line ratio patterns for each bright point. CO shows a declining spectral line energy distribution, consistent with previous studies. HCO{sup +} (1–0) emission is stronger than HCN (1–0) emission, perhaps indicating either more gas at moderate densities or higher optical depth than is commonly seen in more advanced mergers.« less

Transparent Glass Ceramics Doped by Chromium(III) and Chromium(III) and Neodymium(III) as New Materials for Lasers and Luminescent Solar Concentrators.

DTIC Science & Technology

1987-04-30

1.5 ZrO2 * 0.3 As203, 0.024 Cr203, melted under various conditions. Parallel measurements of X-ray diffraction, optical and EPR spectra reveal the...optical and EPR spectra reveal the different formation of gahnite from precursor glass or petalite-like phase. Introduction In a number of recent...conditions on optical and EPR spectra of Cr(III). Further on the parallel changes of spectra and x-ray diffraction patterns are indica- ted. The gahnite

Simultaneous Oxidation and Sequestration of As(III) from Water by Using Redox Polymer-Based Fe(III) Oxide Nanocomposite.

PubMed

Zhang, Xiaolin; Wu, Mengfei; Dong, Hao; Li, Hongchao; Pan, Bingcai

2017-06-06

Water decontamination from As(III) is an urgent but still challenging task. Herein, we fabricated a bifunctional nanocomposite HFO@PS-Cl for highly efficient removal of As(III), with active chlorine covalently binding spherical polystyrene host for in situ oxidation of As(III) to As(V), and Fe(III) hydroxide (HFO) nanoparticles (NPs) embedded inside for specific As(V) removal. HFO@PS-Cl could work effectively in a wide pH range (5-9), and other substances like sulfate, chloride, bicarbonate, silicate, and humic acid exert insignificant effect on As(III) removal. As(III) sequestration is realized via two pathways, that is, oxidation to As(V) by the active chlorine followed by specific As(V) adsorption onto HFO NPs, and As(III) adsorption onto HFO NPs followed by oxidation to As(V). The exhausted HFO@PS-Cl could be refreshed for cyclic runs with insignificant capacity loss by the combined regeneration strategy, that is, alkaline solution to rinse the adsorbed As(V) and NaClO solution to renew the host oxidation capability. In addition, fixed-bed experiments demonstrated that the HFO@PS-Cl column could generate >1760 bed volume (BV) effluent from a synthetic As(III)-containing groundwater to meet the drinking water standard (<10 μg As/L), whereas other two HFO nanocomposites, HFO@PS-N and HFO@D201 could only generate 450 and 600 BV effluents under otherwise identical conditions.

Extraction of Gold(III) from Hydrochloric Acid Solutions with a PVC-based Polymer Inclusion Membrane (PIM) Containing Cyphos(®) IL 104.

PubMed

Bonggotgetsakul, Ya Ya Nutchapurida; Cattrall, Robert W; Kolev, Spas D

2015-12-08

Poly(vinyl chloride) (PVC) based polymer inclusion membranes (PIMs), with different concentrations of Cyphos® IL 104 as the membrane extractant/carrier, were studied for their ability to extract Au(III) from hydrochloric acid solutions. Some of the PIMs also contained one of the following plasticizers or modifiers: 2-nitrophenyloctyl ether, dioctylphthalate, 1-dodecanol, 1-tetradecanol, or tri(2-ethylhexyl) phosphate. The best performance, in terms of extraction rate and amount of Au(III) extracted, was exhibited by a PIM consisting of 25 wt% Cyphos(®) IL 104, 5 wt% 1-dodecanol, and 70 wt% PVC. An almost complete back-extraction of the Au(III) extracted from this membrane was achieved by using a 0.10 mol L(-1) Na₂SO₃ receiver solution at pH 8. The stoichiometry of the extracted Au(III)/Cyphos® IL 104 adduct was determined as [P]⁺ [AuCl₄](-) H⁺ [PO₂](-) where [P]⁺ and [PO₂](-) represent trihexyl(tetradecyl) phosphonium and bis(2,4,4-trimethylpentyl) phosphinate ions, respectively. Back-extraction of Au(III) is suggested to occur by reduction of Au(III) to Au(I), with the formation of the species [Au(SO₃)₂](3-) in the aqueous receiver solution. Loss of 1-dodecanol from the newly developed PIM to the aqueous solutions in contact with it was observed, which indicated that this membrane was suitable for single use in the efficient recovery of Au(III) from hydrochloric acid solutions of electronic scrap or recycled jewelry.

Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

PubMed

Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

2009-05-01

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

Performance analysis of nanodisk and core/shell/shell-nanowire type III-Nitride heterojunction solar cell for efficient energy harvesting

NASA Astrophysics Data System (ADS)

Routray, S. R.; Lenka, T. R.

2017-11-01

Now-a-days III-Nitride nanowires with axial (nanodisk) and radial (core/shell/shell-nanowire) junctions are two unique and potential methods for solar energy harvesting adopted by worldwide researchers. In this paper, polarization behavior of GaN/InGaN/GaN junction and its effect on carrier dynamics of nanodisk and CSS-nanowire type solar cells are intensively studied and compared with its planar counterpart by numerical simulations using commercially available Victory TCAD. It is observed that CSS-NW with hexagonal geometrical shapes are robust to detrimental impact of polarization charges and could be good enough to accelerate carrier collection efficiency as compared to nanodisk and planar solar cells. This numerical study provides an innovative aspect of fundamental device physics with respect to polarization charges in CSS-NW and nanodisk type junction towards photovoltaic applications. The internal quantum efficiencies (IQE) are also discussed to evaluate carrier collection mechanisms and recombination losses in each type of junctions of solar cell. Finally, it is interesting to observe a maximum conversion efficiency of 6.46% with 91.6% fill factor from n-GaN/i-In0.1Ga0.9N/p-GaN CSS-nanowire solar cell with an optimized thickness of 180 nm InGaN layer under one Sun AM1.5 illumination.

Methods for enhancing P-type doping in III-V semiconductor films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Feng; Stringfellow, Gerald; Zhu, Junyi

2017-08-01

Methods of doping a semiconductor film are provided. The methods comprise epitaxially growing the III-V semiconductor film in the presence of a dopant, a surfactant capable of acting as an electron reservoir, and hydrogen, under conditions that promote the formation of a III-V semiconductor film doped with the p-type dopant. In some embodiments of the methods, the epitaxial growth of the doped III-V semiconductor film is initiated at a first hydrogen partial pressure which is increased to a second hydrogen partial pressure during the epitaxial growth process.

Very Green Photosynthesis of Gold Nanoparticles by a Living Aquatic Plant: Photoreduction of AuIII by the Seaweed Ulva armoricana.

PubMed

Mukhoro, Ofhani C; Roos, Wiets D; Jaffer, Mohammed; Bolton, John J; Stillman, Martin J; Beukes, Denzil R; Antunes, Edith

2018-02-01

Light-assisted in vivo synthesis of gold nanoparticles (NPs) from aqueous solutions of dilute Au III salts by a living green marine seaweed (Ulva armoricana) is reported for the first time. NPs synthesised using typical procedures have many associated environmental hazards. The reported methods involve green, nontoxic, eco-friendly synthetic procedures. The formation of AuNPs was extremely rapid (≈15 min) following illumination of the living U. armoricana, while the rate of NP formation in the dark was very slow (over 2 weeks). The properties of the AuNPs formed were confirmed using a battery of spectroscopic techniques. U. armoricana were found to be very efficient in Au 0 uptake, and this, together with the rapid formation of AuNPs under illumination, indicated that the seaweed remained living during NP formation. The TEM images supported this, revealing that the thylakoid membranes and cell structure remained intact. The AuNPs formed on the surface of U. armoricana thallus, along the cell walls and in the chloroplasts. Without further workup, the dried, U. armoricana-supported AuNPs were efficient in the catalytic reduction of 4-nitrophenol, demonstrating the completely green cycle of AuNP formation and catalytic activity. The results mean that an aquatic plant growing in water rich in gold salts could bio-accumulate AuNPs from its aquatic environment, simply with the activation of sunlight. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of the silicon subcell for III-V on silicon multijunction solar cells: Key differences with conventional silicon technology

NASA Astrophysics Data System (ADS)

García-Tabarés, Elisa; Martín, Diego; García, Iván; Lelièvre, Jean François; Rey-Stolle, Ignacio

2012-10-01

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon (Si) bottom cell seem to be attractive candidates to materialize the long sought-for integration of III-V materials on Si for photovoltaic (PV) applications. Such integration would offer a cost breakthrough for PV technology, unifying the low cost of Si and the efficiency potential of III-V multijunction solar cells. The optimization of the Si solar cells properties in flat-plate PV technology is well-known; nevertheless, it has been proven that the behavior of Si substrates is different when processed in an MOVPE reactor In this study, we analyze several factors influencing the bottom subcell performance, namely, 1) the emitter formation as a result of phosphorus diffusion; 2) the passivation quality provided by the GaP nucleation layer; and 3) the process impact on the bottom subcell PV properties.

Biological activity of Fe(III) aquo-complexes towards ferric chelate reductase (FCR).

PubMed

Escudero, Rosa; Gómez-Gallego, Mar; Romano, Santiago; Fernández, Israel; Gutiérrez-Alonso, Ángel; Sierra, Miguel A; López-Rayo, Sandra; Nadal, Paloma; Lucena, Juan J

2012-03-21

In this study we have obtained experimental evidence that confirms the high activity of aquo complexes III and IV towards the enzyme FCR, responsible for the reduction of Fe(III) to Fe(II) in the process of iron acquisition by plants. The in vivo FCR assays in roots of stressed cucumber plants have shown a higher efficiency of the family of complexes III and a striking structure-activity relationship with the nature of the substituent placed in a phenyl group far away from the metal center. The results obtained in this work demonstrate that all the aquo compounds tested interact efficiently with the enzyme FCR and hence constitute a new concept of iron chelates that could be of great use in agronomy.

Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

2018-01-01

Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

Star formation across galactic environments

NASA Astrophysics Data System (ADS)

Young, Jason

I present here parallel investigations of star formation in typical and extreme galaxies. The typical galaxies are selected to be free of active galactic nuclei (AGN), while the extreme galaxies host quasars (the most luminous class of AGN). These two environments are each insightful in their own way; quasars are among the most violent objects in the universe, literally reshaping their host galaxies, while my sample of AGN-free star-forming galaxies ranges from systems larger than the Milky Way to small galaxies which are forming stars at unsustainably high rates. The current paradigm of galaxy formation and evolution suggests that extreme circumstances are key stepping stones in the assembly of galaxies like our Milky Way. To test this paradigm and fully explore its ramifications, this dual approach is needed. My sample of AGN-free galaxies is drawn from the KPNO International Spectroscopic Survey. This Halpha-selected, volume-limited survey was designed to detect star-forming galaxies without a bias toward continuum luminosity. This type of selection ensures that this sample is not biased toward galaxies that are large or nearby. My work studies the KISS galaxies in the mid- and far-infrared using photometry from the IRAC and MIPS instruments aboard the Spitzer Space Telescope. These infrared bands are particularly interesting for star formation studies because the ultraviolet light from young stars is reprocessed into thermal emission in the far-infrared (24mum MIPS) by dust and into vibrational transitions features in the mid-infrared (8.0mum IRAC) by polycyclic aromatic hydrocarbons (PAHs). The work I present here examines the efficiencies of PAH and thermal dust emission as tracers of star-formation rates over a wide range of galactic stellar masses. I find that the efficiency of PAH as a star-formation tracer varies with galactic stellar mass, while thermal dust has a highly variable efficiency that does not systematically depend on galactic stellar mass

Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

PubMed

Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

2016-12-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

Genetically engineered T cells to target EGFRvIII expressing glioblastoma.

PubMed

Bullain, Szofia S; Sahin, Ayguen; Szentirmai, Oszkar; Sanchez, Carlos; Lin, Ning; Baratta, Elizabeth; Waterman, Peter; Weissleder, Ralph; Mulligan, Richard C; Carter, Bob S

2009-09-01

Glioblastoma remains a significant therapeutic challenge, warranting further investigation of novel therapies. We describe an immunotherapeutic strategy to treat glioblastoma based on adoptive transfer of genetically modified T-lymphocytes (T cells) redirected to kill EGFRvIII expressing gliomas. We constructed a chimeric immune receptor (CIR) specific to EGFRvIII, (MR1-zeta). After in vitro selection and expansion, MR1-zeta genetically modified primary human T-cells specifically recognized EGFRvIII-positive tumor cells as demonstrated by IFN-gamma secretion and efficient tumor lysis compared to control CIRs defective in EGFRvIII binding (MRB-zeta) or signaling (MR1-delzeta). MR1-zeta expressing T cells also inhibited EGFRvIII-positive tumor growth in vivo in a xenografted mouse model. Successful targeting of EGFRvIII-positive tumors via adoptive transfer of genetically modified T cells may represent a new immunotherapy strategy with great potential for clinical applications.

Galaxies in the act of quenching star formation

NASA Astrophysics Data System (ADS)

Quai, Salvatore; Pozzetti, Lucia; Citro, Annalisa; Moresco, Michele; Cimatti, Andrea

2018-04-01

Detecting galaxies when their star-formation is being quenched is crucial to understand the mechanisms driving their evolution. We identify for the first time a sample of quenching galaxies selected just after the interruption of their star formation by exploiting the [O III] λ5007/Hα ratio and searching for galaxies with undetected [O III]. Using a sample of ˜174000 star-forming galaxies extracted from the SDSS-DR8 at 0.04 ≤ z < 0.21,we identify the ˜300 quenching galaxy best candidates with low [O III]/Hα, out of ˜26 000 galaxies without [O III] emission. They have masses between 10^{9.7} and 10^{10.8} M_{⊙},consistently with the corresponding growth of the quiescent population at these redshifts. Their main properties (i.e. star-formation rate, colours and metallicities) are comparable to those of the star-forming population, coherently with the hypothesis of recent quenching, but preferably reside in higher-density environments.Most candidates have morphologies similar to star-forming galaxies, suggesting that no morphological transformation has occurred yet. From a survival analysis we find a low fraction of candidates (˜ 0.58% of the star-forming population), leading to a short quenching timescale of tQ ˜ 50 Myr and an e-folding time for the quenching history of τQ ˜ 90 Myr, and their upper limits of tQ < 0.76 Gyr and τQ <1.5 Gyr, assuming as quenching galaxies 50% of objects without [O III] (˜7.5%).Our results are compatible with a 'rapid' quenching scenario of satellites galaxies due to the final phase of strangulation or ram-pressure stripping. This approach represents a robust alternative to methods used so far to select quenched galaxies (e.g. colours, specific star-formation rate, or post-starburst spectra).

Synthesis and characterization of Silica/polyvinyl imidazole/H2PO4-core-shell nanoparticles as recyclable adsorbent for efficient scavenging of Sm(III) and Dy(III) from water.

PubMed

Ettehadi Gargari, Jafar; Sid Kalal, Hossein; Shakeri, Alireza; Khanchi, Alireza

2017-11-01

In this study, we used Silica/polyvinyl imidazole core-shell nanoparticles impregnated with sodium dihydrogen phosphate (SiO 2 /PVI/H 2 PO 4 - NPs) for adsorption of samarium and dysprosium ions from aqueous solutions. The effects of the pH, adsorbent dose, contact time, and initial concentration of the adsorbate on the Core-shell nanoparticles adsorption capacity have been studied. The pH value for maximum removal of Sm (III) and Dy (III) on the core-shell nanoparticles surface were found to be 4. The saturated capacity of SiO 2 /PVI/H 2 PO 4 - NPs was up to 160mg.g -1 and 150mg.g -1 at 25°C for Sm (III) and Dy (III) ions respectively. The obtained uptake data were analyzed by the Langmuir and Freundlich equations using a linearized correlation coefficient at room temperature. The Freundlich isotherm was found to fit well with the equilibrium data. The adsorption kinetics could be modeled by a pseudo-second-order rate expression. Thermodynamic investigation revealed the adsorption process of the studied ions is entropy driven. Furthermore, the performance of regeneration and reutilization were studied. The adsorbed Sm (III) and Dy (III) can be desorbed by 0.5mol/L HCl, with the desorption percentage of 90% for Sm (III) and Dy (III). After five adsorption-desorption cycles, the adsorption capacity shows a slight decrease (about 15%), implying that the SiO 2 /PVI/H 2 PO 4 - NPs can be used as an effective adsorbent for the removal and recovery of Sm(III) and Dy(III) from aqueous solution. The colloid stability of the SiO 2 /PVI/H 2 PO 4 - NPs was investigated by dynamic light scattering measurements. The SiO 2 /PVI/H 2 PO 4 - NPs are stable in adsorption media after five adsorption - desorption cycles. The high stability of SiO 2 /PVI/H 2 PO 4 - NPs can be attributed to steric stabilization by polyvinyl imidazole adsorbed on SiO 2 nanoparticle surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

Simultaneous AuIII Extraction and In Situ Formation of Polymeric Membrane-Supported Au Nanoparticles: A Sustainable Process with Application in Catalysis.

PubMed

Mora-Tamez, Lucía; Esquivel-Peña, Vicente; Ocampo, Ana L; Rodríguez de San Miguel, Eduardo; Grande, Daniel; de Gyves, Josefina

2017-04-10

A polymeric membrane-supported catalyst with immobilized gold nanoparticles (AuNPs) was prepared through the extraction and in situ reduction of Au III salts in a one-step strategy. Polymeric inclusion membranes (PIMs) and polymeric nanoporous membranes (PNMs) were tested as different membrane-support systems. Transport experiments indicated that PIMs composed of cellulose triacetate, 2-nitrophenyloctyl ether, and an aliphatic tertiary amine (Adogen 364 or Alamine 336) were the most efficient supports for Au III extraction. The simultaneous extraction and reduction processes were proven to be the result of a synergic phenomenon in which all the membrane components were involved. Scanning electron microscopy characterization of cross-sectional samples suggested a distribution of AuNPs throughout the membrane. Transmission electron microscopy characterization of the AuNPs indicated average particle sizes of 36.7 and 2.9 nm for the PIMs and PNMs, respectively. AuNPs supported on PIMs allowed for >95.4 % reduction of a 0.05 mmol L -1 4-nitrophenol aqueous solution with 10 mmol L -1 NaBH 4 solution within 25 min. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth of AlGaN alloys under excess group III conditions: Formation of vertical nanorods

NASA Astrophysics Data System (ADS)

Singha, Chirantan; Sen, Sayantani; Pramanik, Pallabi; Palit, Mainak; Das, Alakananda; Roy, Abhra Shankar; Sen, Susanta; Bhattacharyya, Anirban

2018-01-01

Droplet Epitaxy of AlGaN nanostructures was investigated in this work. Growth was carried out by Plasma Assisted Molecular Beam Epitaxy (PA-MBE) under extreme group III rich conditions, where the excess metal remained on the growth surface and formed nanoscale metallic droplets due to the interplay of surface energy, surface diffusion and desorption, all of which are strongly dependent on the relative arrival rates of gallium and aluminum and the substrate temperature. Intermittent exposure of this metallic film to active nitrogen forms various types of nanostructures, whose morphology, composition and luminescence properties were evaluated. Our results indicate that for AlN, the droplet epitaxy process forms random arrays of uniform well oriented [0 0 0 1] nanorods with a height of ∼1 μm and a diameter of 250 nm. For AlGaN grown under excess gallium, and intermittent exposure to the active plasma, structures with diameters of 200 μm to 600 μm and a height of 80 nm were observed. We report the spontaneous formation of lateral concentric heterostructures under these conditions. A single photoluminescence (PL) peak was observed at about 260 nm with a room temperature to 4 K intensity ratio of ∼25%.

The effect of organic compounds in the oxidation kinetics of Cr(III) by H 2O 2

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Gennari, Francesca; Campanella, Luigi; Millero, Frank J.

2008-12-01

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant ( k1) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min -1) for the pseudo first order rate constant k and values approaching zero for k and k. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H 2O 2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H 2O 2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H 2O 2 appear to be lowered probably because of steric hindrance of the chelated Cr(III).

Controllable production of low molecular weight heparins by combinations of heparinase I/II/III.

PubMed

Wu, Jingjun; Zhang, Chong; Mei, Xiang; Li, Ye; Xing, Xin-Hui

2014-01-30

Enzymatic depolymerization of heparin by heparinases is promising for production of low molecular weight heparins (LMWHs) as anticoagulants, due to its mild reaction conditions and high selectivity. Here, different heparinase combinations were used to depolymerize heparin. Heparinase I and heparinase II can depolymerize heparin more efficiently than heparinase III, respectively, but heparinase III was the best able to protect the anticoagulant activities of LMWHs. Heparinase III and heparinase I/II combinations were able to efficiently depolymerize heparin to LMWHs with higher anticoagulant activity than the LMWHs produced by the respective heparinase I and heparinase II. HepIII and HepI is the best combination for maintaining high anti-IIa activity (75.7 ± 4.21 IU/mg) at the same Mw value. Furthermore, considering both the changes in molecular weight and anticoagulant activity, the action patterns of heparinase I and heparinase II were found not to follow the exolytic and processive depolymerizing mechanism from the reducing end of heparin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ultra-high-throughput Production of III-V/Si Wafer for Electronic and Photonic Applications

PubMed Central

Geum, Dae-Myeong; Park, Min-Su; Lim, Ju Young; Yang, Hyun-Duk; Song, Jin Dong; Kim, Chang Zoo; Yoon, Euijoon; Kim, SangHyeon; Choi, Won Jun

2016-01-01

Si-based integrated circuits have been intensively developed over the past several decades through ultimate device scaling. However, the Si technology has reached the physical limitations of the scaling. These limitations have fuelled the search for alternative active materials (for transistors) and the introduction of optical interconnects (called “Si photonics”). A series of attempts to circumvent the Si technology limits are based on the use of III-V compound semiconductor due to their superior benefits, such as high electron mobility and direct bandgap. To use their physical properties on a Si platform, the formation of high-quality III-V films on the Si (III-V/Si) is the basic technology ; however, implementing this technology using a high-throughput process is not easy. Here, we report new concepts for an ultra-high-throughput heterogeneous integration of high-quality III-V films on the Si using the wafer bonding and epitaxial lift off (ELO) technique. We describe the ultra-fast ELO and also the re-use of the III-V donor wafer after III-V/Si formation. These approaches provide an ultra-high-throughput fabrication of III-V/Si substrates with a high-quality film, which leads to a dramatic cost reduction. As proof-of-concept devices, this paper demonstrates GaAs-based high electron mobility transistors (HEMTs), solar cells, and hetero-junction phototransistors on Si substrates. PMID:26864968

Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

PubMed Central

2010-01-01

Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3) pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory. PMID:20836848

Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli.

PubMed

Hatahet, Feras; Nguyen, Van Dat; Salo, Kirsi E H; Ruddock, Lloyd W

2010-09-13

The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3) pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation environment of Pop II stars affected by the feedbacks from Pop III stars

NASA Astrophysics Data System (ADS)

Chiaki, G.; Susa, H.; Hirano, S.

Stars with metallicities abH Fe < -3 are called extremely metal-poor (EMP) stars, and considered to be formed in clouds enriched with metal from a single or several supernovae (SNe) of the first-generation (Pop III) stars. To confirm this, we numerically follow the enrichment process of minihalos (MHs) which have hosted Pop III stars. During their main-sequence (MS), the ionizing photons can not or partly break the gas around the Pop III stars because the halo binding energy is marginally larger than the radiation energy. After SN explosions, the gas continues to accrete along filaments of the large-scale structures, and the gas collapses again in the MHs within ˜ 10 Myr for low-mass MHs (3E 5 M⊙) while ˜ 1 Myr for massive MHs (3E 6 M⊙). The metallicity in the recollapsing regions is 10-4-10-2 Z⊙ /SUB and 10-6-10-5 Z⊙, respectively. This indicates that EMP stars are formed in the clouds enriched by a single SN in low-mass MHs.

Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

USGS Publications Warehouse

Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

2005-01-01

A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

Iodine(III) Reagents in Radical Chemistry

PubMed Central

2017-01-01

Conspectus The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF3, X–CF3 (X = heteroatom), C–Rf (Rf = perfluoroalkyl), X–Rf, C–N3, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF3+”, “Rf+”, “N3+”, “Ar+”, “CN+”, and “X+” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, aryliodonium ylides, aryl(cyano)iodonium triflates, and aryl(perfluoroalkyl)iodonium triflates. Radical generation starting with I(III) reagents can also occur via thermal or light mediated homolysis of the weak hypervalent bond in such reagents. This reactivity can be used for alkane C–H functionalization. We will address important pioneering work in the area but will mainly focus on studies that have been conducted by our group over the last 5 years. We entered the field by investigating transition metal free single electron reduction of Togni type reagents using the readily available sodium 2,2,6,6-tetramethylpiperidine-1-oxyl salt (TEMPONa) as an organic one electron reductant for clean generation of the trifluoromethyl radical and perfluoroalkyl radicals. That valuable approach was later successfully also applied to the generation of azidyl and aryl radicals starting with the corresponding benziodoxole (Zhdankin reagent

Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency

DOE PAGES

Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; ...

2017-05-04

Here, we report a new family of preorganized bislactam- 1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent fblock metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performancemore » of these preorganized compounds.« less

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations.

PubMed

Roberts, Linda C; Hug, Stephan J; Ruettimann, Thomas; Billah, Morsaline; Khan, Abdul Wahab; Rahman, Mohammad Tariqur

2004-01-01

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.

An Analytical Method To Compute Comet Cloud Formation Efficiency And Its Application

NASA Astrophysics Data System (ADS)

Brasser, Ramon; Duncan, M. J.

2007-07-01

A quick analytical method is presented for calculating comet cloud formation efficiency in the case of a single planet or multiple-planet system for planets that are not too eccentric (e_p < 0.2). A method to calculate the fraction of comets that stay under the control of each planet is also presented. The location of the planet(s) in mass-semi-major axis space to form a comet cloud is constrained based on the conditions developed by Tremaine (1993) together with estimates of the likelihood of passing comets between planets; and, in the case of a single, eccentric planet, the additional constraint that it is, by itself, able to accelerate material to lower values of Tisserand parameter within the age of the stellar system without sweeping up the majority of the material beforehand. For a single planet, it turns out the efficiency is mainly a function of planetary mass and semi-major axis of the planet and density of the stellar environment. The theory has been applied to some extrasolar systems and compared to numerical simulations for both these systems and the Solar system, as well as a diffusion scheme based on the energy kick distribution of Everhart (1968). Results agree well with analytical predictions.

Hybrid Integration of III-V Solar Microcells for High Efficiency Concentrated Photovoltaic Modules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tauke-Pedretti, Anna; Cederberg, Jeffery; Cruz-Campa, Jose Luis

The design, fabrication and performance of InGaAs and InGaP/GaAs microcells are presented. These cells are integrated with a Si wafer providing a path for insertion in hybrid concentrated photovoltaic modules. Comparisons are made between bonded cells and cells fabricated on their native wafer. The bonded cells showed no evidence of degradation in spite of the integration process which involved significant processing including the removal of the III-V substrate. Results from a number of hybrid cell configurations were reported. These cells employed integration techniques including wafer level bonding of processed cells and solder bonding of the cells. Lastly, the cells themselvesmore » showed evidence of degradation in spite of the integration process, which involved significant processing including the removal of the III-V substrate.« less

Hybrid Integration of III-V Solar Microcells for High Efficiency Concentrated Photovoltaic Modules

DOE PAGES

Tauke-Pedretti, Anna; Cederberg, Jeffery; Cruz-Campa, Jose Luis; ...

2018-03-09

The design, fabrication and performance of InGaAs and InGaP/GaAs microcells are presented. These cells are integrated with a Si wafer providing a path for insertion in hybrid concentrated photovoltaic modules. Comparisons are made between bonded cells and cells fabricated on their native wafer. The bonded cells showed no evidence of degradation in spite of the integration process which involved significant processing including the removal of the III-V substrate. Results from a number of hybrid cell configurations were reported. These cells employed integration techniques including wafer level bonding of processed cells and solder bonding of the cells. Lastly, the cells themselvesmore » showed evidence of degradation in spite of the integration process, which involved significant processing including the removal of the III-V substrate.« less

Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes.

PubMed

Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi

2012-08-07

The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

Quantum efficiency performances of the NIR European Large Format Array detectors tested at ESTEC

NASA Astrophysics Data System (ADS)

Crouzet, P.-E.; Duvet, L.; de Wit, F.; Beaufort, T.; Blommaert, S.; Butler, B.; Van Duinkerken, G.; ter Haar, J.; Heijnen, J.; van der Luijt, K.; Smit, H.

2015-10-01

Publisher's Note: This paper, originally published on 10/12/2015, was replaced with a corrected/revised version on 10/23/2015. If you downloaded the original PDF but are unable to access the revision, please contact SPIE Digital Library Customer Service for assistance. The Payload Technology Validation Section (SRE-FV) at ESTEC has the goal to validate new technology for future or on-going mission. In this framework, a test set up to characterize the quantum efficiency of near-infrared (NIR) detectors has been created. In the context of the NIR European Large Format Array ("LFA"), 3 deliverables detectors coming from SELEX-UK/ATC (UK) on one side, and CEA/LETI- CEA/IRFU-SOFRADIR (FR) on the other side were characterized. The quantum efficiency of an HAWAII-2RG detector from Teledyne was as well measured. The capability to compare on the same setup detectors from different manufacturers is a unique asset for the future mission preparation office. This publication will present the quantum efficiency results of a HAWAII-2RG detector from Teledyne with a 2.5um cut off compared to the LFA European detectors prototypes developed independently by SELEX-UK/ATC (UK) on one side, and CEA/LETI- CEA/IRFU-SOFRADIR (FR) on the other side.

Impact of Fe(III)-OM complexes and Fe(III) polymerization on SOM pools reactivity under different land uses

NASA Astrophysics Data System (ADS)

Giannetta, B.; Plaza, C.; Zaccone, C.; Siebecker, M. G.; Rovira, P.; Vischetti, C.; Sparks, D. L.

2017-12-01

Soil organic matter (SOM) protection and long-term accumulation are controlled by adsorption to mineral surfaces in different ways, depending on its molecular structure and pedo-climatic conditions. Iron (Fe) oxides are known to be key regulators of the soil carbon (C) cycle, and Fe speciation in soils is highly dependent on environmental conditions and chemical interactions with SOM. However, the molecular structure and hydrolysis of Fe species formed in association with SOM is still poorly described. We hypothesize the existence of two pools of Fe which interact with SOM: mononuclear Fe(III)-SOM complexes and precipitated Fe(III) hydroxides. To verify our hypothesis, we investigated the interactions between Fe(III) and physically isolated soil fractions by means of batch experiments at pH 7. Specifically, we examined the fine silt plus clay (FSi+C) fraction, obtained by ultrasonic dispersion and wet sieving. The soil samples spanned several land uses, including coniferous forest (CFS), grassland (GS), technosols (TS) and agricultural (AS) soils. Solid phase products and supernatants were analyzed for C and Fe content. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis were also performed. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used to assess the main C functional groups involved in C complexation and desorption experiments. Preliminary linear combination fitting (LCF) of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra suggested the formation of ferrihydrite-like polymeric Fe(III) oxides in reacted CFS and GS samples, with higher C and Fe concentration. Conversely, mononuclear Fe(III) OM complexes dominated the speciation for TS and AS samples, characterized by lower C and Fe concentration, inhibiting the hydrolysis and polymerization of Fe (III). This approach will help revealing the mechanisms by which SOM pools can control Fe(III) speciation, and will elucidate how both Fe(III

New La(III) complex immobilized on 3-aminopropyl-functionalized silica as an efficient and reusable catalyst for hydrolysis of phosphate ester bonds.

PubMed

Muxel, Alfredo A; Neves, Ademir; Camargo, Maryene A; Bortoluzzi, Adailton J; Szpoganicz, Bruno; Castellano, Eduardo E; Castilho, Nathalia; Bortolotto, Tiago; Terenzi, Hernán

2014-03-17

Described herein is the synthesis, structure, and monoesterase and diesterase activities of a new mononuclear [La(III)(L(1))(NO3)2] (1) complex (H2L(1) = 2-bis[{(2-pyridylmethyl)-aminomethyl}-6-[N-(2-pyridylmethyl) aminomethyl)])-4-methyl-6-formylphenol) in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate (2,4-BDNPP). When covalently linked to 3-aminopropyl-functionalized silica, 1 undergoes disproportionation to form a dinuclear species (APS-1), whose catalytic efficiency is increased when compared to the homogeneous reaction due to second coordination sphere effects which increase the substrate to complex association constant. The anchored catalyst APS-1 can be recovered and reused for subsequent hydrolysis reactions (five times) with only a slight loss in activity. In the presence of DNA, we suggest that 1 is also converted into the dinuclear active species as observed with APS-1, and both were shown to be efficient in DNA cleavage.

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

Efficient CO2 capture by tertiary amine-functionalized ionic liquids through Li+-stabilized zwitterionic adduct formation

PubMed Central

Yang, Zhen-Zhen

2014-01-01

Summary Highly efficient CO2 absorption was realized through formation of zwitterionic adducts, combining synthetic strategies to ionic liquids (ILs) and coordination. The essence of our strategy is to make use of multidentate cation coordination between Li+ and an organic base. Also PEG-functionalized organic bases were employed to enhance the CO2-philicity. The ILs were reacted with CO2 to form the zwitterionic adduct. Coordination effects between various lithium salts and neutral ligands, as well as the CO2 capacity of the chelated ILs obtained were investigated. For example, the CO2 capacity of PEG150MeBu2N increased steadily from 0.10 to 0.66 (mol CO2 absorbed per mol of base) through the formation of zwitterionic adducts being stabilized by Li+. PMID:25246955

An Efficient Format for Nearly Constant-Time Access to Arbitrary Time Intervals in Large Trace Files

DOE PAGES

Chan, Anthony; Gropp, William; Lusk, Ewing

2008-01-01

A powerful method to aid in understanding the performance of parallel applications uses log or trace files containing time-stamped events and states (pairs of events). These trace files can be very large, often hundreds or even thousands of megabytes. Because of the cost of accessing and displaying such files, other methods are often used that reduce the size of the tracefiles at the cost of sacrificing detail or other information. This paper describes a hierarchical trace file format that provides for display of an arbitrary time window in a time independent of the total size of the file and roughlymore » proportional to the number of events within the time window. This format eliminates the need to sacrifice data to achieve a smaller trace file size (since storage is inexpensive, it is necessary only to make efficient use of bandwidth to that storage). The format can be used to organize a trace file or to create a separate file of annotations that may be used with conventional trace files. We present an analysis of the time to access all of the events relevant to an interval of time and we describe experiments demonstrating the performance of this file format.« less

Uptake of Au(III) Ions by Aluminum Hydroxide and Their Spontaneous Reduction to Elemental Gold (Au(0)).

PubMed

Yokoyama; Matsukado; Uchida; Motomura; Watanabe; Izawa

2001-01-01

The behavior of AuCl(4)(-) ions during the formation of aluminum hydroxide at pH 6 was examined. With an increase in NaCl concentration, the content of gold taken up by aluminum hydroxide decreased, suggesting that chloro-hydroxy complexes of Au(III) ion were taken up due to the formation of Al-O-Au bonds. It was found unexpectedly that the Au(III) ions taken up were spontaneously reduced to elemental gold without addition of a specific reducing reagent and then colloidal gold particles were formed. The mechanisms for the uptake of Au(III) ions by aluminum hydroxide and for their spontaneous reduction are discussed. Copyright 2001 Academic Press.

Ceria modified activated carbon: an efficient arsenic removal adsorbent for drinking water purification

NASA Astrophysics Data System (ADS)

Sawana, Radha; Somasundar, Yogesh; Iyer, Venkatesh Shankar; Baruwati, Babita

2017-06-01

Ceria (CeO2) coated powdered activated carbon was synthesized by a single step chemical process and demonstrated to be a highly efficient adsorbent for the removal of both As(III) and As(V) from water without any pre-oxidation process. The formation of CeO2 on the surface of powdered activated carbon was confirmed by X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy. The percentage of Ce in the adsorbent was confirmed to be 3.5 % by ICP-OES. The maximum removal capacity for As(III) and As(V) was found to be 10.3 and 12.2 mg/g, respectively. These values are comparable to most of the commercially available adsorbents. 80 % of the removal process was completed within 15 min of contact time in a batch process. More than 95 % removal of both As(III) and As(V) was achieved within an hour. The efficiency of removal was not affected by change in pH (5-9), salinity, hardness, organic (1-4 ppm of humic acid) and inorganic anions (sulphate, nitrate, chloride, bicarbonate and fluoride) excluding phosphate. Presence of 100 ppm phosphate reduced the removal significantly from 90 to 18 %. The equilibrium adsorption pattern of both As(III) and As(V) fitted well with the Freundlich model with R 2 values 0.99 and 0.97, respectively. The material shows reusability greater than three times in a batch process (arsenic concentration reduced below 10 ppb from 330 ppb) and a life of at least 100 L in a column study with 80 g material when tested under natural hard water (TDS 1000 ppm, pH 7.8, hardness 600 ppm as CaCO3) spiked with 330 ppb of arsenic.

Efficient whole cell biocatalyst for formate-based hydrogen production.

PubMed

Kottenhahn, Patrick; Schuchmann, Kai; Müller, Volker

2018-01-01

Molecular hydrogen (H 2 ) is an attractive future energy carrier to replace fossil fuels. Biologically and sustainably produced H 2 could contribute significantly to the future energy mix. However, biological H 2 production methods are faced with multiple barriers including substrate cost, low production rates, and low yields. The C1 compound formate is a promising substrate for biological H 2 production, as it can be produced itself from various sources including electrochemical reduction of CO 2 or from synthesis gas. Many microbes that can produce H 2 from formate have been isolated; however, in most cases H 2 production rates cannot compete with other H 2 production methods. We established a formate-based H 2 production method utilizing the acetogenic bacterium Acetobacterium woodii . This organism can use formate as sole energy and carbon source and possesses a novel enzyme complex, the hydrogen-dependent CO 2 reductase that catalyzes oxidation of formate to H 2 and CO 2 . Cell suspensions reached specific formate-dependent H 2 production rates of 71 mmol g protein -1 h -1 (30.5 mmol g CDW -1 h -1 ) and maximum volumetric H 2 evolution rates of 79 mmol L -1 h -1 . Using growing cells in a two-step closed batch fermentation, specific H 2 production rates reached 66 mmol g CDW -1 h -1 with a volumetric H 2 evolution rate of 7.9 mmol L -1  h -1 . Acetate was the major side product that decreased the H 2 yield. We demonstrate that inhibition of the energy metabolism by addition of a sodium ionophore is suitable to completely abolish acetate formation. Under these conditions, yields up to 1 mol H 2 per mol formate were achieved. The same ionophore can be used in cultures utilizing formate as specific switch from a growing phase to a H 2 production phase. Acetobacterium woodii reached one of the highest formate-dependent specific H 2 productivity rates at ambient temperatures reported so far for an organism without genetic modification and converted the

Biomonitoring chromium III or VI soluble pollution by moss chlorophyll fluorescence.

PubMed

Chen, Yang-Er; Mao, Hao-Tian; Ma, Jie; Wu, Nan; Zhang, Chao-Ming; Su, Yan-Qiu; Zhang, Zhong-Wei; Yuan, Ming; Zhang, Huai-Yu; Zeng, Xian-Yin; Yuan, Shu

2018-03-01

We systematically compared the impacts of four Cr salts (chromic chloride, chromic nitrate, potassium chromate and potassium bichromate) on physiological parameters and chlorophyll fluorescence in indigenous moss Taxiphyllum taxirameum. Among the four Cr salts, K 2 Cr 2 O 7 treatment resulted in the most significant decrease in photosynthetic efficiency and antioxidant enzymes, increase in reactive oxygen species (ROS), and obvious cell death. Different form the higher plants, although hexavalent Cr(VI) salt treatments resulted in higher accumulation levels of Cr and were more toxic than Cr(III) salts, Cr(III) also induced significant changes in moss physiological parameters and chlorophyll fluorescence. Our results showed that Cr(III) and Cr(VI) could be monitored distinguishably according to the non-photochemical quenching (NPQ) fluorescence of sporadic purple and sporadic lavender images respectively. Then, the valence states and concentrations of Cr contaminations could be evaluated according to the image of maximum efficiency of PSII photochemistry (Fv/Fm) and the quantum yield of PSII electron transport (ΦPSII). Therefore, this study provides new ideas of moss's sensibility to Cr(III) and a new method to monitor Chromium contaminations rapidly and non-invasively in water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic and antimicrobial studies of La(III), Ce(III), Sm(III) and Y(III) Metformin HCl chelates.

PubMed

Refat, Moamen S; Al-Azab, Fathi M; Al-Maydama, Hussein M A; Amin, Ragab R; Jamil, Yasmin M S; Kobeasy, Mohamed I

2015-05-05

Metal complexes of Metformin hydrochloride were prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes were discussed and synthesized to serve as potential insulin-mimetic. Some physical properties and analytical data of the four complexes were checked. The elemental analysis shows that La(III), Ce(III) Sm(III) and Y(III) formed complexes with Metformin in 1:3 (metal:MF) molar ratio. All the synthesized complexes are white and possess high melting points. These complexes are soluble in dimethylsulfoxide and dimethylformamide, partially soluble in hot methanol and insoluble in water and some other organic solvents. From the spectroscopic (infrared, UV-vis and florescence), effective magnetic moment and elemental analyses data, the formula structures are suggested. The results obtained suggested that Metformin reacted with metal ions as a bidentate ligand through its two imino groups. The molar conductance measurements proved that the Metformin complexes are slightly electrolytic in nature. The kinetic thermodynamic parameters such as: E(∗), ΔH(∗), ΔS(∗) and ΔG(∗) were estimated from the DTG curves. The antibacterial evaluations of the Metformin and their complexes were also performed against some gram positive, negative bacteria as well as fungi. Copyright © 2015 Elsevier B.V. All rights reserved.

Isolation and Characterization of a Soluble NADPH-Dependent Fe(III) Reductase from Geobacter sulfurreducens

PubMed Central

Kaufmann, Franz; Lovley, Derek R.

2001-01-01

NADPH is an intermediate in the oxidation of organic compounds coupled to Fe(III) reduction in Geobacter species, but Fe(III) reduction with NADPH as the electron donor has not been studied in these organisms. Crude extracts of Geobacter sulfurreducens catalyzed the NADPH-dependent reduction of Fe(III)-nitrilotriacetic acid (NTA). The responsible enzyme, which was recovered in the soluble protein fraction, was purified to apparent homogeneity in a four-step procedure. Its specific activity for Fe(III) reduction was 65 μmol · min−1 · mg−1. The soluble Fe(III) reductase was specific for NADPH and did not utilize NADH as an electron donor. Although the enzyme reduced several forms of Fe(III), Fe(III)-NTA was the preferred electron acceptor. The protein possessed methyl viologen:NADP+ oxidoreductase activity and catalyzed the reduction of NADP+ with reduced methyl viologen as electron donor at a rate of 385 U/mg. The enzyme consisted of two subunits with molecular masses of 87 and 78 kDa and had a native molecular mass of 320 kDa, as determined by gel filtration. The purified enzyme contained 28.9 mol of Fe, 17.4 mol of acid-labile sulfur, and 0.7 mol of flavin adenine dinucleotide per mol of protein. The genes encoding the two subunits were identified in the complete sequence of the G. sulfurreducens genome from the N-terminal amino acid sequences derived from the subunits of the purified protein. The sequences of the two subunits had about 30% amino acid identity to the respective subunits of the formate dehydrogenase from Moorella thermoacetica, but the soluble Fe(III) reductase did not possess formate dehydrogenase activity. This soluble Fe(III) reductase differs significantly from previously characterized dissimilatory and assimilatory Fe(III) reductases in its molecular composition and cofactor content. PMID:11443080

The role of order-disorder transitions in the quest for molecular multiferroics: structural and magnetic neutron studies of a mixed valence iron(II)-iron(III) formate framework.

PubMed

Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J Alberto; Lemée-Cailleau, Marie-Hélène; Mason, Sax A; Pardo, Emilio; Lloret, Francesc; Zhao, Jiong-Peng; Bu, Xian-He; Simonet, Virginie; Colin, Claire V; Rodríguez-Carvajal, Juan

2012-12-05

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH(2)(CH(3))(2)](n)[Fe(III)Fe(II)(HCOO)(6)](n). The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [Fe(III)Fe(II)(HCOO)(6)](n) framework. In the low-temperature phase, a change in space group from P31c to R3c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different Fe(II) and Fe(III) magnetic moments.

Gold(III) chloride catalyzed synthesis of chiral substituted 3-formyl furans from carbohydrates: application in the synthesis of 1,5-dicarbonyl derivatives and furo[3,2-c]pyridine.

PubMed

Mal, Kanchan; Sharma, Abhinandan; Das, Indrajit

2014-09-08

This report describes a gold(III)-catalyzed efficient general route to densely substituted chiral 3-formyl furans under extremely mild conditions from suitably protected 5-(1-alkynyl)-2,3-dihydropyran-4-one using H2 O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne-gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti-endo-dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2 O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2 O to result in a substituted furo[3,2-c]pyran derivative, as anticipated. The similar furo[3,2-c]pyran skeleton with a hybrid carbohydrate-furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3-formyl furan. The corresponding protected 5-(1-alkynyl)-2,3-dihydropyran-4-one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3-formyl furan derivatives, a TiBr4 -catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5-dicarbonyl compounds, which on treatment with NH4 OAc in slightly acidic conditions afforded substituted furo[3,2-c]pyridine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficacy and efficiency in formative assessment: an informed reflection on the value of partial marking

NASA Astrophysics Data System (ADS)

Seaton, Katherine A.

2013-10-01

This article presents an informed reflection on the evolution of teacher-to-learner feedback provided on written assignments in first-year university mathematics subjects. The feedback provided addresses not only mathematical accuracy and skills, but also the development of graduate attributes, such as discipline-appropriate written communication. Effective and efficient practices that have been collectively refined and enhanced, for more than a decade, are described and examined. This model for formative assessment in mathematics subjects is critiqued in the light of the scholarly literature on feedback and assessment.

Investigation of Low Cost Substrate Approaches for III-V Solar Cells

NASA Astrophysics Data System (ADS)

Lichty, Marlene Lydia

With the need for cleaner energy sources, which can displace fossil fuel, the solar cell industry is of particular interest due to the abundancy of the Sun. Silicon currently dominates terrestrial applications, but efficiency improvements have saturated. III-V based solar cells have reported the highest efficiencies, however, high costs due to substrates and fabrication processes have limited these devices to specialty applications, such as space. In order to reduce the cost associated with fabricating III-V semiconductor substrate material, two different approaches were taken in this work with a particular focus on making III-Vs more applicable outside of specialty applications, including InP, InAsnd Ge. Typical material characterization techniques were used to analyze the samples and processes studied in this thesis. The first process examined was the direct epitaxial growth of III-V materials by MOCVD on cheaper substrates. More specifically, the direct growth of InP and InAs on metal foils. A growth time study and surface coverage analysis was performed for the growth of InP. A characterization study was then conducted on the second process, the aluminum- induced crystallization of germanium to determine the effects this process had on the surface. Crystalline InP, InAs and Ge were successfully characterized in this work, and show promise for use in cheaper III-V alternatives to terrestrial energy solutions.

TiO2-photocatalyzed As(III) oxidation in a fixed-bed, flow-through reactor.

PubMed

Ferguson, Megan A; Hering, Janet G

2006-07-01

Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally

Redox Cycling, pH Dependence, and Ligand Effects of Mn(III) in Oxalate Decarboxylase from Bacillus subtilis.

PubMed

Twahir, Umar T; Ozarowski, Andrew; Angerhofer, Alexander

2016-11-29

This contribution describes electron paramagnetic resonance (EPR) experiments on Mn(III) in oxalate decarboxylase of Bacillus subtilis, an interesting enzyme that catalyzes the redox-neutral dissociation of oxalate into formate and carbon dioxide. Chemical redox cycling provides strong evidence that both Mn centers can be oxidized, although the N-terminal Mn(II) appears to have the lower reduction potential and is most likely the carrier of the +3 oxidation state under moderate oxidative conditions, in agreement with the general view that it represents the active site. Significantly, Mn(III) was observed in untreated OxDC in succinate and acetate buffers, while it could not be directly observed in citrate buffer. Quantitative analysis showed that up to 16% of the EPR-visible Mn is in the +3 oxidation state at low pH in the presence of succinate buffer. The fine structure and hyperfine structure parameters of Mn(III) are affected by small carboxylate ligands that can enter the active site and have been recorded for formate, acetate, and succinate. The results from a previous report [Zhu, W., et al. (2016) Biochemistry 55, 429-434] could therefore be reinterpreted as evidence of formate-bound Mn(III) after the enzyme is allowed to turn over oxalate. The pH dependence of the Mn(III) EPR signal compares very well with that of enzymatic activity, providing strong evidence that the catalytic reaction of oxalate decarboxylase is driven by Mn(III), which is generated in the presence of dioxygen.

Efficient solar-driven synthesis, carbon capture, and desalinization, STEP: solar thermal electrochemical production of fuels, metals, bleach.

PubMed

Licht, S

2011-12-15

STEP (solar thermal electrochemical production) theory is derived and experimentally verified for the electrosynthesis of energetic molecules at solar energy efficiency greater than any photovoltaic conversion efficiency. In STEP the efficient formation of metals, fuels, chlorine, and carbon capture is driven by solar thermal heated endothermic electrolyses of concentrated reactants occuring at a voltage below that of the room temperature energy stored in the products. One example is CO(2) , which is reduced to either fuels or storable carbon at a solar efficiency of over 50% due to a synergy of efficient solar thermal absorption and electrochemical conversion at high temperature and reactant concentration. CO(2) -free production of iron by STEP, from iron ore, occurs via Fe(III) in molten carbonate. Water is efficiently split to hydrogen by molten hydroxide electrolysis, and chlorine, sodium, and magnesium from molten chlorides. A pathway is provided for the STEP decrease of atmospheric carbon dioxide levels to pre-industial age levels in 10 years. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fe(II) formation after interaction of the amyloid β-peptide with iron-storage protein ferritin.

PubMed

Balejcikova, Lucia; Siposova, Katarina; Kopcansky, Peter; Safarik, Ivo

2018-05-09

The interaction of amyloid β-peptide (Aβ) with the iron-storage protein ferritin was studied in vitro. We have shown that Aβ during fibril formation process is able to reduce Fe(III) from the ferritin core (ferrihydrite) to Fe(II). The Aβ-mediated Fe(III) reduction yielded a two-times-higher concentration of free Fe(II) than the spontaneous formation of Fe(II) by the ferritin itself. We suggest that Aβ can also act as a ferritin-specific metallochaperone-like molecule capturing Fe(III) from the ferritin ferrihydrite core. Our observation may partially explain the formation of Fe(II)-containing minerals in human brains suffering by neurodegenerative diseases.

Fe(III) and S0 reduction by Pelobacter carbinolicus

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.; Widma, P.K.

1995-01-01

There is a close phylogenetic relationship between Pelobacter species and members of the genera Desulfuromonas and Geobacter, and yet there has been a perplexing lack of physiological similarities. Pelobacter species have been considered to have a fermentative metabolism. In contrast, Desulfuromonas and Geobacter species have a respiratory metabolism with Fe(III) serving as the common terminal electron acceptor in all species. However, the ability of Pelobacter species to reduce Fe(III) had not been previously evaluated. When a culture of Pelobacter carbinolicus that had grown by fermentation of 2,3- butanediol was inoculated into the same medium supplemented with Fe(III), the Fe(III) was reduced. There was less accumulation of ethanol and more production of acetate in the presence of Fe(III). P. carbinolicus grew with ethanol as the sole electron donor and Fe(III) as the sole electron acceptor. Ethanol was metabolized to acetate. Growth was also possible on Fe(III) with the oxidation of propanol to propionate or butanol to butyrate if acetate was provided as a carbon source. P. carbinolicus appears capable of conserving energy to support growth from Fe(III) respiration as it also grew with H2 or formate as the electron donor and Fe(III) as the electron acceptor. Once adapted to Fe(III) reduction, P. carbinolicus could also grow on ethanol or H2 with S0 as the electron acceptor. P. carbinolicus did not contain detectable concentrations of the c-type cytochromes that previous studies have suggested are involved in electron transport to Fe(III) in other organisms that conserve energy to support growth from Fe(III) reduction. These results demonstrate that P. carbinolicus may survive in some sediments as an Fe(III) or S0 reducer rather than growing fermentatively on rare substrates or syntrophically as an ethanol-oxidizing acetogen. These studies also suggest that the ability to use Fe(III) as a terminal electron acceptor may be an important unifying feature of the

Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates.

PubMed

Draksharapu, Apparao; Angelone, Davide; Quesne, Matthew G; Padamati, Sandeep K; Gómez, Laura; Hage, Ronald; Costas, Miquel; Browne, Wesley R; de Visser, Sam P

2015-03-27

Fe III -hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe III -hypohalite intermediates of possible relevance to iron halogenases. We show that Fe III -OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the Fe III -OCl, and ultimately Fe IV =O, species and provide indirect evidence for a short-lived Fe II -OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases.

Alteration of BRCA1 expression affects alcohol-induced transcription of RNA Pol III-dependent genes.

PubMed

Zhong, Qian; Shi, Ganggang; Zhang, Yanmei; Lu, Lei; Levy, Daniel; Zhong, Shuping

2015-02-01

Emerging evidence has indicated that alcohol consumption is an established risk factor for breast cancer. Deregulation of RNA polymerase III (Pol III) transcription enhances cellular Pol III gene production, leading to an increase in translational capacity to promote cell transformation and tumor formation. We have reported that alcohol intake increases Pol III gene transcription to promote cell transformation and tumor formation in vitro and in vivo. Studies revealed that tumor suppressors, pRb, p53, PTEN and Maf1 repress the transcription of Pol III genes. BRCA1 is a tumor suppressor and its mutation is tightly related to breast cancer development. However, it is not clear whether BRCA1 expression affects alcohol-induced transcription of Pol III genes. At the present studies, we report that restoring BRCA1 in HCC 1937 cells, which is a BRCA1 deficient cell line, represses Pol III gene transcription. Expressing mutant or truncated BRCA1 in these cells does not affect the ability of repression on Pol III genes. Our analysis has demonstrated that alcohol induces Pol III gene transcription. More importantly, overexpression of BRCA1 in estrogen receptor positive (ER+) breast cancer cells (MCF-7) decreases the induction of tRNA(Leu) and 5S rRNA genes by alcohol, whereas reduction of BRCA1 by its siRNA slightly increases the transcription of the class of genes. This suggests that BRCA1 is associated with alcohol-induced deregulation of Pol III genes. These studies for the first time demonstrate the role of BRCA1 in induction of Pol III genes by alcohol and uncover a novel mechanism of alcohol-associated breast cancer. Copyright © 2014 Elsevier B.V. All rights reserved.

Low-Cost III-V Photovoltaic Materials by Chloride Vapor Transport Deposition Using Safe Solid Precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boettcher, Shannon; Aloni, Shaul; Weiss, Robert

Si-based photovoltaic devices dominate the market. As photovoltaic (PV) manufacturing costs have plummeted, technologies which increase efficiency have become critical. Si cell efficiencies are nearing theoretical limits and Si-based PV modules are unlikely to reach the 25-30% efficiency range. The use of III-V semiconductors is an obvious technical solution to improve efficiency, especially if they can be integrated directly with existing Si technology as tandems. High coefficients of light absorption along with tunable bandgaps and lattice constants have resulted in record conversion efficiencies for both one-sun and concentrator PV applications. GaAs, for example, has been used to manufacture single-junction photovoltaicsmore » with world-record efficiencies of 28.8% at one sun.2 However, costs for III-Vs must be dramatically reduced to produce cost-effective, high-efficiency PV solutions. III-V costs are controlled by two factors: semiconductor growth and the substrate. III-V growth is dominated today by metal-organic vapor phase epitaxy (MOVPE) with a lesser role played by molecular beam epitaxy (MBE). MOVPE costs are high due to the expense and low utilization (~30%) of precursors, modest growth rates (~100 nm min-1), equipment complexity, and safety infrastructure needed to handle toxic, pyrophoric gases.3 MBE costs are high due to slow growth rates and limitations of scalability. Details comparing plausible low-cost III-V growth methods are available in a review article published as a result of this project. The primary goal of this project was to demonstrate that close-spaced vapor transport (CSVT) using chloride (from HCl) as a transport agent can be used for the rapid growth of device-ready III-V layers from safe, solid-source precursors. In pursuit of this goal, we designed, built, and installed a new Cl-CSVT reactor based on insights from our previous H2O-CSVT growth system and in collaboration with equipment professionals at Malachite Technologies

Successive ion layer adsorption and reaction (SILAR) technique synthesis of Al(III)-8-hydroxy-5-nitrosoquinolate nano-sized thin films: characterization and factors optimization.

PubMed

Haggag, Sawsan M S; Farag, A A M; Abdel Refea, M

2013-02-01

Nano Al(III)-8-hydroxy-5-nitrosoquinolate [Al(III)-(HNOQ)(3)] thin films were synthesized by the rapid, direct, simple and efficient successive ion layer adsorption and reaction (SILAR) technique. Thin film formation optimized factors were evaluated. Stoichiometry and structure were confirmed by elemental analysis and FT-IR. The particle size (27-71 nm) was determined using scanning electron microscope (SEM). Thermal stability and thermal parameters were determined by thermal gravimetric analysis (TGA). Optical properties were investigated using spectrophotometric measurements of transmittance and reflectance at normal incidence. Refractive index, n, and absorption index, k, were determined. Spectral behavior of the absorption coefficient in the intrinsic absorption region revealed a direct allowed transition with 2.45 eV band gap. The current-voltage (I-V) characteristics of [Al(III)-(HNOQ)(3)]/p-Si heterojunction was measured at room temperature. The forward and reverse I-V characteristics were analyzed. The calculated zero-bias barrier height (Φ(b)) and ideality factor (n) showed strong bias dependence. Energy distribution of interface states (N(ss)) was obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

III-nitrides on oxygen- and zinc-face ZnO substrates

NASA Astrophysics Data System (ADS)

Namkoong, Gon; Burnham, Shawn; Lee, Kyoung-Keun; Trybus, Elaissa; Doolittle, W. Alan; Losurdo, Maria; Capezzuto, Pio; Bruno, Giovanni; Nemeth, Bill; Nause, Jeff

2005-10-01

The characteristics of III-nitrides grown on zinc- and oxygen-face ZnO by plasma-assisted molecular beam epitaxy were investigated. The reflection high-energy electron diffraction pattern indicates formation of a cubic phase at the interface between III-nitride and both Zn- and O-face ZnO. The polarity indicates that Zn-face ZnO leads to a single polarity, while O-face ZnO forms mixed polarity of III-nitrides. Furthermore, by using a vicinal ZnO substrate, the terrace-step growth of GaN was realized with a reduction by two orders of magnitude in the dislocation-related etch pit density to ˜108cm-2, while a dislocation density of ˜1010cm-2 was obtained on the on-axis ZnO substrates.

Dissolved Mn(III) in water treatment works: Prevalence and significance.

PubMed

Johnson, Karen L; McCann, Clare M; Wilkinson, John-Luke; Jones, Matt; Tebo, Bradley M; West, Martin; Elgy, Christine; Clarke, Catherine E; Gowdy, Claire; Hudson-Edwards, Karen A

2018-09-01

Dissolved Mn(III) has been identified at all stages throughout a Water Treatment Works (WTW) receiving inflow from a peaty upland catchment in NE England. Ninety percent of the influent total manganese into the WTW is particulate Mn, in the form of Mn oxide (>0.2 μm). Approximately 9% (mean value, n = 22, range of 0-100%) of the dissolved (<0.2 μm) influent Mn is present as dissolved Mn(III). Mn(III) concentrations are highest (mean of 49% of total dissolved Mn; n = 26, range of 17-89%) within the WTW where water comes into contact with the organic-rich sludges which are produced as waste products in the WTW. These Mn(III)-containing wastewaters are recirculated to the head of the works and constitute a large input of Mn(III) into the WTW. This is the first report of Mn(III) being identified in a WTW. The ability of Mn(III) to act as both an oxidant and a reductant is of interest to the water industry. Understanding the formation and removal of Mn(III) within may help reduce Mn oxide deposits in pipe networks. Further understanding how the ratio of Mn(III) to Mn(II) can be used to optimise dissolved Mn removal would save the water industry significant money in reducing discoloration 'events' at the customers' tap. Copyright © 2018. Published by Elsevier Ltd.

Microbial reduction of Fe(III) and turnover of acetate in Hawaiian soils.

PubMed

Küsel, Kirsten; Wagner, Christine; Trinkwalter, Tanja; Gössner, Anita S; Bäumler, Rupert; Drake, Harold L

2002-04-01

Soils contain anoxic microzones, and acetate is an intermediate during the turnover of soil organic carbon. Due to negligible methanogenic activities in well-drained soils, acetate accumulates under experimentally imposed short-term anoxic conditions. In contrast to forest, agricultural, and prairie soils, grassland soils from Hawaii rapidly consumed rather than formed acetate when incubated under anoxic conditions. Thus, alternative electron acceptors that might be linked to the anaerobic oxidation of soil organic carbon in Hawaiian soils were assessed. Under anoxic conditions, high amounts of Fe(II) were formed by Hawaiian soils as soon as soils were depleted of nitrate. Rates of Fe(II) formation for different soils ranged from 0.01 to 0.31 micromol (g dry weight soil)(-1) h(-1), but were not positively correlated to increasing amounts of poorly crystallized iron oxides. In general, sulfate-reducing and methanogenic activities were negligible. Supplemental acetate was rapidly oxidized to CO2 via the sequential reduction of nitrate and Fe(III) in grassland soil (obtained near Kaena State Park). Supplemental H2 stimulated the formation of Fe(II), but H2-utilizing acetogens appeared to also be involved in the consumption of H2. Approximately 270 micromol Fe(III) (g dry weight soil)(-1) was available for Fe(III)-reducing bacteria, and acetate became a stable end product when Fe(III) was depleted in long-term incubations. Most-probable-number estimates of H2- and acetate-utilizing Fe(III) reducers and of H2-utilizing acetogens were similar. These results indicate that (i) the microbial reduction of Fe(III) is an important electron-accepting process for the anaerobic oxidation of organic matter in Fe(III)-rich Hawaiian soils of volcanic origin, and (ii) acetate, formed by the combined activity of fermentative and acetogenic bacteria, is an important trophic link in anoxic microsites of these soils.

Amphiphilic complexes of Ho(iii), Dy(iii), Tb(iii) and Eu(iii) for optical and high field magnetic resonance imaging.

PubMed

Harris, Michael; Henoumont, Céline; Peeters, Wannes; Toyouchi, Shuichi; Vander Elst, Luce; Parac-Vogt, Tatjana N

2018-05-29

Lanthanides, holmium(iii), dysprosium(iii), and terbium(iii), were coordinated to an amphiphilic DOTA bis-coumarin derivative and then further assembled with an amphiphilic europium(iii) DTPA bis-coumarin derivative into mono-disperse micelles. The self-assembled micelles were characterized and assessed for their potential as bimodal contrast agents for high field magnetic resonance and optical imaging applications. All micelles showed a high transverse relaxation (r2) of 46, 34, and 30 s-1 mM-1 at 500 MHz and 37 °C for Dy(iii), Ho(iii) and Tb(iii), respectively, which is a result of the high magnetic moment of these lanthanides and the long rotational correlation time of the micelles. The quantum yield in aqueous solution ranged from 1.8% for Tb/Eu to 1.4% for Dy/Eu and 1.0% for the Ho/Eu micelles. Multi-photon excited emission spectroscopy has shown that due to the two-photon absorption of the coumarin chromophore the characteristic Eu(iii) emission could be observed upon excitation at 800 nm, demonstrating the usefulness of the system for in vivo fluorescence imaging applications. To the best of our knowledge, this is the first example reporting the potential of a holmium(iii) chelate as a negative MRI contrast agent.

Stomatin-Like Protein 2 Is Required for In Vivo Mitochondrial Respiratory Chain Supercomplex Formation and Optimal Cell Function

PubMed Central

Mitsopoulos, Panagiotis; Chang, Yu-Han; Wai, Timothy; König, Tim; Dunn, Stanley D.; Langer, Thomas

2015-01-01

Stomatin-like protein 2 (SLP-2) is a mainly mitochondrial protein that is widely expressed and is highly conserved across evolution. We have previously shown that SLP-2 binds the mitochondrial lipid cardiolipin and interacts with prohibitin-1 and -2 to form specialized membrane microdomains in the mitochondrial inner membrane, which are associated with optimal mitochondrial respiration. To determine how SLP-2 functions, we performed bioenergetic analysis of primary T cells from T cell-selective Slp-2 knockout mice under conditions that forced energy production to come almost exclusively from oxidative phosphorylation. These cells had a phenotype characterized by increased uncoupled mitochondrial respiration and decreased mitochondrial membrane potential. Since formation of mitochondrial respiratory chain supercomplexes (RCS) may correlate with more efficient electron transfer during oxidative phosphorylation, we hypothesized that the defect in mitochondrial respiration in SLP-2-deficient T cells was due to deficient RCS formation. We found that in the absence of SLP-2, T cells had decreased levels and activities of complex I-III2 and I-III2-IV1-3 RCS but no defects in assembly of individual respiratory complexes. Impaired RCS formation in SLP-2-deficient T cells correlated with significantly delayed T cell proliferation in response to activation under conditions of limiting glycolysis. Altogether, our findings identify SLP-2 as a key regulator of the formation of RCS in vivo and show that these supercomplexes are required for optimal cell function. PMID:25776552

Removal of chromium(III) from aqueous waste solution by liquid-liquid extraction in a circular microchannel.

PubMed

Luo, Jian Hong; Li, Jun; Guo, Lei; Zhu, Xin Hua; Dai, Shuang; Li, Xing

2017-11-01

A new circular microchannel device has been proposed for the removal of chromium(III) from aqueous waste solution by using kerosene as a diluent and (2-ethylhexyl) 2-ethylhexyl phosphonate as an extractant. The proposed device has several advantages such as a flexible and easily adaptable design, easy maintenance, and cheap setup without the requirement of microfabrication. To study the extraction efficiency and advantages of the circular microchannel device in the removal of chromium(III), the effects of various operating conditions such as the inner diameter of the channel, the total flow velocity, the phase ratio, the initial pH of aqueous waste solution, the reaction temperature and the initial concentration of extractant on the extraction efficiency are investigated and the optimal process conditions are obtained. The results show that chromium(III) in aqueous waste solution can be effectively removed with (2-ethylhexyl) 2-ethylhexyl phosphonate in the circular microchannel. Under optimized conditions, an extraction efficiency of chromium(III) of more than 99% can be attained and the aqueous waste solution can be discharged directly, which can meet the Chinese national emission standards.

Statistical aspects of the TNK-S2B trial of tenecteplase versus alteplase in acute ischemic stroke: an efficient, dose-adaptive, seamless phase II/III design.

PubMed

Levin, Bruce; Thompson, John L P; Chakraborty, Bibhas; Levy, Gilberto; MacArthur, Robert; Haley, E Clarke

2011-08-01

TNK-S2B, an innovative, randomized, seamless phase II/III trial of tenecteplase versus rt-PA for acute ischemic stroke, terminated for slow enrollment before regulatory approval of use of phase II patients in phase III. (1) To review the trial design and comprehensive type I error rate simulations and (2) to discuss issues raised during regulatory review, to facilitate future approval of similar designs. In phase II, an early (24-h) outcome and adaptive sequential procedure selected one of three tenecteplase doses for phase III comparison with rt-PA. Decision rules comparing this dose to rt-PA would cause stopping for futility at phase II end, or continuation to phase III. Phase III incorporated two co-primary hypotheses, allowing for a treatment effect at either end of the trichotomized Rankin scale. Assuming no early termination, four interim analyses and one final analysis of 1908 patients provided an experiment-wise type I error rate of <0.05. Over 1,000 distribution scenarios, each involving 40,000 replications, the maximum type I error in phase III was 0.038. Inflation from the dose selection was more than offset by the one-half continuity correction in the test statistics. Inflation from repeated interim analyses was more than offset by the reduction from the clinical stopping rules for futility at the first interim analysis. Design complexity and evolving regulatory requirements lengthened the review process. (1) The design was innovative and efficient. Per protocol, type I error was well controlled for the co-primary phase III hypothesis tests, and experiment-wise. (2a) Time must be allowed for communications with regulatory reviewers from first design stages. (2b) Adequate type I error control must be demonstrated. (2c) Greater clarity is needed on (i) whether this includes demonstration of type I error control if the protocol is violated and (ii) whether simulations of type I error control are acceptable. (2d) Regulatory agency concerns that protocols

Tuning of "antenna effect" of Eu(III) in ternary systems in aqueous medium through binding with protein.

PubMed

Ghorai, Shyamal Kr; Samanta, Swarna Kamal; Mukherjee, Manini; Saha Sardar, Pinki; Ghosh, Sanjib

2013-02-04

A simple ternary system containing a protein [human serum albumin (HSA)/bovine serum albumin (BSA)], tetracycline hydrochloride (TC), and Eu(III) in suitable aqueous buffer medium at physiological pH (= 7.2) has been shown to exhibit highly efficient "antenna effect" compared to the binary complex of TC with Eu(III) (Eu(3)TC). The ternary system containing E. coli alkaline phosphatase (AP), TC, and Eu(III), however, shows a slight enhancement of Eu(III) emission, although the binding constant of AP with TC is 2 orders of magnitude greater than with BSA/HSA. The enhanced emission of bound TC in the binary systems containing proteins and TC gets quenched in the ternary systems containing HSA/BSA, showing the efficient energy transfer (ET) from TC to Eu(III). Steady state and time-resolved emission studies of each component in all the ternary systems in H(2)O and in D(2)O medium reveal that Eu(III) is very well protected from the O-H oscillator in the ternary system containing HSA/BSA compared to that containing AP. The docking studies locating the binding site of TC in the proteins suggest that TC binds near the surface of AP. In the case of HSA/BSA, TC resides in the interior of the protein resulting in a large shielding effect of Eu(III). The rotational correlation time (θ(c)) determined from the anisotropy decay of bound TC in the complexes and the accessible surface area (ASA) of the ligand in the complexes obtained from the docking studies also support the contention that Eu(3)TC is more exposed to solvent in the case of the ternary system consisting of AP, TC, and Eu(III). The calculated radiative lifetime and the sensitization efficiency ratio of Eu(III) in all the systems clearly demonstrate the protein mediated tuning of "antenna effect" in Eu(III).

Star formation rates and efficiencies in the Galactic Centre

NASA Astrophysics Data System (ADS)

Barnes, A. T.; Longmore, S. N.; Battersby, C.; Bally, J.; Kruijssen, J. M. D.; Henshaw, J. D.; Walker, D. L.

2017-08-01

The inner few hundred parsecs of the Milky Way harbours gas densities, pressures, velocity dispersions, an interstellar radiation field and a cosmic ray ionization rate orders of magnitude higher than the disc; akin to the environment found in star-forming galaxies at high redshift. Previous studies have shown that this region is forming stars at a rate per unit mass of dense gas which is at least an order of magnitude lower than in the disc, potentially violating theoretical predictions. We show that all observational star formation rate diagnostics - both direct counting of young stellar objects and integrated light measurements - are in agreement within a factor two, hence the low star formation rate (SFR) is not the result of the systematic uncertainties that affect any one method. As these methods trace the star formation over different time-scales, from 0.1 to 5 Myr, we conclude that the SFR has been constant to within a factor of a few within this time period. We investigate the progression of star formation within gravitationally bound clouds on ˜parsec scales and find 1-4 per cent of the cloud masses are converted into stars per free-fall time, consistent with a subset of the considered 'volumetric' star formation models. However, discriminating between these models is obstructed by the current uncertainties on the input observables and, most importantly and urgently, by their dependence on ill-constrained free parameters. The lack of empirical constraints on these parameters therefore represents a key challenge in the further verification or falsification of current star formation theories.

Facile and Efficient Decontamination of Thorium from Rare Earths Based on Selective Selenite Crystallization.

PubMed

Wang, Yaxing; Lu, Huangjie; Dai, Xing; Duan, Tao; Bai, Xiaojing; Cai, Yawen; Yin, Xuemiao; Chen, Lanhua; Diwu, Juan; Du, Shiyu; Zhou, Ruhong; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Liu, Ning; Wang, Shuao

2018-02-19

The coexistence of radioactive contaminants (e.g., thorium, uranium, and their daughters) in rare earth minerals introduces significant environmental, economic, and technological hurdles in modern rare earth production. Efficient, low cost, and green decontamination strategies are therefore desired to ameliorate this problem. We report here a single-step and quantitative decontamination strategy of thorium from rare earths based on a unique periodic trend in the formation of crystalline selenite compounds across the lanthanide series, where Ce(III) is fully oxidized in situ to Ce(IV). This gives rise to a crystallization system that is highly selective to trap tetravalent f-blocks while all other trivalent lanthanides completely remain in solution when coexist. These results are bolstered by first-principles calculations of lattice energies and an examination of bonding in these compounds. This system is contrasted with typical natural and synthetic systems, where trivalent and tetravalent f-block elements often cocrystallize. The separation factors after one round of crystallization were determined from binary systems of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Yb(III) to reach 2.1 × 10 5 , 1.2 × 10 5 , and 9 × 10 4 , respectively. Selective crystallization of thorium from a simulated monazite composite yields a separation factor of 1.9 × 10 3 with nearly quantitative removal of thorium.

Strategies in Interventional Radiology: Formation of an Interdisciplinary Center of Vascular Anomalies - Chances and Challenges for Effective and Efficient Patient Management.

PubMed

Sadick, Maliha; Dally, Franz Josef; Schönberg, Stefan O; Stroszczynski, Christian; Wohlgemuth, Walter A

2017-10-01

Background  Radiology is an interdisciplinary field dedicated to the diagnosis and treatment of numerous diseases and is involved in the development of multimodal treatment concepts. Method  Interdisciplinary case management, a broad spectrum of diagnostic imaging facilities and dedicated endovascular radiological treatment options are valuable tools that allow radiology to set up an interdisciplinary center for vascular anomalies. Results  Image-based diagnosis combined with endovascular treatment options is an essential tool for the treatment of patients with highly complex vascular diseases. These vascular anomalies can affect numerous parts of the body so that a multidisciplinary treatment approach is required for optimal patient care. Conclusion  This paper discusses the possibilities and challenges regarding effective and efficient patient management in connection with the formation of an interdisciplinary center for vascular anomalies with strengthening of the clinical role of radiologists. Key points   · Vascular anomalies, which include vascular tumors and malformations, are complex to diagnose and treat.. · There are far more patients with vascular anomalies requiring therapy than interdisciplinary centers for vascular anomalies - there is currently a shortage of dedicated interdisciplinary centers for vascular anomalies in Germany that can provide dedicated care for affected patients.. · Radiology includes a broad spectrum of diagnostic and minimally invasive therapeutic tools which allow the formation of an interdisciplinary center for vascular anomalies for effective, efficient and comprehensive patient management.. Citation Format · Sadick M, Dally FJ, Schönberg SO et al. Strategies in Interventional Radiology: Formation of an Interdisciplinary Center of Vascular Anomalies - Chances and Challenges for Effective and Efficient Patient Management. Fortschr Röntgenstr 2017; 189: 957 - 966. © Georg Thieme Verlag KG Stuttgart · New

Delayed or No Feedback? Gas Outflows in Type 2 AGNs. III

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woo, Jong-Hak; Son, Donghoon; Bae, Hyun-Jin, E-mail: woo@astro.snu.ac.kr, E-mail: hjbae@galaxy.yonsei.ac.kr

2017-04-20

We present gas kinematics based on the [O iii] λ 5007 line and their connection to galaxy gravitational potential, active galactic nucleus (AGN) energetics, and star formation, using a large sample of ∼110,000 AGNs and star-forming (SF) galaxies at z < 0.3. Gas and stellar velocity dispersions are comparable to each other in SF galaxies, indicating that the ionized gas kinematics can be accounted by the gravitational potential of host galaxies. In contrast, AGNs clearly show non-gravitational kinematics, which is comparable to or stronger than the virial motion caused by the gravitational potential. The [O iii] velocity–velocity dispersion (VVD) diagrammore » dramatically expands toward high values as a function of AGN luminosity, implying that the outflows are AGN-driven, while SF galaxies do not show such a trend. We find that the fraction of AGNs with a signature of outflow kinematics, steeply increases with AGN luminosity and Eddington ratio. In particular, the majority of luminous AGNs presents strong non-gravitational kinematics in the [O iii] profile. AGNs with strong outflow signatures show on average similar specific star formation rates (sSFRs) to those of star-forming galaxies. In contrast, AGNs with weak or no outflows have an order of magnitude lower sSFRs, suggesting that AGNs with current strong outflows do now show any negative AGN feedback and that it may take dynamical time to impact on star formation over galactic scales.« less

Methods for improved growth of group III nitride buffer layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melnik, Yurity; Chen, Lu; Kojiri, Hidehiro

Methods are disclosed for growing high crystal quality group III-nitride epitaxial layers with advanced multiple buffer layer techniques. In an embodiment, a method includes forming group III-nitride buffer layers that contain aluminum on suitable substrate in a processing chamber of a hydride vapor phase epitaxy processing system. A hydrogen halide or halogen gas is flowing into the growth zone during deposition of buffer layers to suppress homogeneous particle formation. Some combinations of low temperature buffers that contain aluminum (e.g., AlN, AlGaN) and high temperature buffers that contain aluminum (e.g., AlN, AlGaN) may be used to improve crystal quality and morphologymore » of subsequently grown group III-nitride epitaxial layers. The buffer may be deposited on the substrate, or on the surface of another buffer. The additional buffer layers may be added as interlayers in group III-nitride layers (e.g., GaN, AlGaN, AlN).« less

Structure and membrane remodeling activity of ESCRT-III helical polymers

PubMed Central

McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; Skowyra, Michael L.; Saunders, Marissa G.; Naismith, Teresa V.; Colf, Leremy A.; Afonine, Pavel; Arthur, Christopher; Sundquist, Wesley I.; Hanson, Phyllis I.; Frost, Adam

2015-01-01

The Endosomal Sorting Complexes Required for Transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 Å resolution cryo-EM reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, CHMP1B and IST1. The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecture, and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively-curved membranes in vitro and in vivo. Our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature. PMID:26634441

Loss of GltB Inhibits Biofilm Formation and Biocontrol Efficiency of Bacillus subtilis Bs916 by Altering the Production of γ-Polyglutamate and Three Lipopeptides

PubMed Central

Luo, Chuping; Fang, Xianwen; Xiang, Yaping; Wang, Xiaoyu; Zhang, Rongsheng; Chen, Zhiyi

2016-01-01

Aims This study examined the contribution of GltB on biofilm formation and biocontrol efficiency of B. subtilis Bs916. Methods and Results The gltB gene was identified through a biofilm phenotype screen and a bioinformatics analysis of serious biofilm formation defects, and then a gltB single knockout mutant was constructed using homologous recombination. This mutant demonstrated severe deficits in biofilm formation and colonisation along with significantly altered production ofγ-polyglutamate (γ-PGA) and three lipopeptide antibiotics (LPs) as measured by a transcriptional analysis of both the wild type B. subtilis Bs916 and the gltB mutant. Consequently, the mutant strain retained almost no antifungal activity against Rhizoctonia solani and exhibited decreased biocontrol efficiency against rice sheath blight. Very few gltB mutant cells colonised the rice stem, and they exhibited no significant nutrient chemotaxis compared to the wild type B. subtilis Bs916. The mechanism underlying these deficits in the gltB mutant appears to be decreased significantly in production of γ-PGA and a reduction in the production of both bacillomycin L and fengycin. Biofilm restoration of gltB mutant by additionγ-PGA in the EM medium demonstrated that biofilm formation was able to restore significantly at 20 g/L. Conclusions GltB regulates biofilm formation by altering the production ofγ-PGA, the LPs bacillomycin L and fengcin and influences bacterial colonisation on the rice stem, which consequently leads to poor biocontrol efficiency against rice sheath blight. Significance and Impact of Study This is the first report of a key regulatory protein (GltB) that is involved in biofilm regulation and its regulation mechanism and biocontrol efficiency by B. subtilis. PMID:27223617

Thermodynamic study on the role of hydrogen during the MOVPE growth of group III nitrides

NASA Astrophysics Data System (ADS)

Koukitu, Akinori; Taki, Tetsuya; Takahashi, Naoyuki; Seki, Hisashi

1999-02-01

The role of hydrogen during the MOVPE growth of group III nitrides is investigated from a thermodynamic point of view. The effect of hydrogen is reported for the driving force for the deposition of binary nitrides as functions of growth temperature and V/III ratio. The effect of hydrogen for the InGaN growth is discussed for the vapor-solid relationship, the formation of compositional inhomogeneity and input partial pressure of the group III elements. The difference between the growth reaction of the indium containing nitrides and that of other III-V compounds is also discussed.

Biogenic Magnetite Formation through Anaerobic Biooxidation of Fe(II)

PubMed Central

Chaudhuri, Swades K.; Lack, Joseph G.; Coates, John D.

2001-01-01

The presence of isotopically light carbonates in association with fine-grained magnetite is considered to be primarily due to the reduction of Fe(III) by Fe(III)-reducing bacteria in the environment. Here, we report on magnetite formation by biooxidation of Fe(II) coupled to denitrification. This metabolism offers an alternative environmental source of biogenic magnetite. PMID:11375205

Uranium (III)-Plutonium (III) co-precipitation in molten chloride

NASA Astrophysics Data System (ADS)

Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

2018-02-01

Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

Discovery of extreme [O III] λ5007 Å outflows in high-redshift red quasars

NASA Astrophysics Data System (ADS)

Zakamska, Nadia L.; Hamann, Fred; Pâris, Isabelle; Brandt, W. N.; Greene, Jenny E.; Strauss, Michael A.; Villforth, Carolin; Wylezalek, Dominika; Alexandroff, Rachael M.; Ross, Nicholas P.

2016-07-01

Black hole feedback is now a standard component of galaxy formation models. These models predict that the impact of black hole activity on its host galaxy likely peaked at z = 2-3, the epoch of strongest star formation activity and black hole accretion activity in the Universe. We used XSHOOTER on the Very Large Telescope to measure rest-frame optical spectra of four z ˜ 2.5 extremely red quasars with infrared luminosities ˜1047 erg s-1. We present the discovery of very broad (full width at half max = 2600-5000 km s-1), strongly blueshifted (by up to 1500 km s-1) [O III] λ5007 Å emission lines in these objects. In a large sample of type 2 and red quasars, [O III] kinematics are positively correlated with infrared luminosity, and the four objects in our sample are on the extreme end in both [O III] kinematics and infrared luminosity. We estimate that at least 3 per cent of the bolometric luminosity in these objects is being converted into the kinetic power of the observed wind. Photo-ionization estimates suggest that the [O III] emission might be extended on a few kpc scales, which would suggest that the extreme outflow is affecting the entire host galaxy of the quasar. These sources may be the signposts of the most extreme form of quasar feedback at the peak epoch of galaxy formation, and may represent an active `blow-out' phase of quasar evolution.

Enhanced cellular uptake and in vitro antitumor activity of short-chain fatty acid acylated daunorubicin-GnRH-III bioconjugates.

PubMed

Hegedüs, Rózsa; Manea, Marilena; Orbán, Erika; Szabó, Ildikó; Kiss, Eva; Sipos, Eva; Halmos, Gábor; Mező, Gábor

2012-10-01

Here we report on the synthesis and biochemical characterization (enzymatic stability, cellular uptake, in vitro antitumor activity, membrane interaction and GnRH-receptor binding affinity) of novel short-chain fatty acid (SCFA) acylated daunorubicin-GnRH-III bioconjugates, which may serve as drug delivery systems for targeted cancer chemotherapy. Ser in position 4 of GnRH-III was replaced by Lys, followed by the acylation of its ε-amino group with various fatty acids. SCFAs are potentially chemoprotective agents by suppressing the growth of cancer cells and therefore may enhance the antitumor activity of the bioconjugates. We found that all synthesized bioconjugates had high cytostatic effect in vitro, were stable in cell culture medium for 6 h and degraded in the presence of rat liver lysosomal homogenate leading to the formation of an oxime bond-linked daunorubicin-Lys as the smallest active metabolite. In the presence of α-chymotrypsin, all compounds were digested, the degradation rate strongly depending on the type of fatty acid. The bioconjugate containing Lys(nBu) in position 4 was taken up most efficiently by the cancer cells and exerted higher in vitro cytostatic effect than the previously developed GnRH-III((4)Lys(Ac), (8)Lys(Dau = Aoa)) or the parent GnRH-III(Dau = Aoa) bioconjugate. Our results could be explained by the increased binding affinity of the newly developed compound containing Lys(nBu) to the GnRH receptors. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Side Chain Engineering on Medium Bandgap Copolymers to Suppress Triplet Formation for High-Efficiency Polymer Solar Cells.

PubMed

Xue, Lingwei; Yang, Yankang; Xu, Jianqiu; Zhang, Chunfeng; Bin, Haijun; Zhang, Zhi-Guo; Qiu, Beibei; Li, Xiaojun; Sun, Chenkai; Gao, Liang; Yao, Jia; Chen, Xiaofeng; Yang, Yunxu; Xiao, Min; Li, Yongfang

2017-10-01

Suppression of carrier recombination is critically important in realizing high-efficiency polymer solar cells. Herein, it is demonstrated difluoro-substitution of thiophene conjugated side chain on donor polymer can suppress triplet formation for reducing carrier recombination. A new medium bandgap 2D-conjugated D-A copolymer J91 is designed and synthesized with bi(alkyl-difluorothienyl)-benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit, for taking the advantages of the synergistic fluorination on the backbone and thiophene side chain. J91 demonstrates enhanced absorption, low-lying highest occupied molecular orbital energy level, and higher hole mobility, in comparison with its control polymer J52 without fluorination on the thiophene side chains. The transient absorption spectra indicate that J91 can suppress the triplet formation in its blend film with n-type organic semiconductor acceptor m-ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2,3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene). With these favorable properties, a higher power conversion efficiency of 11.63% with high V OC of 0.984 V and high J SC of 18.03 mA cm -2 is obtained for the polymer solar cells based on J91/m-ITIC with thermal annealing. The improved photovoltaic performance by thermal annealing is explained from the morphology change upon thermal annealing as revealed by photoinduced force microscopy. The results indicate that side chain engineering can provide a new solution to suppress carrier recombination toward high efficiency, thus deserves further attention. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative adsorption of Eu(III) and Am(III) on TPD.

PubMed

Fan, Q H; Zhao, X L; Ma, X X; Yang, Y B; Wu, W S; Zheng, G D; Wang, D L

2015-09-01

Comparative adsorption behaviors of Eu(III) and Am(III) on thorium phosphate diphosphate (TPD), i.e., Th4(PO4)4P2O7, have been studied using a batch approach and surface complexation model (SCM) in this study. The results showed that Eu(III) and Am(III) adsorption increased to a large extent with the increase in TPD dose. Strong pH-dependence was observed in both Eu(III) and Am(III) adsorption processes, suggesting that inner-sphere complexes (ISCs) were possibly responsible for the adsorption of Eu(III) and Am(III). Meanwhile, the adsorption of Eu(III) and Am(III) decreased to a different extent with the increase in ion strength, which was possibly related to outer-sphere complexes and/or ion exchange. In the presence of fulvic acid (FA), the adsorption of Eu(III) and Am(III) showed high enhancement mainly due to the ternary surface complexes of TPD-FA-Eu(3+) and TPD-FA-Am(3+). The SCM showed that one ion exchange (≡S3Am/Eu) and two ISCs (≡(XO)2Am/EuNO3 and ≡(YO)2Am/EuNO3) seemed more reasonable to quantitatively describe the adsorption edges of both Eu(III) and Am(III). Our findings obviously showed that Eu(III) could be a good analogue to study actinide behaviors in practical terms. However, it should be kept in mind that there are still obvious differences between the characteristics of Eu(III) and Am(III) in some special cases, for instance, the complex ability with organic matter and adsorption affinity to a solid surface.

Observational Corollaries of Proto-AGN: Understanding Formation of Supermassive Black Hole Seeds

NASA Astrophysics Data System (ADS)

Shlosman, Isaac

2016-10-01

Formation of supermassive black holes (SMBHs) is still an enigma. Recent detections of high-z quasars which harbor massive SMBHs provide a challenge to models of structure buildup in the universe. Main alternatives for the formation of SMBH seeds are (1) remnants of Population III stars, and (2) a direct baryonic collapse within dark matter (DM) halos of 10^8 Mo -- first halos whose virial temperature exceeds 10^4 K, and which can lead to the formation of proto-AGN -- luminous pre-SMBH objects. Potentially, this can involve both high-z objects as well as low-z dwarf galaxies in voids. We focus on the direct collapse in 10^8 Mo halos which circumvents the pitfalls of Pop III remnants. The collapse can proceed via a radiation pressure-supported quasistar -- with a modified blackbody continuum. Such a configuration requires a very efficient angular momentum transfer. Or, it can form a thick, differentially rotating, self-gravitating disk, which is associated with an X-ray-infrared continuum and Seyfert-level luminosity, anisotropic emission, massive bi-conical outflows, and will be a powerful source of the Ly-alpha emission. We propose to perform radiative transfer in the continuum and hydrogen lines (e.g., Lyman and Balmer), using our models of proto-AGN, and do it on-the-fly -- concurrently with the collapse. We shall test the path to quasistellar and disky proto-AGN, produce first synthetic spectra of proto-AGN, and address the issue of feasibility of their detection by the JWST. Finally, we shall develop the strategy of searching for these objects at high- and low-z, based on the specific features in the spectra and associated variability.

Ellagic acid inhibits iron-mediated free radical formation

NASA Astrophysics Data System (ADS)

Dalvi, Luana T.; Moreira, Daniel C.; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

2017-02-01

Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50 μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1 min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

Behind the lines–actions of bacterial type III effector proteins in plant cells

PubMed Central

Büttner, Daniela

2016-01-01

Pathogenicity of most Gram-negative plant-pathogenic bacteria depends on the type III secretion (T3S) system, which translocates bacterial effector proteins into plant cells. Type III effectors modulate plant cellular pathways to the benefit of the pathogen and promote bacterial multiplication. One major virulence function of type III effectors is the suppression of plant innate immunity, which is triggered upon recognition of pathogen-derived molecular patterns by plant receptor proteins. Type III effectors also interfere with additional plant cellular processes including proteasome-dependent protein degradation, phytohormone signaling, the formation of the cytoskeleton, vesicle transport and gene expression. This review summarizes our current knowledge on the molecular functions of type III effector proteins with known plant target molecules. Furthermore, plant defense strategies for the detection of effector protein activities or effector-triggered alterations in plant targets are discussed. PMID:28201715

mzDB: A File Format Using Multiple Indexing Strategies for the Efficient Analysis of Large LC-MS/MS and SWATH-MS Data Sets*

PubMed Central

Bouyssié, David; Dubois, Marc; Nasso, Sara; Gonzalez de Peredo, Anne; Burlet-Schiltz, Odile; Aebersold, Ruedi; Monsarrat, Bernard

2015-01-01

The analysis and management of MS data, especially those generated by data independent MS acquisition, exemplified by SWATH-MS, pose significant challenges for proteomics bioinformatics. The large size and vast amount of information inherent to these data sets need to be properly structured to enable an efficient and straightforward extraction of the signals used to identify specific target peptides. Standard XML based formats are not well suited to large MS data files, for example, those generated by SWATH-MS, and compromise high-throughput data processing and storing. We developed mzDB, an efficient file format for large MS data sets. It relies on the SQLite software library and consists of a standardized and portable server-less single-file database. An optimized 3D indexing approach is adopted, where the LC-MS coordinates (retention time and m/z), along with the precursor m/z for SWATH-MS data, are used to query the database for data extraction. In comparison with XML formats, mzDB saves ∼25% of storage space and improves access times by a factor of twofold up to even 2000-fold, depending on the particular data access. Similarly, mzDB shows also slightly to significantly lower access times in comparison with other formats like mz5. Both C++ and Java implementations, converting raw or XML formats to mzDB and providing access methods, will be released under permissive license. mzDB can be easily accessed by the SQLite C library and its drivers for all major languages, and browsed with existing dedicated GUIs. The mzDB described here can boost existing mass spectrometry data analysis pipelines, offering unprecedented performance in terms of efficiency, portability, compactness, and flexibility. PMID:25505153

Low-Metallicity Star Formation: From the First Stars to Dwarf Galaxies

NASA Astrophysics Data System (ADS)

Hunt, Leslie K.; Madden, Suzanne C.; Schneider, Raffaella

2008-12-01

Preface; SOC and LOC; Participants; Life at the conference; Conference photo; Session I. Population III and Metal-Free Star Formation: 1. Open questions in the study of population III star formation S. C. O. Glover, P. C. Clark, T. H. Greif, J. L. Johnson, V. Bromm, R. S. Klessen and A. Stacy; 2. Protostar formation in the early universe Naoki Yoshida; 3. Population III.1 stars: formation, feedback and evolution of the IMF Jonathan C. Tan; 4. The formation of the first galaxies and the transition to low-mass star formation T. H. Greif, D. R. G. Schleicher, J. L. Johnson, A.-K. Jappsen, R. S. Klessen, P. C. Clark, S. C. O. Glover, A. Stacy and V. Bromm; 5. Low-metallicity star formation: the characteristic mass and upper mass limit Kazuyuki Omukai; 6. Dark stars: dark matter in the first stars leads to a new phase of stellar evolution Katherine Freese, Douglas Spolyar, Anthony Aguirre, Peter Bodenheimer, Paolo Gondolo, J. A. Sellwood and Naoki Yoshida; 7. Effects of dark matter annihilation on the first stars F. Iocco, A. Bressan, E. Ripamonti, R. Schneider, A. Ferrara and P. Marigo; 8. Searching for Pop III stars and galaxies at high redshift Daniel Schaerer; 9. The search for population III stars Sperello di Serego Alighieri, Jaron Kurk, Benedetta Ciardi, Andrea Cimatti, Emanuele Daddi and Andrea Ferrara; 10. Observational search for population III stars in high-redshift galaxies Tohru Nagao; Session II. Metal Enrichment, Chemical Evolution, and Feedback: 11. Cosmic metal enrichment Andrea Ferrara; 12. Insights into the origin of the galaxy mass-metallicity relation Henry Lee, Eric F. Bell and Rachel S. Somerville; 13. LSD and AMAZE: the mass-metallicity relation at z > 3 F. Mannucci and R. Maiolino; 14. Three modes of metal-enriched star formation at high redshift Britton D. Smith, Matthew J. Turk, Steinn Sigurdsson, Brian W. O'Shea and Michael L. Norman; 15. Primordial supernovae and the assembly of the first galaxies Daniel Whalen, Bob Van Veelen, Brian W. O

Reaction landscape of a pentadentate N5-ligated Mn(II) complex with O2˙- and H2O2 includes conversion of a peroxomanganese(III) adduct to a bis(μ-oxo)dimanganese(III,IV) species.

PubMed

Leto, Domenick F; Chattopadhyay, Swarup; Day, Victor W; Jackson, Timothy A

2013-09-28

Herein we describe the chemical reactivity of the mononuclear [Mn(II)(N4py)(OTf)](OTf) (1) complex with hydrogen peroxide and superoxide. Treatment of 1 with one equivalent superoxide at -40 °C in MeCN formed the peroxomanganese(III) adduct, [Mn(III)(O2)(N4py)](+) (2) in ~30% yield. Complex 2 decayed over time and the formation of the bis(μ-oxo)dimanganese(III,IV) complex, [Mn(III)Mn(IV)(μ-O)2(N4py)2](3+) (3) was observed. When 2 was formed in higher yields (~60%) using excess superoxide, the [Mn(III)(O2)(N4py)](+) species thermally decayed to Mn(II) species and 3 was formed in no greater than 10% yield. Treatment of [Mn(III)(O2)(N4py)](+) with 1 resulted in the formation of 3 in ~90% yield, relative to the concentration of [Mn(III)(O2)(N4py)](+). This reaction mimics the observed chemistry of Mn-ribonucleotide reductase, as it features the conversion of two Mn(II) species to an oxo-bridged Mn(III)Mn(IV) compound using O2(-) as oxidant. Complex 3 was independently prepared through treatment of 1 with H2O2 and base at -40 °C. The geometric and electronic structures of 3 were probed using electronic absorption, electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and X-ray absorption (XAS) spectroscopies. Complex 3 was structurally characterized by X-ray diffraction (XRD), which revealed the N4py ligand bound in an unusual tetradentate fashion.

Cardiac Epithelial-Mesenchymal Transition Is Blocked by Monomethylarsonous Acid (III)

PubMed Central

Huang, Tianfang; Barnett, Joey V.; Camenisch, Todd D.

2014-01-01

Arsenic exposure during embryonic development can cause ischemic heart pathologies later in adulthood which may originate from impairment in proper blood vessel formation. The arsenic-associated detrimental effects are mediated by arsenite (iAsIII) and its most toxic metabolite, monomethylarsonous acid [MMA (III)]. The impact of MMA (III) on coronary artery development has not yet been studied. The key cellular process that regulates coronary vessel development is the epithelial-mesenchymal transition (EMT). During cardiac EMT, activated epicardial progenitor cells transform to mesenchymal cells to form the cellular components of coronary vessels. Smad2/3 mediated TGFβ2 signaling, the key regulator of cardiac EMT, is disrupted by arsenite exposure. In this study, we compared the cardiac toxicity of MMA (III) with arsenite. Epicardial progenitor cells are 15 times more sensitive to MMA (III) cytotoxicity when compared with arsenite. MMA (III) caused a significant blockage in epicardial cellular transformation and invasion at doses 10 times lower than arsenite. Key EMT genes including TGFβ ligands, TβRIII, Has2, CD44, Snail1, TBX18, and MMP2 were down regulated by MMA (III) exposure. MMA (III) disrupted Smad2/3 activation at a dose 20 times lower than arsenite. Both arsenite and MMA (III) significantly inhibited Erk1/2 and Erk5 phosphorylation. Nuclear translocation of Smad2/3 and Erk5 was also blocked by arsenical exposure. However, p38 activation, as well as smooth muscle differentiation, was refractory to the inhibition by the arsenicals. Collectively, these findings revealed that MMA (III) is a selective disruptor of cardiac EMT and as such may predispose to arsenic-associated cardiovascular disorders. PMID:25145660

Ferrate(VI)-prompted removal of metals in aqueous media: mechanistic delineation of enhanced efficiency via metal entrenchment in magnetic oxides.

PubMed

Prucek, Robert; Tuček, Jiří; Kolařík, Jan; Hušková, Ivana; Filip, Jan; Varma, Rajender S; Sharma, Virender K; Zbořil, Radek

2015-02-17

The removal efficiency of heavy metal ions (cadmium(II), Cd(II); cobalt(II), Co(II); nickel(II), Ni(II); copper(II), Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)) was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective removal of Co(II), Ni(II), and Cu(II) from water was observed at a low Fe-to-heavy metal ion ratio (Fe/M(II) = 2:1) while a removal efficiency of 70% was seen for Cd(II) ions at a high Fe/Cd(II) weight ratio of 15:1. The role of ionic radius and metal valence state was explored by conducting similar removal experiments using Al(III) ions. The unique combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in-field Mössbauer spectroscopy, and magnetization measurements enabled the delineation of several distinct mechanisms for the Fe(VI)-prompted removal of metal ions. Under a Fe/M weight ratio of 5:1, Co(II), Ni(II), and Cu(II) were removed by the formation of MFe2O4 spinel phase and partially through their structural incorporation into octahedral positions of γ-Fe2O3 (maghemite) nanoparticles. In comparison, smaller sized Al(III) ions got incorporated easily into the tetrahedral positions of γ-Fe2O3 nanoparticles. In contrast, Cd(II) ions either did not form the spinel ferrite structure or were not incorporated into the lattic of iron(III) oxide phase due to the distinct electronic structure and ionic radius. Environmentally friendly removal of heavy metal ions at a much smaller dosage of Fe than those of commonly applied iron-containing coagulants and the formation of ferrimagnetic species preventing metal ions leaching back into the environment and allowing their magnetic separation are highlighted.

Fundamental Studies and Development of III-N Visible LEDs for High-Power Solid-State Lighting Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dupuis, Russell

The goal of this program is to understand in a fundamental way the impact of strain, defects, polarization, and Stokes loss in relation to unique device structures upon the internal quantum efficiency (IQE) and efficiency droop (ED) of III-nitride (III-N) light-emitting diodes (LEDs) and to employ this understanding in the design and growth of high-efficiency LEDs capable of highly-reliable, high-current, high-power operation. This knowledge will be the basis for our advanced device epitaxial designs that lead to improved device performance. The primary approach we will employ is to exploit new scientific and engineering knowledge generated through the application of amore » set of unique advanced growth and characterization tools to develop new concepts in strain-, polarization-, and carrier dynamics-engineered and low-defect materials and device designs having reduced dislocations and improved carrier collection followed by efficient photon generation. We studied the effects of crystalline defect, polarizations, hole transport, electron-spillover, electron blocking layer, underlying layer below the multiplequantum- well active region, and developed high-efficiency and efficiency-droop-mitigated blue LEDs with a new LED epitaxial structures. We believe new LEDs developed in this program will make a breakthrough in the development of high-efficiency high-power visible III-N LEDs from violet to green spectral region.« less

Thermodynamics of complexation in an aqueous solution of Tb(III) nitrate at 298 K

NASA Astrophysics Data System (ADS)

Lobacheva, O. L.; Berlinskii, I. V.; Dzhevaga, N. V.

2017-01-01

The pH of the formation of hydroxo complexes and hydrates in an aqueous solution of terbium Tb(III) is determined using combined means of potentiometric and conductometric titration. The stability constants of the hydroxo complexes, the products of hydroxide solubility, and the Gibbs energy of terbium hydroxo complex formation are calculated.

Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes.

PubMed

Taha, Mohamed; Khan, Imran; Coutinho, João A P

2016-04-01

With many metal-based drugs extensively used today in the treatment of cancer, attention has focused on the development of new coordination compounds with antitumor activity with europium(III) complexes recently introduced as novel anticancer drugs. The aim of this work is to design new Eu(III) complexes with gallic acid, an antioxida'nt phenolic compound. Gallic acid was chosen because it shows anticancer activity without harming health cells. As antioxidant, it helps to protect human cells against oxidative damage that implicated in DNA damage, cancer, and accelerated cell aging. In this work, the formation of binary and ternary complexes of Eu(III) with gallic acid, primary ligand, and amino acids alanine, leucine, isoleucine, and tryptophan was studied by glass electrode potentiometry in aqueous solution containing 0.1M NaNO3 at (298.2 ± 0.1) K. Their overall stability constants were evaluated and the concentration distributions of the complex species in solution were calculated. The protonation constants of gallic acid and amino acids were also determined at our experimental conditions and compared with those predicted by using conductor-like screening model for realistic solvation (COSMO-RS) model. The geometries of Eu(III)-gallic acid complexes were characterized by the density functional theory (DFT). The spectroscopic UV-visible and photoluminescence measurements are carried out to confirm the formation of Eu(III)-gallic acid complexes in aqueous solutions. Copyright © 2016 Elsevier Inc. All rights reserved.

Photoinduced Cobalt(III)-Trifluoromethyl Bond Activation Enables Arene C-H Trifluoromethylation.

PubMed

Harris, Caleb F; Kuehner, Christopher S; Bacsa, John; Soper, Jake D

2018-01-26

Visible-light capture activates a thermodynamically inert Co III -CF 3 bond for direct C-H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [( S OCO)Co III (CF 3 )(MeCN) 2 ] (2), but in non-coordinating solvents the complex is red, square pyramidal [( S OCO)Co III (CF 3 )(MeCN)] (3). Both are thermally stable, and 2 is stable in light. But exposure of 3 to low-energy light results in facile homolysis of the Co III -CF 3 bond, releasing . CF 3 radical, which is efficiently trapped by TEMPO . or (hetero)arenes. The homolytic aromatic substitution reactions do not require a sacrificial or substrate-derived oxidant because the Co II by-product of Co III -CF 3 homolysis produces H 2 . The photophysical properties of 2 and 3 provide a rationale for the disparate light stability. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Approach for Enhanced Scandium and Titanium Leaching Efficiency from Bauxite Residue with Suppressed Silica Gel Formation.

PubMed

Alkan, Gözde; Yagmurlu, Bengi; Cakmakoglu, Seckin; Hertel, Tobias; Kaya, Şerif; Gronen, Lars; Stopic, Srecko; Friedrich, Bernd

2018-04-04

The need of light weight alloys for future transportation industry puts Sc and Ti under a sudden demand. While these metals can bring unique and desired properties to alloys, lack of reliable sources brought forth a supply problem which can be solved by valorization of the secondary resources. Bauxite residue (red mud), with considerable Ti and Sc content, is a promising resource for secure supply of these metals. Due to drawbacks of the direct leaching route from bauxite residue, such as silica gel formation and low selectivity towards these valuable metals, a novel leaching process based on oxidative leaching conditions, aiming more efficient and selective leaching but also considering environmental aspects via lower acid consumption, was investigated in this study. Combination of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ) was utilized as the leaching solution, where various acid concentrations, solid-to-liquid ratios, leaching temperatures and times were examined in a comparative manner. Leaching with 2.5 M H 2 O 2 : 2.5 M H 2 SO 4 mixture at 90 °C for 30 min was observed to be the best leaching conditions with suppressed silica gel formation and the highest reported leaching efficiency with high S/L ratio for Sc and Ti; 68% and 91%; respectively.

15.3%-Efficient GaAsP Solar Cells on GaP/Si Templates

DOE PAGES

Vaisman, Michelle; Fan, Shizhao; Nay Yaung, Kevin; ...

2017-07-26

As single-junction Si solar cells approach their practical efficiency limits, a new pathway is necessary to increase efficiency in order to realize more cost-effective photovoltaics. Integrating III-V cells onto Si in a multijunction architecture is a promising approach that can achieve high efficiency while leveraging the infrastructure already in place for Si and III-V technology. In this Letter, we demonstrate a record 15.3%-efficient 1.7 eV GaAsP top cell on GaP/Si, enabled by recent advances in material quality in conjunction with an improved device design and a high-performance antireflection coating. Furthermore, we present a separate Si bottom cell with a 1.7more » eV GaAsP optical filter to absorb most of the visible light with an efficiency of 6.3%, showing the feasibility of monolithic III-V/Si tandems with >20% efficiency. Through spectral efficiency analysis, we also compare our results to previously published GaAsP and Si devices, projecting tandem GaAsP/Si efficiencies of up to 25.6% based on current state-of-the-art individual subcells. With the aid of modeling, we further illustrate a realistic path toward 30% GaAsP/Si tandems for high-efficiency, monolithically integrated photovoltaics.« less

Europium(III)-doped A2Hf2O7 (A = Y, Gd, Lu) nanoparticles: Influence of annealing temperature, europium(III) concentration and host cation on the luminescent properties

NASA Astrophysics Data System (ADS)

Papan, Jelena; Jovanović, Dragana J.; Vuković, Katarina; Smits, Krisjanis; Đorđević, Vesna; Dramićanin, Miroslav

2016-11-01

The detailed analyses of structure and luminescence of europium(III)-doped A2Hf2O7 (A = Y, Gd, Lu) nanoparticles is presented. Samples were prepared by time and cost effective combustion method that utilize polyethylene glycol both as a chelating agent and as a fuel, with different europium(III) concentrations (from 1 to 12 at.%), annealed at temperatures ranging from 800 to 1400 °C, and with alternating A3+ cation in the A2Hf2O7 host. Then, structural variations between materials were analysed by X-ray diffraction and structural refinement, while the changes in the luminescence were assessed from the Judd-Ofelt analyses of emission spectra. Nanoparticles prepared at the lowest temperature (800 °C) had the smallest particle size of ∼6 nm and showed the highest quantum efficiency when doped with 1 and 2 at.% of europium(III). Radiative transition rate and quantum efficiency of emission showed Lu2Hf2O7 > Gd2Hf2O7 > Y2Hf2O7 trend.

Amber light-emitting diode comprising a group III-nitride nanowire active region

DOEpatents

Wang, George T.; Li, Qiming; Wierer, Jr., Jonathan J.; Koleske, Daniel

2014-07-22

A temperature stable (color and efficiency) III-nitride based amber (585 nm) light-emitting diode is based on a novel hybrid nanowire-planar structure. The arrays of GaN nanowires enable radial InGaN/GaN quantum well LED structures with high indium content and high material quality. The high efficiency and temperature stable direct yellow and red phosphor-free emitters enable high efficiency white LEDs based on the RGYB color-mixing approach.

Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

NASA Astrophysics Data System (ADS)

Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.

2016-05-01

Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4-fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.

Strongly Circularly Polarized Emission from Water-Soluble Eu(III)- and Tb(III)-Based Complexes: A Structural and Spectroscopic Study.

PubMed

Leonzio, Marco; Melchior, Andrea; Faura, Georgina; Tolazzi, Marilena; Zinna, Francesco; Di Bari, Lorenzo; Piccinelli, Fabio

2017-04-17

Water-soluble Eu(III) and Tb(III) complexes with N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetic acid (H 2 bpcd) have been synthesized and characterized in their racemic and enantiopure forms. The ligand has been designed to bind Ln(III) ions, providing a dissymmetric environment able to solicit strong chiroptical features while at the same time leaving a few coordination sites available for engaging further ancillary ligands. Potentiometric studies show that Ln(III) complexes have a relatively good stability and that at pH 7 the [Ln(bpcd)] + species is largely dominant. DFT calculations carried out on the (S,S)-[Y(bpcd)(H 2 O) 5 ] + complexes (the closed-shell equivalents of [Eu(bpcd)(H 2 O) 5 ] + and [Tb(bpcd)(H 2 O) 5 ] + ) indicate that the two trans-O,O and trans-N py ,N py configurations are equally stable in solution and present two coordinated water molecules. This is in agreement with the hydration number ∼2.6 determined by luminescence lifetime measurements on Tb(III) and Eu(III) complexes. A detailed optical and chiroptical spectroscopic characterization has been carried out and reveals that the complexes display an efficient luminescence in the visible spectral range accompanied by a strong CPL activity. A value for g lum (around 0.1 on the top of the 546 nm band) for the Tb-based complex has been found. This is one of the highest g lum values measured up to now for chiral Tb complexes. These results suggest that in principle Tb(bpcd)Cl is suitable to be employed as a CPL bioprobe for relevant analytes in aqueous media.

Effects of Pop III to PopII transition on the lowest metallicity stars in dwarf galaxies

NASA Astrophysics Data System (ADS)

Zhang, Yimiao; Keres, Dusan; FIRE Team

2018-01-01

We examine the effects of the enrichments from Population III (Pop III) stars on the formation and properties of the first generation of the Population II (Pop II) stars. Pop III stars begin to transition towards Pop II stars when the metals dispersed in Pop III supernovae pollute the nearby gas. However, details of this transition are still largely unknown. We use dwarf galaxy simulations from the Feedback In Realistic Environments (FIRE) project to identify the star-forming gas that is likely to be pre-enriched by Pop III supernovae and follow the stars that form in such gas. This pre-enrichment will leave the signature in the lowest metallicity stars that can be used to better constrain the details of the Pop III-to-Pop II transition.

Structure and membrane remodeling activity of ESCRT-III helical polymers

DOE PAGES

McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; ...

2015-12-18

The endosomal sorting complexes required for transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure, and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 angstrom resolution cryogenic electron microscopy reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, charged multivesicular body protein 1B (CHMP1B) and increased sodium tolerance 1 (IST1). The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecturemore » and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively curved membranes in vitro and in vivo. In conclusion, our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature.« less

Efficient stereoscopic contents file format on the basis of ISO base media file format

NASA Astrophysics Data System (ADS)

Kim, Kyuheon; Lee, Jangwon; Suh, Doug Young; Park, Gwang Hoon

2009-02-01

A lot of 3D contents haven been widely used for multimedia services, however, real 3D video contents have been adopted for a limited applications such as a specially designed 3D cinema. This is because of the difficulty of capturing real 3D video contents and the limitation of display devices available in a market. However, diverse types of display devices for stereoscopic video contents for real 3D video contents have been recently released in a market. Especially, a mobile phone with a stereoscopic camera has been released in a market, which provides a user as a consumer to have more realistic experiences without glasses, and also, as a content creator to take stereoscopic images or record the stereoscopic video contents. However, a user can only store and display these acquired stereoscopic contents with his/her own devices due to the non-existence of a common file format for these contents. This limitation causes a user not share his/her contents with any other users, which makes it difficult the relevant market to stereoscopic contents is getting expanded. Therefore, this paper proposes the common file format on the basis of ISO base media file format for stereoscopic contents, which enables users to store and exchange pure stereoscopic contents. This technology is also currently under development for an international standard of MPEG as being called as a stereoscopic video application format.

Limitation of thiamine pyrophosphate supply to growing Escherichia coli switches metabolism to efficient D-lactate formation.

PubMed

Tian, Kangming; Niu, Dandan; Liu, Xiaoguang; Prior, Bernard A; Zhou, Li; Lu, Fuping; Singh, Suren; Wang, Zhengxiang

2016-01-01

Efficient production of D-lactate by engineered Escherichia coli entails balancing cell growth and product synthesis. To develop a metabolic switch to implement a desirable transition from cell growth to product fermentation, a thiamine auxotroph B0013-080A was constructed in a highly efficient D-lactate producer E. coli strain B0013-070. This was achieved by inactivation of thiE, a gene encoding a thiamine phosphate synthase for biosynthesis of thiamine monophosphate. The resultant mutant B0013-080A failed to grow on the medium in the absence of thiamine yet growth was restored when exogenous thiamine was provided. A linear relationship between cell mass formation and amount of thiamine supplemented was mathematically determined in a shake flask experiment and confirmed in a 7-L bioreactor system. This calculation revealed that ∼ 95-96 thiamine molecules per cell were required to satisfy cell growth. This relationship was employed to develop a novel fermentation process for D-lactate production by using thiamine as a limiting condition. A D-lactate productivity of 4.11 g · L(-1) · h(-1) from glycerol under microaerobic condition and 3.66 g · L(-1) · h(-1) from glucose under anaerobic condition was achieved which is 19.1% and 10.2% higher respectively than the parental strain. These results revealed a convenient and reliable method to control cell growth and improve D-lactate fermentation. This control strategy could be applied to other biotechnological processes that require optimal allocation of carbon between cell growth and product formation. © 2015 Wiley Periodicals, Inc.

A Review of Four Text-Formatting Programs.

ERIC Educational Resources Information Center

Press, Larry

1980-01-01

The author compares four formatting programs which run under CP/M: Script-80, Text Processing System (TPS), TEX, and Textwriter III. He summarizes his experience with these programs and his detailed report on 154 program characteristics. (Author/SJL)

Co(III) as mediator in phenol destruction using electrochemical oxidation

NASA Astrophysics Data System (ADS)

Herlina, Herlina; Derlini, Derlini; Muhammad, Razali

2017-03-01

Mediated electrochemical oxidation is one of the method for oxidation of organic compound by using a mediator. This method has been developed because have several advantages which low cost and efficient, the exhaust gas does not contain toxic materials and hazardous waste and the process take place at a relatively low temperature. Electrochemical oxidation of organic compounds using metal ion mediator is one alternative method that is appropriate for the treatment of organic waste. Co(III) is a strong oxidizing agent used as a mediator has been prepared in Pt electrodes. The concentration of Co(III) formed during oxidation determined by potentiometric titration where Co(III) aliquot was added into Fe(II) excess solution and the remaining Fe(II) which did not react has been titrated with Ce(IV). In optimum condition, Co(III) was then used to oxidize the organic compound into carbon dioxide. The parameters has been studied are the standard oxidation potential of mediator, acid concentration and temperature. The results obtained at potential of 6 Volt, with nitric acid 4 M and temperature of 25°C give result 23.86% where Co (II) is converted to Co(III) within 2 hours. The addition of silver nitrate can increase the concentration of Co(III). At the optimum conditions, the mediator ion Co(III) can destructed to 66.44% of phenol compound oxidized into carbon dioxide.

Efficient surface formation route of interstellar hydroxylamine through NO hydrogenation. II. The multilayer regime in interstellar relevant ices

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Ioppolo, S.; Lamberts, T.; Zhen, J. F.; Cuppen, H. M.; Linnartz, H.

2012-08-01

Hydroxylamine (NH2OH) is one of the potential precursors of complex pre-biotic species in space. Here, we present a detailed experimental study of hydroxylamine formation through nitric oxide (NO) surface hydrogenation for astronomically relevant conditions. The aim of this work is to investigate hydroxylamine formation efficiencies in polar (water-rich) and non-polar (carbon monoxide-rich) interstellar ice analogues. A complex reaction network involving both final (N2O, NH2OH) and intermediate (HNO, NH2O., etc.) products is discussed. The main conclusion is that hydroxyl-amine formation takes place via a fast and barrierless mechanism and it is found to be even more abundantly formed in a water-rich environment at lower temperatures. In parallel, we experimentally verify the non-formation of hydroxylamine upon UV photolysis of NO ice at cryogenic temperatures as well as the non-detection of NC- and NCO-bond bearing species after UV processing of NO in carbon monoxide-rich ices. Our results are implemented into an astrochemical reaction model, which shows that NH2OH is abundant in the solid phase under dark molecular cloud conditions. Once NH2OH desorbs from the ice grains, it becomes available to form more complex species (e.g., glycine and β-alanine) in gas phase reaction schemes.

Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1989-01-01

The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

A Ferredoxin Disulfide Reductase Delivers Electrons to the Methanosarcina barkeri Class III Ribonucleotide Reductase

DOE PAGES

Wei, Yifeng; Li, Bin; Prakash, Divya; ...

2015-11-04

Two subtypes of class III anaerobic ribonucleotide reductases (RNRs) studied so far couple the reduction of ribonucleotides to the oxidation of formate, or the oxidation of NADPH via thioredoxin and thioredoxin reductase. Certain methanogenic archaea contain a phylogenetically distinct third subtype of class III RNR, with distinct active-site residues. Here we report the cloning and recombinant expression of the Methanosarcina barkeri class III RNR and show that the electrons required for ribonucleotide reduction can be delivered by a [4Fe-4S] protein ferredoxin disulfide reductase, and a conserved thioredoxin-like protein NrdH present in the RNR operon. The diversity of class III RNRsmore » reflects the diversity of electron carriers used in anaerobic metabolism« less

Spectroscopic, structural characterizations and antioxidant capacity of the chromium (III) niacinamide compound as a diabetes mellitus drug model

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; El-Megharbel, Samy M.; Hussien, M. A.; Hamza, Reham Z.; Al-Omar, Mohamed A.; Naglah, Ahmed M.; Afifi, Walid M.; Kobeasy, Mohamed I.

2017-02-01

New binuclear chromium (III) niacinamide compound with chemical formula [Cr2(Nic)(Cl)6(H2O)4]·H2O was obtained upon the reaction of chromium (III) chloride with niacinamide (Nic) in methanol solvent at 60 °C. The proposed structure was discussed with the help of microanalytical analyses, conductivity, spectroscopic (FT-IR and UV-vis.), magnetic calculations, thermogravimetric analyses (TG/TGA), and morphological studies (X-ray of solid powder and scan electron microscopy. The infrared spectrum of free niacinamide in comparison with its chromium (III) compound indicated that the chelation mode occurs via both nitrogen atoms of pyridine ring and primary -NH2 group. The efficiency of chromium (III) niacinamide compound in decreasing of glucose level of blood and HbA1c in case of diabetic rats was checked. The ameliorating gluconeogenic enzymes, lipid profile and antioxidant defense capacities are considered as an indicator of the efficiency of new chromium (III) compound as antidiabetic drug model.

Role of the ancillary ligand N,N-dimethylaminoethanol in the sensitization of Eu(III) and Tb(III) luminescence in dimeric beta-diketonates.

PubMed

Eliseeva, Svetlana V; Kotova, Oxana V; Gumy, Frédéric; Semenov, Sergey N; Kessler, Vadim G; Lepnev, Leonid S; Bünzli, Jean-Claude G; Kuzmina, Natalia P

2008-04-24

Two types of dimeric complexes [Ln2(hfa)6(mu2-O(CH2)2NHMe2)2] and [Ln(thd)2(mu2,eta2-O(CH2)2NMe2)]2 (Ln = YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- = hexafluoroacetylacetonato, thd- = dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the beta-diketonate. In [Tb2(hfa)6(mu2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1...Tb2 separation of 3.684(1) A. In [Tb(thd)2(mu2,eta2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1...Tb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 degrees C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield Q(L)Ln = 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the beta-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both beta-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2

Hydrodynamical simulations and semi-analytic models of galaxy formation: two sides of the same coin

NASA Astrophysics Data System (ADS)

Neistein, Eyal; Khochfar, Sadegh; Dalla Vecchia, Claudio; Schaye, Joop

2012-04-01

In this work we develop a new method to turn a state-of-the-art hydrodynamical cosmological simulation of galaxy formation (HYD) into a simple semi-analytic model (SAM). This is achieved by summarizing the efficiencies of accretion, cooling, star formation and feedback given by the HYD, as functions of the halo mass and redshift. The SAM then uses these functions to evolve galaxies within merger trees that are extracted from the same HYD. Surprisingly, by turning the HYD into a SAM, we conserve the mass of individual galaxies, with deviations at the level of 0.1 dex, on an object-by-object basis, with no significant systematics. This is true for all redshifts, and for the mass of stars and gas components, although the agreement reaches 0.2 dex for satellite galaxies at low redshift. We show that the same level of accuracy is obtained even in case the SAM uses only one phase of gas within each galaxy. Moreover, we demonstrate that the formation history of one massive galaxy provides sufficient information for the SAM to reproduce the population of galaxies within the entire cosmological box. The reasons for the small scatter between the HYD and SAM galaxies are as follows. (i) The efficiencies are matched as functions of the halo mass and redshift, meaning that the evolution within merger trees agrees on average. (ii) For a given galaxy, efficiencies fluctuate around the mean value on time-scales of 0.2-2 Gyr. (iii) The various mass components of galaxies are obtained by integrating the efficiencies over time, averaging out these fluctuations. We compare the efficiencies found here to standard SAM recipes and find that they often deviate significantly. For example, here the HYD shows smooth accretion that is less effective for low-mass haloes, and is always composed of hot or dilute gas; cooling is less effective at high redshift, and star formation changes only mildly with cosmic time. The method developed here can be applied in general to any HYD, and can thus

Mössbauer study of the thermal decomposition of alkali tris(oxalato)ferrates(III)

NASA Astrophysics Data System (ADS)

Brar, A. S.; Randhawa, B. S.

1985-07-01

The thermal decomposition of alkali (Li,Na,K,Cs,NH 4) tris(oxalato)ferrates(III) has been studied at different temperatures up to 700°C using Mössbauer, infrared spectroscopy, and thermogravimetric techniques. The formation of different intermediates has been observed during thermal decomposition. The decomposition in these complexes starts at different temperatures, i.e., at 200°C in the case of lithium, cesium, and ammonium ferrate(III), 250°C in the case of sodium, and 270°C in the case of potassium tris(oxalato)ferrate(III). The intermediates, i.e., Fe 11C 2O 4, K 6Fe 112(ox) 5. and Cs 2Fe 11 (ox) 2(H 2O) 2, are formed during thermal decomposition of lithium, potassium, and cesium tris(oxalato)ferrates(III), respectively. In the case of sodium and ammonium tris(oxalato)ferrates(III), the decomposition occurs without reduction to the iron(II) state and leads directly to α-Fe 2O 3.

Transferable tight binding model for strained group IV and III-V heterostructures

NASA Astrophysics Data System (ADS)

Tan, Yaohua; Povolotskyi, Micheal; Kubis, Tillmann; Boykin, Timothy; Klimeck, Gerhard

Modern semiconductor devices have reached critical device dimensions in the range of several nanometers. For reliable prediction of device performance, it is critical to have a numerical efficient model that are transferable to material interfaces. In this work, we present an empirical tight binding (ETB) model with transferable parameters for strained IV and III-V group semiconductors. The ETB model is numerically highly efficient as it make use of an orthogonal sp3d5s* basis set with nearest neighbor inter-atomic interactions. The ETB parameters are generated from HSE06 hybrid functional calculations. Band structures of strained group IV and III-V materials by ETB model are in good agreement with corresponding HSE06 calculations. Furthermore, the ETB model is applied to strained superlattices which consist of group IV and III-V elements. The ETB model turns out to be transferable to nano-scale hetero-structure. The ETB band structures agree with the corresponding HSE06 results in the whole Brillouin zone. The ETB band gaps of superlattices with common cations or common anions have discrepancies within 0.05eV.

Efficient formation of heterokaryotic sclerotia in the filamentous fungus Aspergillus oryzae.

PubMed

Wada, Ryuta; Jin, Feng Jie; Koyama, Yasuji; Maruyama, Jun-ichi; Kitamoto, Katsuhiko

2014-01-01

Heterokaryon formation by hyphal fusion occurs during a sexual/parasexual cycle in filamentous fungi, and therefore, it is biotechnologically important for crossbreeding. In the industrial filamentous fungus Aspergillus oryzae, a parasexual cycle has been reported, and it was recently suggested that sexual reproduction should be possible. However, as A. oryzae enters into hyphal fusion with a much lower frequency than Neurospora crassa, the process of heterokaryon formation has not been extensively characterized in A. oryzae. Here, we developed a detection system for heterokaryon formation by expressing red or green fluorescent proteins in nuclei and conferring uridine/uracil or adenine auxotrophy to MAT1-1 and MAT1-2 strains of A. oryzae. The heterokaryon formation of A. oryzae was investigated in paired culture using the genetically modified strains. No sclerotial formation was observed in the hyphal contact regions of the two strains with the same auxotrophy, whereas numerous sclerotia were formed between the strains with different auxotrophies. In most of the formed sclerotia, the uridine/uracil and adenine auxotrophies were complemented, and both red and green fluorescence were detected, indicating that heterokaryotic fusants were formed by hyphal fusion before or during sclerotial formation. Moreover, overexpressing the sclR gene, which encodes a transcription factor promoting sclerotial formation, increased the number of heterokaryotic sclerotia formed between the two auxotrophic strains. Notably, these effects in sclerotial formation of heterokaryotic fusants were observed independently of the mating type pairing combinations. Taken together, these findings demonstrated that paring of different auxotrophs and sclR overexpression promote the formation of heterokaryotic sclerotia in A. oryzae.

Thiocyanato Chromium (III) Complexes: Separation by Paper Electrophoresis and Estimate of Stability Constants

ERIC Educational Resources Information Center

Larsen, Erik; Eriksen, J.

1975-01-01

Describes an experiment wherein the student can demonstrate the existence of all the thiocyanato chromium complexes, estimate the stepwise formation constants, demonstrate the robustness of chromium III complexes, and show the principles of paper electrophoresis. (GS)

STAR FORMATION IN DISK GALAXIES. III. DOES STELLAR FEEDBACK RESULT IN CLOUD DEATH?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tasker, Elizabeth J.; Wadsley, James; Pudritz, Ralph

2015-03-01

Stellar feedback, star formation, and gravitational interactions are major controlling forces in the evolution of giant molecular clouds (GMCs). To explore their relative roles, we examine the properties and evolution of GMCs forming in an isolated galactic disk simulation that includes both localized thermal feedback and photoelectric heating. The results are compared with the three previous simulations in this series, which consists of a model with no star formation, star formation but no form of feedback, and star formation with photoelectric heating in a set with steadily increasing physical effects. We find that the addition of localized thermal feedback greatlymore » suppresses star formation but does not destroy the surrounding GMC, giving cloud properties closely resembling the run in which no stellar physics is included. The outflows from the feedback reduce the mass of the cloud but do not destroy it, allowing the cloud to survive its stellar children. This suggests that weak thermal feedback such as the lower bound expected for a supernova may play a relatively minor role in the galactic structure of quiescent Milky-Way-type galaxies, compared to gravitational interactions and disk shear.« less

Have We Finally Found Pop III Stars?

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2015-08-01

Elusive Population: Population III stars — the theoretical generation of extremely metal-poor stars that should have been formed in the early universe before metals existed — have been conspicuously absent in observations. But a team led by David Sobral (Institute of Astrophysics and Space Sciences, University of Lisbon, and Leiden Observatory) may have changed this paradigm with their recent detection of an extremely bright galaxy in the early universe. The team's broad survey of distant galaxies using ESO's Very Large Telescope provides a glimpse of the universe as it was only 800 million years after the Big Bang. The survey uncovered several unusually bright galaxies — including the brightest galaxy ever seen at this distance, an important discovery by itself. But further scrutiny of this galaxy, named CR7, produced an even more exciting find: a bright pocket of the galaxy contained no sign of any metals. Follow-up with other telescopes confirmed this initial detection. Formation Waves: Sobral and his team postulate that we are observing this galaxy at just the right time to have caught a cluster of Population III stars — the bright, metal-free region of the galaxy — at the end of a wave of early star formation. The observations of CR7 also suggest the presence of regular stars in clumps around the metal-free pocket. These older, surrounding clusters may have formed stars first, helping to ionize a local bubble in the galaxy and allowing us to now observe the light from CR7. It was previously thought that Population III stars might only be found in small, dim galaxies, making them impossible for us to detect. But CR7 provides an interesting alternative: this galaxy is bright, and the candidate Population III stars are surrounded by clusters of normal stars. This suggests that these first-generation stars might in fact be easier to detect than was originally thought. Additional follow-up observations with other telescopes will help to confirm the

Mechanisms of gold bioaccumulation by filamentous cyanobacteria from gold(III)-chloride complex.

PubMed

Lengke, Maggy F; Ravel, Bruce; Fleet, Michael E; Wanger, Gregory; Gordon, Robert A; Southam, Gordon

2006-10-15

The mechanisms of gold bioaccumulation by cyanobacteria (Plectonema boryanum UTEX 485) from gold(III)-chloride solutions have been studied at three gold concentrations (0.8,1.7, and 7.6 mM) at 25 degrees C, using both fixed-time laboratory and real-time synchrotron radiation absorption spectroscopy (XAS) experiments. Interaction of cyanobacteria with aqueous gold(III)-chloride initially promoted the precipitation of nanoparticles of amorphous gold(I)-sulfide at the cell walls, and finally deposited metallic gold in the form of octahedral (111) platelets (approximately 10 nm to 6 microm) near cell surfaces and in solutions. The XAS results confirm that the reduction mechanism of gold(III)-chloride to metallic gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I)-sulfide.

Testing the universality of the star-formation efficiency in dense molecular gas

NASA Astrophysics Data System (ADS)

Shimajiri, Y.; André, Ph.; Braine, J.; Könyves, V.; Schneider, N.; Bontemps, S.; Ladjelate, B.; Roy, A.; Gao, Y.; Chen, H.

2017-08-01

Context. Recent studies with, for example, Spitzer and Herschel have suggested that star formation in dense molecular gas may be governed by essentially the same "law" in Galactic clouds and external galaxies. This conclusion remains controversial, however, in large part because different tracers have been used to probe the mass of dense molecular gas in Galactic and extragalactic studies. Aims: We aimed to calibrate the HCN and HCO+ lines commonly used as dense gas tracers in extragalactic studies and to test the possible universality of the star-formation efficiency in dense gas (≳104 cm-3), SFEdense. Methods: We conducted wide-field mapping of the Aquila, Ophiuchus, and Orion B clouds at 0.04 pc resolution in the J = 1 - 0 transition of HCN, HCO+, and their isotopomers. For each cloud, we derived a reference estimate of the dense gas mass MHerschelAV > 8, as well as the strength of the local far-ultraviolet (FUV) radiation field, using Herschel Gould Belt survey data products, and estimated the star-formation rate from direct counting of the number of Spitzer young stellar objects. Results: The H13CO+(1-0) and H13CN(1-0) lines were observed to be good tracers of the dense star-forming filaments detected with Herschel. Comparing the luminosities LHCN and LHCO+ measured in the HCN and HCO+ lines with the reference masses MHerschelAV > 8, the empirical conversion factors αHerschel - HCN (=MHerschelAV > 8/LHCN) and αHerschel - HCO+ (=MHerschelAV > 8/LHCO+) were found to be significantly anti-correlated with the local FUV strength. In agreement with a recent independent study of Orion B by Pety et al., the HCN and HCO+ lines were found to trace gas down to AV ≳ 2. As a result, published extragalactic HCN studies must be tracing all of the moderate density gas down to nH2 ≲ 103 cm-3. Estimating the contribution of this moderate density gas from the typical column density probability distribution functions in nearby clouds, we obtained the following G0

What Determines Star Formation Rates?

NASA Astrophysics Data System (ADS)

Evans, Neal John

2017-06-01

The relations between star formation and gas have received renewed attention. We combine studies on scales ranging from local (within 0.5 kpc) to distant galaxies to assess what factors contribute to star formation. These include studies of star forming regions in the Milky Way, the LMC, nearby galaxies with spatially resolved star formation, and integrated galaxy studies. We test whether total molecular gas or dense gas provides the best predictor of star formation rate. The star formation ``efficiency," defined as star formation rate divided by mass, spreads over a large range when the mass refers to molecular gas; the standard deviation of the log of the efficiency decreases by a factor of three when the mass of relatively dense molecular gas is used rather than the mass of all the molecular gas. We suggest ways to further develop the concept of "dense gas" to incorporate other factors, such as turbulence.

A Highly Efficient Heterogenized Iridium Complex for the Catalytic Hydrogenation of Carbon Dioxide to Formate.

PubMed

Park, Kwangho; Gunasekar, Gunniya Hariyanandam; Prakash, Natarajan; Jung, Kwang-Deog; Yoon, Sungho

2015-10-26

A heterogenized catalyst on a highly porous covalent triazine framework was synthesized and characterized to have a coordination environment similar to that of its homogeneous counterpart. The catalyst efficiently converted CO2 into formate through hydrogenation with a turnover number of 5000 after 2 h and an initial turnover frequency of up to 5300 h(-1) ; both of these values are the highest reported to date for a heterogeneous catalyst, which makes it attractive toward industrial application. Furthermore, the synthesized catalyst was found to be stable in air and was recycled by simple filtration without significant loss of catalytic activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Los Angeles International Airport Runway Incursion Studies: Phase III--Center-Taxiway Simulation

NASA Technical Reports Server (NTRS)

Madson, Michael D.

2004-01-01

Phase III of the Los Angeles International Airport Runway Incursion Studies was conducted, under an agreement with HNTB Corporation, at the NASA Ames FutureFlight Central (FFC) facility in June 2003. The objective of the study was the evaluation of a new center-taxiway concept at LAX. This study is an extension of the Phase I and Phase II studies previously conducted at FFC. This report presents results from Phase III of the study, in which a center-taxiway concept between runways 25L and 25R was simulated and evaluated. Phase III data were compared objectively against the Baseline data. Subjective evaluations by participating LAX controllers were obtained with regard to workload, efficiency, and safety criteria. To facilitate a valid comparison between Baseline and Phase III data, the same scenarios were used for Phase III that were tested during Phases I and II. This required briefing participating controllers on differences in airport and airline operations between 2001 and today.

Magnetic Nature of the CrIII–LnIII Interactions in [CrIII 2LnIII 3] Clusters with Slow Magnetic Relaxation

PubMed Central

Xiang, Shuo; Wang, Jin; Bao, Dong‐Xu; Li, Yun‐Chun

2018-01-01

Abstract Two 3d‐4f hetero‐metal pentanuclear complexes with the formula {[CrIII 2LnIII 3L10(OH)6(H2O)2]Et3NH} [Ln=Tb (1), Dy (2); HL=pivalic acid, Et3N=triethylamine] have been produced. The metal core of each cluster is made up of a trigonal bipyramid with three LnIII ions (plane) and two CrIII ions (above and below) held together by six μ 3‐OH bridges. Also reported with this series is the diamagnetic CrIII–YIII analogue (3). Fortunately, we successfully prepared AlIII–LnIII analogues with the formula {[AlIII 2LnIII 3L10(OH)6(H2O)2]Et3NH⋅H2O} [Ln=Tb (4), Dy (5)], containing diamagnetic AlIII ions, which can be used to evaluate the CrIII–LnIII magnetic nature through a diamagnetic substitution method. Subsequently, static (dc) magnetic susceptibility studies reveal dominant ferromagnetic interactions between CrIII and LnIII ions. Dynamic (ac) magnetic susceptibility studies show frequency‐dependent out‐of‐phase (χ′′) signals for [CrIII 2TbIII 3] (1), [CrIII 2DyIII 3] (2), and [AlIII 2DyIII 3] (5), which are derived from the single‐ion behavior of LnIII ions and/or the CrIII–LnIII ferromagnetic interactions. PMID:29435404

Synthesis, antiproliferative activity and mechanism of gallium(III)-thiosemicarbazone complexes as potential anti-breast cancer agents.

PubMed

Qi, Jinxu; Yao, Qian; Qian, Kun; Tian, Liang; Cheng, Zhen; Yang, Dongmei; Wang, Yihong

2018-05-14

Five thiosemicarbazone ligands were synthesized and characterized by condensation with different aldehydes or ketones by 4-phenylthiosemicarbazone. The representative dichlorido[2-(Di-2-pyridinylmethylene)-Nphenylhydrazinecarbothioamide-N,N,S]-gallium(III) (Ga4) was characterized by X-ray single crystal diffraction, which was 1:1 ligand/Ga(III) complexes. The structure-activity relationship of these ligands and Ga (III) complexes have been investigated, and the results demonstrate that the formation of Ga (III) complexes have significant antiproliferative activity over the corresponding ligands. The anticancer mechanism of gallium (III) complexes has been studied in detail, which is typical agents that effect on the mitochondrial apoptotic pathway. The ability of gallium (III) complexes to inhibit the cell cycle does not enhanced with the increasing concentrations, whereas the ability to promote apoptosis is concentration-dependent. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution

NASA Astrophysics Data System (ADS)

Dumpala, Rama Mohana Rao; Rawat, Neetika; Boda, Anil; Ali, Sk. Musharaf; Tomar, B. S.

2018-02-01

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i = 1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO > IANO > NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study.

PubMed

Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H M; Bochmann, Manfred

2018-06-21

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied by using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, by using the pincer compounds [(C^N^C)AuR] (R=C 6 F 5 , CH=CMe 2 , Me and p-C 6 H 4 X, where X=OMe, F, H, tBu, Cl, CF 3 , or NO 2 ) as starting materials (C^N^C=2,6-(4'-tBuC 6 H 3 ) 2 pyridine dianion). Protodeauration followed by addition of one equivalent SMe 2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe 2 )] + . Upon addition of a second SMe 2 pyridine is displaced, which triggers the reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl)>k(aryl)≫k(C 6 F 5 )>k(Me). Vinyl-aryl coupling is particularly fast, 1.15×10 -3  L mol -1  s -1 at 221 K, whereas both C 6 F 5 and Me couplings encountered higher barriers for the C-C bond forming step. The use of P(p-tol) 3 in place of SMe 2 greatly accelerates the C-C couplings. Computational modelling shows that in the C^N-bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. The C-C bond formation is the rate-limiting step. In the non-chelating case, reductive C(sp 2 )-C(sp 2 ) elimination from three-coordinate ions [(Ar 1 )(Ar 2 )AuL] + is almost barrier-free, particularly if L=phosphine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular modeling study on the relative stabilities of the flotation products for arsenic-containing minerals: dixanthogens and arsenic(III) xanthates.

PubMed

Yekeler, Meftuni; Yekeler, Hülya

2005-04-15

The interactions of As(III) ion with C(2)H(5)OCS(-)(2) and C(2)H(5)SCS(-)(2), known as the most popular collector ions, were studied by density functional theory (DFT) at the B3LYP/6-31G** level in connection with the arsenic-containing minerals realgar, orpiment, and arsenopyrite. The dixanthogen formations of these ions were also investigated at the same level of theory. The central purpose of this paper is to compare the stabilities of the major flotation products, namely As(III) xanthates and dixanthogens. The results show that the magnitudes of the interaction energies for the formations of As(III) xanthates and dixanthogens increase when the oxygen atom is replaced by the sulfur atom in C(2)H(5)OCS(-)(2). Therefore, the C(2)H(5)OCS(-)(2) ion is preferred in these formations. The results obtained are in agreement with the experimental data reported.

Lanthanide luminescent displacement assays: the sensing of phosphate anions using Eu(III)-cyclen-conjugated gold nanoparticles in aqueous solution.

PubMed

Massue, Julien; Quinn, Susan J; Gunnlaugsson, Thorfinnur

2008-06-04

1.Eu, a cyclen based Eu(III)-thiol conjugate, was incorporated onto the surface of water-soluble gold nanoparticles to give AuNP-1.Eu. The self-assembly between AuNP-1.Eu and the antenna 2 resulted in the formation of the highly luminescent lanthanide system, AuNP-1.Eu-2, at pH 7.4. The sensing of flavin monophosphate 3 is demonstrated, whereby 3 displaced the antenna 2 in AuNP-1.Eu-2, resulting in the formation of AuNP-1.Eu-3 and quenching of the Eu(III) emission.

On the Star Formation-AGN Connection at zeta (is) approximately greater than 0.3

NASA Technical Reports Server (NTRS)

LaMassa, Stephanie M.; Heckman, T. M.; Ptak, Andrew; Urry, C. Megan

2013-01-01

Using the spectra of a sample of approximately 28,000 nearby obscured active galaxies from Data Release 7 of the Sloan Digital Sky Survey (SDSS), we probe the connection between active galactic nucleus (AGN) activity and star formation over a range of radial scales in the host galaxy. We use the extinction-corrected luminosity of the [O iii] 5007A line as a proxy of intrinsic AGN power and supermassive black hole (SMBH) accretion rate. The star formation rates (SFRs) are taken from the MPA-JHU value-added catalog and are measured through the 3 inch SDSS aperture. We construct matched samples of galaxies covering a range in redshifts. With increasing redshift, the projected aperture size encompasses increasing amounts of the host galaxy. This allows us to trace the radial distribution of star formation as a function of AGN luminosity. We find that the star formation becomes more centrally concentrated with increasing AGN luminosity and Eddington ratio. This implies that such circumnuclear star formation is associated with AGN activity, and that it increasingly dominates over omnipresent disk star formation at higher AGN luminosities, placing critical constraints on theoretical models that link host galaxy star formation and SMBH fueling. We parameterize this relationship and find that the star formation on radial scales (is) less than 1.7 kpc, when including a constant disk component, has a sub-linear dependence on SMBH accretion rate: SFR in proportion to solar mass(sup 0.36), suggesting that angular momentum transfer through the disk limits accretion efficiency rather than the supply from stellar mass loss.

Angiotensin II-producing enzyme III from acidified serum of nephrectomized dogs.

PubMed

Haas, E; Lewis, L; Koshy, T J; Varde, A U; Renerts, L; Bagai, R C

1989-09-01

A highly active angiotensin-producing enzyme (enzyme III) was obtained from the serum of bilaterally nephrectomized dogs by acid treatment and ammonium sulfate fractionation. An inactive precursor (proenzyme III) was converted to enzyme III during prolonged storage (or by treatment with acid or with cathepsin G or by incubation at 38 degrees C as described in the following paper). Enzyme III reacted maximally at pH 7.7 and it produced up to 400 ng of angiotensin II/mL serum/h (i.e., amounts 4000 times higher than that generated by the endogenous renin present in serum after bilateral nephrectomy). Enzyme III produced angiotensin II at identical rates when either dog angiotensinogen or angiotensin I was used as substrate, but the rate was 710 times higher with synthetic tetradecapeptide renin substrate. Enzyme III is not identical to renin, cathepsin G, tonin, enzyme I, enzyme II, the calcium-dependent angiotensin I-converting enzyme, or the calcium-independent carboxy peptidase, which acts by sequential cleavage of angiotensin I. Enzyme III was inhibited by alpha-1-antitrypsin, diisopropyl fluorophosphate, and lima bean trypsin inhibitor (hence it is a serine proteinase). It was not inhibited by Captopril, Teprotide, or Enalapril. It had been reported previously that cathepsin G released from neutrophil granulocytes, by producing high local concentrations of angiotensin II, may provide a mobile means for modulating blood flow in tissue microvasculature during the inflammatory response. The present study offers a new, additional pathway, by enzyme III, for a similar rapid formation of angiotensin II from serum protein substrate or angiotensin I.

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

PubMed Central

Wilson, Justin J.

2012-01-01

Oxidation of the acetate-bridged half-lantern platinum(II) complex, cis-[PtII(NH3)2(µ-OAc)2PtII(NH3)2](NO3)2, [1](NO3)2, with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species, cis-[XPtIII(NH3)2(µ-OAc)2PtIII(NH3)2X](NO3)2, where X is Cl in [2](NO3)2, or Br in [3](NO3)2, respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈ 2.6 Å) Pt–Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt–X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of 1H, 13C, 14N, and 195Pt NMR spectroscopy was used to characterize [1]2+–[3]2+ in solution. All resonances shift downfield upon oxidation of [1]2+ to [2]2+ and [3]2+. For the platinum(III) complexes, the 14N and 195Pt resonances exhibit decreased linewidths by comparison to those of [1]2+. Density functional theory (DFT) calculations suggest that the decrease in 14N linewidth arises from a diminished electric field gradient (EFG) at the 14N nuclei in the higher valent compounds. The oxidation of [1](NO3)2 with the alternative oxidizing agent, bis(trifluoroacetoxy) iodobenzene, affords the novel tetranuclear complex, cis-[(O2CCF3)PtIII(NH3)2(µ-OAc)2PtIII(NH3)(µ-NH2)]2(NO3)4, [4](NO3)4, also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed. PMID:22946515

Synthesis and in vitro microbial evaluation of La(III), Ce(III), Sm(III) and Y(III) metal complexes of vitamin B6 drug

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.

2014-06-01

Metal complexes of pyridoxine mono hydrochloride (vitamin B6) are prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes are investigated. Some physical properties, conductivity, analytical data and the composition of the four pyridoxine complexes are discussed. The elemental analysis shows that the formed complexes of La(III), Ce(III), Sm(III) and Y(III) with pyridoxine are of 1:2 (metal:PN) molar ratio. All the synthesized complexes are brown in color and possess high melting points. These complexes are partially soluble in hot methanol, dimethylsulfoxide and dimethylformamide and insoluble in water and some other organic solvents. Elemental analysis data, spectroscopic (IR, UV-vis. and florescence), effective magnetic moment in Bohr magnetons and the proton NMR suggest the structures. However, definite particle size is determined by invoking the X-ray powder diffraction and scanning electron microscopy data. The results obtained suggested that pyridoxine reacted with metal ions as a bidentate ligand through its phenolate oxygen and the oxygen of the adjacent group at the 4‧-position. The molar conductance measurements proved that the pyridoxine complexes are electrolytic in nature. The kinetic and thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves. The antibacterial evaluation of the pyridoxine and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

Gallium(iii) and iron(iii) complexes of quinolone antimicrobials.

PubMed

Mjos, Katja Dralle; Cawthray, Jacqueline F; Polishchuk, Elena; Abrams, Michael J; Orvig, Chris

2016-08-16

Iron is an essential nutrient for many microbes. According to the "Trojan Horse Hypothesis", biological systems have difficulties distinguishing between Fe(3+) and Ga(3+), which constitutes the antimicrobial efficacy of the gallium(iii) ion. Nine novel tris(quinolono)gallium(iii) complexes and their corresponding iron(iii) analogs have been synthesized and fully characterized. Quinolone antimicrobial agents from three drug generations were used in this study: ciprofloxacin, enoxacin, fleroxacin, levofloxacin, lomefloxacin, nalidixic acid, norfloxacin, oxolinic acid, and pipemidic acid. The antimicrobial efficacy of the tris(quinolono)gallium(iii) complexes was studied against E. faecalis and S. aureus (both Gram-positive), as well as E. coli, K. pneumonia, and P. aeruginosa (all Gram-negative) in direct comparison to the tris(quinolono)iron(iii) complexes and the corresponding free quinolone ligands at various concentrations. For the tris(quinolono)gallium(iii) complexes, no combinational antimicrobial effects between Ga(3+) and the quinolone antimicrobial agents were observed.

9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

PubMed

Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

2013-05-14

parameters well prompting the coordination of PQ(˙-) to the M(III) ions. The comparatively shorter C-O lengths, 1.268(4) and 1.266(5) Å and the longer C-C length, 1.466(6) Å, are consistent with the PQ chelation to osmium(II) ion in 4(+). The reversible anodic waves at 0.22, 0.22, and 0.18 V of 1-3, referenced by the Fc(+)/Fc couple, are assigned to the PQ(˙-)/PQ couple forming PQ complexes as trans/cis-[M(III)(PQ)(PPh3)2X2](+) while the cathodic waves at -0.92 and -0.89 V of 2 and 3 are due to formations of PQ(2-) complexes as trans-[M(III)(PQ(2-))(PPh3)2X2](-). 1 displays two overlapping cathodic waves at -0.72(89), -1.0(120) V. EPR spectrum of the frozen glass of 1(-) along with DFT calculations detected the contribution of both the valence tautomers, trans-[Ru(III)(PQ(2-))(PPh3)2Cl2](-) (g1 = g2 = 2.456; g3 = 1.983) and trans-[Ru(II)(PQ(˙-))(PPh3)2X2](-) (g(iso) = 1.999) in the anion. The characteristic lower energy absorption bands of 1 and 2 at 700 nm were assigned to CSS-OSS perturbation MLCT those are absent in paramagnetic 3, 1(+), 2(+), 1(-), 2(-) and 4(+) complexes, investigated by spectro-electrochemical measurements and time dependent (TD) DFT calculations on 1Me, 2Me, 1Me(+) and 1Me(-).

Radiation transfer of models of massive star formation. III. The evolutionary sequence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yichen; Tan, Jonathan C.; Hosokawa, Takashi, E-mail: yichen.zhang@yale.edu, E-mail: jt@astro.ufl.edu, E-mail: takashi.hosokawa@phys.s.u-tokyo.ac.jp

2014-06-20

We present radiation transfer simulations of evolutionary sequences of massive protostars forming from massive dense cores in environments of high mass surface densities, based on the Turbulent Core Model. The protostellar evolution is calculated with a multi-zone numerical model, with the accretion rate regulated by feedback from an evolving disk wind outflow cavity. The disk evolution is calculated assuming a fixed ratio of disk to protostellar mass, while the core envelope evolution assumes an inside-out collapse of the core with a fixed outer radius. In this framework, an evolutionary track is determined by three environmental initial conditions: the core massmore » M{sub c} , the mass surface density of the ambient clump Σ{sub cl}, and the ratio of the core's initial rotational to gravitational energy β {sub c}. Evolutionary sequences with various M{sub c} , Σ{sub cl}, and β {sub c} are constructed. We find that in a fiducial model with M{sub c} = 60 M {sub ☉}, Σ{sub cl} = 1 g cm{sup –2}, and β {sub c} = 0.02, the final mass of the protostar reaches at least ∼26 M {sub ☉}, making the final star formation efficiency ≳ 0.43. For each of the evolutionary tracks, radiation transfer simulations are performed at selected stages, with temperature profiles, spectral energy distributions (SEDs), and multiwavelength images produced. At a given stage, the envelope temperature depends strongly on Σ{sub cl}, with higher temperatures in a higher Σ{sub cl} core, but only weakly on M{sub c} . The SED and MIR images depend sensitively on the evolving outflow cavity, which gradually widens as the protostar grows. The fluxes at ≲ 100 μm increase dramatically, and the far-IR peaks move to shorter wavelengths. The influence of Σ{sub cl} and β {sub c} (which determines disk size) are discussed. We find that, despite scatter caused by different M{sub c} , Σ{sub cl}, β {sub c}, and inclinations, sources at a given evolutionary stage appear in similar

Revised SNAP III Training Manual

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moss, Calvin Elroy; Gonzales, Samuel M.; Myers, William L.

The Shielded Neutron Assay Probe (SNAP) technique was developed to determine the leakage neutron source strength of a radioactive object. The original system consisted of an Eberline TM Mini-scaler and discrete neutron detector. The system was operated by obtaining the count rate with the Eberline TM instrument, determining the absolute efficiency from a graph, and calculating the neutron source strength by hand. In 2003 the SNAP III, shown in Figure 1, was designed and built. It required the operator to position the SNAP, and then measure the source-to-detector and detectorto- reflector distances. Next the operator entered the distance measurements andmore » started the data acquisition. The SNAP acquired the required count rate and then calculated and displayed the leakage neutron source strength (NSS). The original design of the SNAP III is described in SNAP III Training Manual (ER-TRN-PLN-0258, Rev. 0, January 2004, prepared by William Baird) This report describes some changes that have been made to the SNAP III. One important change is the addition of a LEMO connector to provide neutron detection output pulses for input to the MC-15. This feature is useful in active interrogation with a neutron generator because the MC-15 has the capability to only record data when it is not gated off by a pulse from the neutron generator. This avoids recording of a lot of data during the generator pulses that are not useful. Another change was the replacement of the infrared RS-232 serial communication output by a similar output via a 4-pin LEMO connector. The current document includes a more complete explanation of how to estimate the amount of moderation around a neutron-emitting source.« less

Mineral ecophysiological evidence for microbial activity in banded iron formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dr. Yi-Liang; Konhauser, Dr, Kurt; Cole, David R

2011-01-01

The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Westernmore » Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.« less

Sorption of Cr(III) ion from aqueous solution by two kinds of modified diatomite.

PubMed

Li, Er; Zeng, Xiangying

2012-01-01

Raw diatomite modified by microemulsion (DMM) and manganese oxide (MnD) were used for the removal of Cr(III) ions from aqueous solution. The characteristics and performance of these two types of modified diatomite on Cr(III) ion adsorption were compared. The results indicate that the Cr(III) ion adsorption capacities of diatomite were considerably improved after modifications by manganese oxide (MnO) and microemulsion. The surface area of MnD was increased because of the formation of MnO on the diatomite surface, and that of DMM was promoted owing to the existence of the hydrolyzed aromatic acid. Because of the stronger surface ionized function, the adsorption performance of Cr(III) ions in DMM was better than that in MnD. Within the experimental range of pH (i.e. 2.2-6.3), the Cr(III) ion removal of DMM (35-70%) was higher than that of MnD (33-59%) owing to the different electrostatic forces between the Cr(III) ion and the surface of the modified diatomite. The Cr(III) ion removal in MnD and DMM was improved with the increase of synthetic solution concentration in volumes from 0 to 2,500 mL.

Efficient biosynthesis of d-ribose using a novel co-feeding strategy in Bacillus subtilis without acid formation.

PubMed

Cheng, J; Zhuang, W; Li, N N; Tang, C L; Ying, H J

2017-01-01

Normally, low d-ribose production was identified as responsible for plenty of acid formation by Bacillus subtilis due to its carbon overflow. An approach of co-feeding glucose and sodium citrate is developed here and had been proved to be useful in d-ribose production. This strategy is critical because it affects the cell concentration, the productivity of d-ribose and, especially, the formation of by-products such as acetoin, lactate and acetate. d-ribose production was increased by 59·6% from 71·06 to 113·41 g l -1 without acid formation by co-feeding 2·22 g l -1  h -1 glucose and 0·036 g l -1  h -1 sodium citrate to a 60 g l -1 glucose reaction system. Actually, the cell density was also enhanced from 11·51 to 13·84 g l -1 . These parameters revealed the importance of optimization and modelling of the d-ribose production process. Not only could zero acid formation was achieved over a wide range of co-feeding rate by reducing glycolytic flux drastically but also the cell density and d-ribose yield were elevated by increasing the hexose monophosphate pathway flux. Bacillus subtilis usually produce d-ribose accompanied by plenty of organic acids when glucose is used as a carbon source, which is considered to be a consequence of mismatched glycolytic and tricarboxylic acid cycle capacities. This is the first study to provide high-efficiency biosynthesis of d-ribose without organic acid formation in B. subtilis, which would be lower than the cost of separation and purification. The strain transketolase-deficient B. subtilis CGMCC 3720 can be potentially applied to the production of d-ribose in industry. © 2016 The Society for Applied Microbiology.

Fragmentation during primordial star formation

NASA Astrophysics Data System (ADS)

Dutta, Jayanta

Understanding the physics of the very first stars in the universe, the so-called Population III (or Pop III) stars, is crucial in determining how the universe evolved into what we observe today. In the standard model of Pop III star formation, the baryonic matter, mainly atomic hydrogen, collapses gravitationally into small Dark Matter (DM) minihalos. However, so far there is little understanding on how the thermal, dynamical and chemical evolution of the primordial gas depend on the initial configuration of the minihalos (for example, rotation of the unstable clumps inside minihalos, turbulence, formation of molecular hydrogen and cosmic variance of the minihalos). We use the modified version of the Gadget-2 code, a three-dimensional smoothed particle hydrodynamics (SPH) simulations, to follow the evolution of the collapsing gas in both idealized as well as more realistic minihalos. Unlike some earlier cosmological calculations, the implementation of sink particles allows us to follow the evolution of the accretion disk that builds up in the centre of each minihalo and fragments. We find that the fragmentation behavior depends on the adopted choice of three-body H2 formation rate coefficient. The increasing cooling rate during rapid conversion of the atomic to molecular hydrogen is offset by the heating due to gas contraction. We propose that the H2 cooling, the heating due to H2 formation and compressional heating together set a density and temperature structure in the disk that favors fragmentation. We also find that the cloud's initial degree of rotation has a significant effect on the thermal and dynamical evolution of the collapsing gas. Clouds with higher rotation exhibit spiral-arm-like structures that become gravitationally unstable to fragmentation on several scales. These type of clouds tend to fragment more and have lower accretion rates compared to their slowly rotating counterparts. In addition, we find that the distribution of specific angular

III-V/Active-Silicon Integration for Low-Cost High-Performance Concentrator Photovoltaics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ringel, Steven

This FPACE project was motivated by the need to establish the foundational pathway to achieve concentrator solar cell efficiencies greater than 50%. At such an efficiency, DOE modeling projected that a III-V CPV module cost of $0.50/W or better could be achieved. Therefore, the goal of this project was to investigate, develop and advance a III-V/Si mulitjunction (MJ) CPV technology that can simultaneously address the primary cost barrier for III-V MJ solar cells while enabling nearly ideal MJ bandgap profiles that can yield efficiencies in excess of 50% under concentrated sunlight. The proposed methodology was based on use of ourmore » recently developed GaAsP metamorphic graded buffer as a pathway to integrate unique GaAsP and Ga-rich GaInP middle and top junctions having bandgaps that are adjustable between 1.45 – 1.65 eV and 1.9 – 2.1 eV, respectively, with an underlying, 1.1 eV active Si subcell/substrate. With this design, the Si can be an active component sub-cell due to the semi-transparent nature of the GaAsP buffer with respect to Si as well as a low-cost alternative substrate that is amenable to scaling with existing Si foundry infrastructure, providing a reduction in materials cost and a low cost path to manufacturing at scale. By backside bonding of a SiGe, a path to exceed 50% efficiency is possible. Throughout the course of this effort, an expansive range of new understanding was achieved that has stimulated worldwide efforts in III-V/Si PV R&D that spanned materials development, metamorphic device optimization, and complete III-V/Si monolithic integration. Highlights include the demonstration of the first ideal GaP/Si interfaces grown by industry-standard MOCVD processes, the first high performance metamorphic tunnel junctions designed for III-V/Si integration, record performance of specific metamorphic sub-cell designs, the first fully integrated GaInP/GaAsP/Si double (1.7 eV/1.1 eV) and triple (1.95 eV/1.5 eV/1.1 eV) junction solar cells, the

Petroleum systems of Zhu III depression in Pearl River Mouth Basin, South China Sea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weilin, Zhu; Li Mingbi; Wu Peikang

Zhu III depression is located in the west part of Pearl River Mouth Basin, and covers an area of 11,000 sq km. Until now more than twenty wells have been drilled in the depression and its surrounding area, and all oil-gas fields and oil-gas discoveries are concentrated inside the depression. Integrated study indicates that there are two petroleum systems in Zhu III depression. One is Wenchang - Zhuhai, Zhujiang oil system which is mainly distributed in Wenchang B sag in the southwest part of the depression. Its source rock, the Wenchang formation is mainly composed of dark mudstone of lacustrinemore » facies, with thicknesses up to more than 1000 m. Its reservoir includes tidal sandstone of transitional facies of Zhuhai formation and neritic sandstone of the lower part of Zhujiang formation. Through bounding faults and margin coarse sediment zone, oil generated from the Wenchang formation migrated into overlying sandstone of Zhuhai formation, which was overlaid by mudstone beds of bay facies of Zhuhai formation or neritic facies of Zhujiang formation, and formed oil accumulations. The other system is Enping - Zhuhai gas system, distributed in Wenchang A sag in the northeast part of the depression, whose source rock in the Enping formation deposited in the contracting stage of the lake, dominated by swamp coal measure in lithology and terrestrial plant clastics in kerogen components. The gas generated from Enping formation directly migrated into overlying tidal sandstone of Zhuhai formation and formed gas accumulations. Therefore, exploration in Wenchang A sag in the northeast part of the depression is for gas accumulations, and oil accumulations in Wenchang B sag in the southwest part of the depression, while oil-gas mixed accumulations are likely to be found in the transitional area of two systems.« less

The Use of Chromium(III) to Supercharge Peptides by Protonation at Low Basicity Sites

NASA Astrophysics Data System (ADS)

Feng, Changgeng; Commodore, Juliette J.; Cassady, Carolyn J.

2015-02-01

The addition of chromium(III) nitrate to solutions of peptides with seven or more residues greatly increases the formation of doubly protonated peptides, [M + 2H]2+, by electrospray ionization. The test compound heptaalanine has only one highly basic site (the N-terminal amino group) and undergoes almost exclusive single protonation using standard solvents. When Cr(III) is added to the solution, abundant [M + 2H]2+ forms, which involves protonation of the peptide backbone or the C-terminus. Salts of Al(III), Mn(II), Fe(III), Fe(II), Cu(II), Zn (II), Rh(III), La(III), Ce(IV), and Eu(III) were also studied. Although several metal ions slightly enhance protonation, Cr(III) has by far the greatest ability to generate [M + 2H]2+. Cr(III) does not supercharge peptide methyl esters, which suggests that the mechanism involves interaction of Cr(III) with a carboxylic acid group. Other factors may include the high acidity of hexa-aquochromium(III) and the resistance of Cr(III) to reduction. Nitrate salts enhance protonation more than chloride salts and a molar ratio of 10:1 Cr(III):peptide produces the most intense [M + 2H]2+. Cr(III) also supercharges numerous other small peptides, including highly acidic species. For basic peptides, Cr(III) increases the charge state (2+ versus 1+) and causes the number of peptide molecules being protonated to double or triple. Chromium(III) does not supercharge the proteins cytochrome c and myoglobin. The ability of Cr(III) to enhance [M + 2H]2+ intensity may prove useful in tandem mass spectrometry because of the resulting overall increase in signal-to-noise ratio, the fact that [M + 2H]2+ generally dissociate more readily than [M + H]+, and the ability to produce [M + 2H]2+ precursors for electron-based dissociation techniques.

Electrostatic Interactions between Elongated Monomers Drive Filamentation of Drosophila Shrub, a Metazoan ESCRT-III Protein.

PubMed

McMillan, Brian J; Tibbe, Christine; Jeon, Hyesung; Drabek, Andrew A; Klein, Thomas; Blacklow, Stephen C

2016-08-02

The endosomal sorting complex required for transport (ESCRT) is a conserved protein complex that facilitates budding and fission of membranes. It executes a key step in many cellular events, including cytokinesis and multi-vesicular body formation. The ESCRT-III protein Shrub in flies, or its homologs in yeast (Snf7) or humans (CHMP4B), is a critical polymerizing component of ESCRT-III needed to effect membrane fission. We report the structural basis for polymerization of Shrub and define a minimal region required for filament formation. The X-ray structure of the Shrub core shows that individual monomers in the lattice interact in a staggered arrangement using complementary electrostatic surfaces. Mutations that disrupt interface salt bridges interfere with Shrub polymerization and function. Despite substantial sequence divergence and differences in packing interactions, the arrangement of Shrub subunits in the polymer resembles that of Snf7 and other family homologs, suggesting that this intermolecular packing mechanism is shared among ESCRT-III proteins. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Dipicolinate Complexes of Gallium(III) and Lanthanum(III).

PubMed

Weekes, David M; Ramogida, Caterina F; Jaraquemada-Peláez, Maria de Guadalupe; Patrick, Brian O; Apte, Chirag; Kostelnik, Thomas I; Cawthray, Jacqueline F; Murphy, Lisa; Orvig, Chris

2016-12-19

Three dipicolinic acid amine-derived compounds functionalized with a carboxylate (H 3 dpaa), phosphonate (H 4 dppa), and bisphosphonate (H 7 dpbpa), as well as their nonfunctionalized analogue (H 2 dpa), were successfully synthesized and characterized. The 1:1 lanthanum(III) complexes of H 2 dpa, H 3 dpaa, and H 4 dppa, the 1:2 lanthanum(III) complex of H 2 dpa, and the 1:1 gallium(III) complex of H 3 dpaa were characterized, including via X-ray crystallography for [La 4 (dppa) 4 (H 2 O) 2 ] and [Ga(dpaa)(H 2 O)]. H 2 dpa, H 3 dpaa, and H 4 dppa were evaluated for their thermodynamic stability with lanthanum(III) via potentiometric and either UV-vis spectrophotometric (H 3 dpaa) or NMR spectrometric (H 2 dpa and H 4 dppa) titrations, which showed that the carboxylate (H 3 dpaa) and phosphonate (H 4 dppa) containing ligands enhanced the lanthanum(III) complex stability by 3-4 orders of magnitude relative to the unfunctionalized ligand (comparing log β ML and pM values) at physiological pH. In addition, potentiometric titrations with H 3 dpaa and gallium(III) were performed, which gave significantly (8 orders of magnitude) higher thermodynamic stability constants than with lanthanum(III). This was predicted to be a consequence of better size matching between the dipicolinate cavity and gallium(III), which was also evident in the aforementioned crystal structures. Because of a potential link between lanthanum(III) and osteoporosis, the ligands were tested for their bone-directing properties via a hydroxyapatite (HAP) binding assay, which showed that either a phosphonate or bisphosphonate moiety was necessary in order to elicit a chemical binding interaction with HAP. The oral activity of the ligands and their metal complexes was also assessed by experimentally measuring log P o/w values using the shake-flask method, and these were compared to a currently prescribed osteoporosis drug (alendronate). Because of the potential therapeutic applications of the radionuclides

The evolution of galaxies. III - Metal-enhanced star formation

NASA Technical Reports Server (NTRS)

Talbot, R. J., Jr.; Arnett, W. D.

1973-01-01

The problem of the paucity of low-metal-abundance low-mass stars is discussed. One alternative to the variable-initial-mass-function (VIMF) solution is proposed. It is shown that this solution - metal-enhanced star formation - satisfies the classical test which prompted the VIMF hypothesis. Furthermore, with no additional parameters it provides improved fits to other tests - e.g., inhomogeneities in the abundances in young stars, concordance of all nucleo-cosmochronologies, and a required yield of heavy-element production which is consistent with current stellar evolution theory. In this model the age of the Galaxy is 18.6 plus or minus 5.7 b.y.

Megacity pollution by modern Diesel cars: New insights into the nature and formation of volatile nano-particles with high lung intrusion efficiency

NASA Astrophysics Data System (ADS)

Arnold, F.; Reichl, U.; Muschik, Ch.; Roiger, A.; Schlager, H.; Pirjola, L.; Rönkkö, T.; Keskinen, J.; Rothe, D.; Lähde, T.

2009-04-01

Aerosol particles generated by Diesel vehicles represent mayor health affecting air pollutants in cities and near motor ways. To mitigate the Diesel particle pollution problem, Diesel vehicles become increasingly fitted or retro-fitted with modern exhaust after treatment systems (ATS), which remove most engine-generated primary particles, particularly soot. Unfortunately however, ATS have undesired side effects including also the formation of low vapour pressure gases, which may undergo nucleation and condensation leading to volatile nucleation particles (NUP). NUP are substantially smaller (diameters: 5-15 nm) than soot particles (diameters: 40-100 nm), and therefore may be termed real nano-particles. NUP can intrude with maximum efficiency the lowest, least protected, and most vulnerable compartment of the human lung. However, the chemical nature and mechanism of formation of NUP are only poorly explored. Using a novel mass spectrometric method, we have made the first on line and off line measurements of low vapour pressure NUP precursor gases in the exhaust of a modern heavy duty Diesel vehicle engine, operated with and without ATS and combusting low and ultra-low sulphur fuels including also bio fuel. In addition, we have made accompanying NUP measurements and NUP model simulations. The on line measurements involved a CIMS (Chemical Ionization Mass Spectrometry) method originally developed by MPIK. They took place directly in the Diesel exhaust and had a large sensitivity and a fast time response (1 s). The off line measurements involved adsorption of exhaust gases on stainless steel, followed by thermo desorption and detection of desorbed exhaust molecules by CIMS. We find that modern Diesel ATS strongly increase the formation of hydroxyl radicals, which induce conversion of fuel sulphur to the important NUP precursor gaseous sulphuric acid. We also find that appreciable amounts of di-carboxylic acids survive the passage of the ATS or are even formed by the

Low-Fe(III) Greenalite Was a Primary Mineral From Neoarchean Oceans

NASA Astrophysics Data System (ADS)

Johnson, Jena E.; Muhling, Janet R.; Cosmidis, Julie; Rasmussen, Birger; Templeton, Alexis S.

2018-04-01

Banded iron formations (BIFs) represent chemical precipitation from Earth's early oceans and therefore contain insights into ancient marine biogeochemistry. However, BIFs have undergone multiple episodes of alteration, making it difficult to assess the primary mineral assemblage. Nanoscale mineral inclusions from 2.5 billion year old BIFs and ferruginous cherts provide new evidence that iron silicates were primary minerals deposited from the Neoarchean ocean, contrasting sharply with current models for BIF inception. Here we used multiscale imaging and spectroscopic techniques to characterize the best preserved examples of these inclusions. Our integrated results demonstrate that these early minerals were low-Fe(III) greenalite. We present potential pathways in which low-Fe(III) greenalite could have formed through changes in saturation state and/or iron oxidation and reduction. Future constraints for ancient ocean chemistry and early life's activities should include low-Fe(III) greenalite as a primary mineral in the Neoarchean ocean.

Standard interface files and procedures for reactor physics codes, version III

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carmichael, B.M.

Standards and procedures for promoting the exchange of reactor physics codes are updated to Version-III status. Standards covering program structure, interface files, file handling subroutines, and card input format are included. The implementation status of the standards in codes and the extension of the standards to new code areas are summarized. (15 references) (auth)

Toward a III-V Multijunction Space Cell Technology on Si

NASA Technical Reports Server (NTRS)

Ringel, S. A.; Lueck, M. R.; Andre, C. L.; Fitzgerald, E. A.; Wilt, D. M.; Scheiman, D.

2007-01-01

High efficiency compound semiconductor solar cells grown on Si substrates are of growing interest in the photovoltaics community for both terrestrial and space applications. As a potential substrate for III-V compound photovoltaics, Si has many advantages over traditional Ge and GaAs substrates that include higher thermal conductivity, lower weight, lower material costs, and the potential to leverage the extensive manufacturing base of the Si industry. Such a technology that would retain high solar conversion efficiency at reduced weight and cost would result in space solar cells that simultaneously possess high specific power (W/kg) and high power density (W/m2). For terrestrial solar cells this would result in high efficiency III-V concentrators with improved thermal conductivity, reduced cost, and via the use of SiGe graded interlayers as active component layers the possibility of integrating low bandgap sub-cells that could provide for extremely high conversion efficiency.1 In addition to photovoltaics, there has been an historical interest in III-V/Si integration to provide optical interconnects in Si electronics, which has become of even greater relevance recently due to impending bottlenecks in CMOS based circuitry. As a result, numerous strategies to integrate GaAs with Si have been explored with the primary issue being the approx.4% lattice mismatch between GaAs and Si. Among these efforts, relaxed, compositionally-graded SiGe buffer layers where the substrate lattice constant is effectively tuned from Si to that of Ge so that a close lattice match to subsequent GaAs overlayers have shown great promise. With this approach, threading dislocation densities (TDDs) of approx.1 x 10(exp 6)/sq cm have been uniformly achieved in relaxed Ge layers on Si,5 leading to GaAs on Si with minority carrier lifetimes greater than 10 ns,6 GaAs single junction solar cells on Si with efficiencies greater than 18%,7 InGaAs CW laser diodes on Si,8 and room temperature GaInP red

2-and 1-D coordination polymers of Dy(III) and Ho(III) with near infrared and visible luminescence by efficient charge-transfer antenna ligand

NASA Astrophysics Data System (ADS)

Oylumluoglu, Gorkem; Coban, Mustafa Burak; Kocak, Cagdas; Aygun, Muhittin; Kara, Hulya

2017-10-01

Two new lanthanide-based coordination complexes, [Dy(2-stp).2(H2O)]n (1) and {[Ho(2-stp).3(H2O)]·(H2O)}n (2) [2-stp = 2-sulfoterephthalic acid] were synthesized by hydrothermal reaction and characterized by elemental analysis, UV, IR, single crystal X-ray diffraction and solid state photoluminescence. DyIII and HoIII atoms are eight-coordinated and adopt a distorted square-antiprismatic geometry in complexes 1 and 2, respectively. In compound 1, Dy atoms are coordinated by four bridging 2-stp ligands forming two-dimensional (2D) layer, while Ho atoms by three bridging 2-stp ligands creating one dimensional (1D) double chains in 2. In addition, complexes 1 and 2 display in the solid state and at room temperature an intense yellow emission, respectively; this photoluminescence is achieved by an indirect process (antenna effect). The excellent luminescent performances make these complexes very good candidates for potential luminescence materials.

Invert biopanning: A novel method for efficient and rapid isolation of scFvs by phage display technology.

PubMed

Rahbarnia, Leila; Farajnia, Safar; Babaei, Hossein; Majidi, Jafar; Veisi, Kamal; Tanomand, Asghar; Akbari, Bahman

2016-11-01

Phage display is a prominent screening technique for development of novel high affinity antibodies against almost any antigen. However, removing false positive clones in screening process remains a challenge. The aim of this study was to develop an efficient and rapid method for isolation of high affinity scFvs by removing NSBs without losing rare specific clones. Therefore, a novel two rounds strategy called invert biopanning was developed for isolating high affinity scFvs against EGFRvIII antigen from human scFv library. The efficiency of invert biopanning method (procedure III) was analyzed by comparing with results of conventional biopanning methods (procedures I and II). According to the results of polyclonal ELISA, the second round of procedure III displayed highest binding affinity against EGFRvIII peptide accompanied by lowest NSB comparing to other two procedures. Several positive clones were identified among output phages of procedure III by monoclonal phage ELISA which displayed high affinity to EGFRvIII antigen. In conclusion, results of our study indicate that invert biopanning is an efficient method for avoiding NSBs and conservation of rare specific clones during screening of a scFv phage library. Novel anti EGFRvIII scFv isolated could be a promising candidate for potential use in treatment of EGFRvIII expressing cancers. Copyright © 2016 International Alliance for Biological Standardization. Published by Elsevier Ltd. All rights reserved.

Tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle

NASA Astrophysics Data System (ADS)

Zhang, Aiqin; Yang, Yamin; Zhai, Guangmei; Jia, Husheng; Xu, Bingshe

2016-02-01