Improving the Process of Adjusting the Parameters of Finite Element Models of Healthy Human Intervertebral Discs by the Multi-Response Surface Method.

PubMed

Gómez, Fátima Somovilla; Lorza, Rubén Lostado; Bobadilla, Marina Corral; García, Rubén Escribano

2017-09-21

The kinematic behavior of models that are based on the finite element method (FEM) for modeling the human body depends greatly on an accurate estimate of the parameters that define such models. This task is complex, and any small difference between the actual biomaterial model and the simulation model based on FEM can be amplified enormously in the presence of nonlinearities. The current paper attempts to demonstrate how a combination of the FEM and the MRS methods with desirability functions can be used to obtain the material parameters that are most appropriate for use in defining the behavior of Finite Element (FE) models of the healthy human lumbar intervertebral disc (IVD). The FE model parameters were adjusted on the basis of experimental data from selected standard tests (compression, flexion, extension, shear, lateral bending, and torsion) and were developed as follows: First, three-dimensional parameterized FE models were generated on the basis of the mentioned standard tests. Then, 11 parameters were selected to define the proposed parameterized FE models. For each of the standard tests, regression models were generated using MRS to model the six stiffness and nine bulges of the healthy IVD models that were created by changing the parameters of the FE models. The optimal combination of the 11 parameters was based on three different adjustment criteria. The latter, in turn, were based on the combination of stiffness and bulges that were obtained from the standard test FE simulations. The first adjustment criteria considered stiffness and bulges to be equally important in the adjustment of FE model parameters. The second adjustment criteria considered stiffness as most important, whereas the third considered the bulges to be most important. The proposed adjustment methods were applied to a medium-sized human IVD that corresponded to the L3-L4 lumbar level with standard dimensions of width = 50 mm, depth = 35 mm, and height = 10 mm. Agreement between the kinematic behavior that was obtained with the optimized parameters and that obtained from the literature demonstrated that the proposed method is a powerful tool with which to adjust healthy IVD FE models when there are many parameters, stiffnesses, and bulges to which the models must adjust.

Improving the Process of Adjusting the Parameters of Finite Element Models of Healthy Human Intervertebral Discs by the Multi-Response Surface Method

PubMed Central

Somovilla Gómez, Fátima

2017-01-01

The kinematic behavior of models that are based on the finite element method (FEM) for modeling the human body depends greatly on an accurate estimate of the parameters that define such models. This task is complex, and any small difference between the actual biomaterial model and the simulation model based on FEM can be amplified enormously in the presence of nonlinearities. The current paper attempts to demonstrate how a combination of the FEM and the MRS methods with desirability functions can be used to obtain the material parameters that are most appropriate for use in defining the behavior of Finite Element (FE) models of the healthy human lumbar intervertebral disc (IVD). The FE model parameters were adjusted on the basis of experimental data from selected standard tests (compression, flexion, extension, shear, lateral bending, and torsion) and were developed as follows: First, three-dimensional parameterized FE models were generated on the basis of the mentioned standard tests. Then, 11 parameters were selected to define the proposed parameterized FE models. For each of the standard tests, regression models were generated using MRS to model the six stiffness and nine bulges of the healthy IVD models that were created by changing the parameters of the FE models. The optimal combination of the 11 parameters was based on three different adjustment criteria. The latter, in turn, were based on the combination of stiffness and bulges that were obtained from the standard test FE simulations. The first adjustment criteria considered stiffness and bulges to be equally important in the adjustment of FE model parameters. The second adjustment criteria considered stiffness as most important, whereas the third considered the bulges to be most important. The proposed adjustment methods were applied to a medium-sized human IVD that corresponded to the L3–L4 lumbar level with standard dimensions of width = 50 mm, depth = 35 mm, and height = 10 mm. Agreement between the kinematic behavior that was obtained with the optimized parameters and that obtained from the literature demonstrated that the proposed method is a powerful tool with which to adjust healthy IVD FE models when there are many parameters, stiffnesses, and bulges to which the models must adjust. PMID:28934161

Coexistence of Cu, Fe, Pb, and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash.

PubMed

Fujimori, Takashi; Tanino, Yuta; Takaoka, Masaki

2014-01-01

We investigated chemical determinants of the generation of chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs), in fly ash from municipal solid waste incineration. The influences of the following on aromatic-Cls formation in model fly ash (MFA) were systematically examined quantitatively and statistically: (i) inorganic chlorides (KCl, NaCl, CaCl2), (ii) base materials (SiO2, Al2O3, CaCO3), (iii) metal oxides (CuO, Fe2O3, PbO, ZnO), (iv) metal chlorides (CuCl2, FeCl3, PbCl2, ZnCl2), and (v) "coexisting multi-models." On the basis of aromatic-Cls concentrations, the ∑CBzs/∑PCBs ratio, and the similarity between distribution patterns, MFAs were categorized into six groups. The results and analysis indicated that the formation of aromatic-Cls depended strongly on the "coexistence condition", namely multimodels composed of not only metal chlorides, but also of metal oxides. The precise replication of metal chloride to oxide ratios, such as the precise ratios of Cu-, Fe-, Pb-, and Zn-chlorides and oxides, may be an essential factor in changing the thermochemical formation patterns of aromatic-Cls. Although CuCl2 acted as a promoter of aromatic-Cls generation, statistical analyses implied that FeCl3 also largely influenced the generation of aromatic-Cls under mixture conditions. Various additional components of fly ash were also comprehensively analyzed.

Linearized Flux Evolution (LiFE): A technique for rapidly adapting fluxes from full-physics radiative transfer models

NASA Astrophysics Data System (ADS)

Robinson, Tyler D.; Crisp, David

2018-05-01

Solar and thermal radiation are critical aspects of planetary climate, with gradients in radiative energy fluxes driving heating and cooling. Climate models require that radiative transfer tools be versatile, computationally efficient, and accurate. Here, we describe a technique that uses an accurate full-physics radiative transfer model to generate a set of atmospheric radiative quantities which can be used to linearly adapt radiative flux profiles to changes in the atmospheric and surface state-the Linearized Flux Evolution (LiFE) approach. These radiative quantities describe how each model layer in a plane-parallel atmosphere reflects and transmits light, as well as how the layer generates diffuse radiation by thermal emission and by scattering light from the direct solar beam. By computing derivatives of these layer radiative properties with respect to dynamic elements of the atmospheric state, we can then efficiently adapt the flux profiles computed by the full-physics model to new atmospheric states. We validate the LiFE approach, and then apply this approach to Mars, Earth, and Venus, demonstrating the information contained in the layer radiative properties and their derivatives, as well as how the LiFE approach can be used to determine the thermal structure of radiative and radiative-convective equilibrium states in one-dimensional atmospheric models.

GPGPU-based explicit finite element computations for applications in biomechanics: the performance of material models, element technologies, and hardware generations.

PubMed

Strbac, V; Pierce, D M; Vander Sloten, J; Famaey, N

2017-12-01

Finite element (FE) simulations are increasingly valuable in assessing and improving the performance of biomedical devices and procedures. Due to high computational demands such simulations may become difficult or even infeasible, especially when considering nearly incompressible and anisotropic material models prevalent in analyses of soft tissues. Implementations of GPGPU-based explicit FEs predominantly cover isotropic materials, e.g. the neo-Hookean model. To elucidate the computational expense of anisotropic materials, we implement the Gasser-Ogden-Holzapfel dispersed, fiber-reinforced model and compare solution times against the neo-Hookean model. Implementations of GPGPU-based explicit FEs conventionally rely on single-point (under) integration. To elucidate the expense of full and selective-reduced integration (more reliable) we implement both and compare corresponding solution times against those generated using underintegration. To better understand the advancement of hardware, we compare results generated using representative Nvidia GPGPUs from three recent generations: Fermi (C2075), Kepler (K20c), and Maxwell (GTX980). We explore scaling by solving the same boundary value problem (an extension-inflation test on a segment of human aorta) with progressively larger FE meshes. Our results demonstrate substantial improvements in simulation speeds relative to two benchmark FE codes (up to 300[Formula: see text] while maintaining accuracy), and thus open many avenues to novel applications in biomechanics and medicine.

Injury risk functions based on population-based finite element model responses: Application to femurs under dynamic three-point bending.

PubMed

Park, Gwansik; Forman, Jason; Kim, Taewung; Panzer, Matthew B; Crandall, Jeff R

2018-02-28

The goal of this study was to explore a framework for developing injury risk functions (IRFs) in a bottom-up approach based on responses of parametrically variable finite element (FE) models representing exemplar populations. First, a parametric femur modeling tool was developed and validated using a subject-specific (SS)-FE modeling approach. Second, principal component analysis and regression were used to identify parametric geometric descriptors of the human femur and the distribution of those factors for 3 target occupant sizes (5th, 50th, and 95th percentile males). Third, distributions of material parameters of cortical bone were obtained from the literature for 3 target occupant ages (25, 50, and 75 years) using regression analysis. A Monte Carlo method was then implemented to generate populations of FE models of the femur for target occupants, using a parametric femur modeling tool. Simulations were conducted with each of these models under 3-point dynamic bending. Finally, model-based IRFs were developed using logistic regression analysis, based on the moment at fracture observed in the FE simulation. In total, 100 femur FE models incorporating the variation in the population of interest were generated, and 500,000 moments at fracture were observed (applying 5,000 ultimate strains for each synthesized 100 femur FE models) for each target occupant characteristics. Using the proposed framework on this study, the model-based IRFs for 3 target male occupant sizes (5th, 50th, and 95th percentiles) and ages (25, 50, and 75 years) were developed. The model-based IRF was located in the 95% confidence interval of the test-based IRF for the range of 15 to 70% injury risks. The 95% confidence interval of the developed IRF was almost in line with the mean curve due to a large number of data points. The framework proposed in this study would be beneficial for developing the IRFs in a bottom-up manner, whose range of variabilities is informed by the population-based FE model responses. Specifically, this method mitigates the uncertainties in applying empirical scaling and may improve IRF fidelity when a limited number of experimental specimens are available.

Parameterized Finite Element Modeling and Buckling Analysis of Six Typical Composite Grid Cylindrical Shells

NASA Astrophysics Data System (ADS)

Lai, Changliang; Wang, Junbiao; Liu, Chuang

2014-10-01

Six typical composite grid cylindrical shells are constructed by superimposing three basic types of ribs. Then buckling behavior and structural efficiency of these shells are analyzed under axial compression, pure bending, torsion and transverse bending by finite element (FE) models. The FE models are created by a parametrical FE modeling approach that defines FE models with original natural twisted geometry and orients cross-sections of beam elements exactly. And the approach is parameterized and coded by Patran Command Language (PCL). The demonstrations of FE modeling indicate the program enables efficient generation of FE models and facilitates parametric studies and design of grid shells. Using the program, the effects of helical angles on the buckling behavior of six typical grid cylindrical shells are determined. The results of these studies indicate that the triangle grid and rotated triangle grid cylindrical shell are more efficient than others under axial compression and pure bending, whereas under torsion and transverse bending, the hexagon grid cylindrical shell is most efficient. Additionally, buckling mode shapes are compared and provide an understanding of composite grid cylindrical shells that is useful in preliminary design of such structures.

Structure prediction of Fe(II) 2-oxoglutarate dioxygenase from a psychrophilic yeast Glaciozyma antarctica PI12

NASA Astrophysics Data System (ADS)

Yusof, Nik Yusnoraini; Bakar, Farah Diba Abu; Mahadi, Nor Muhammad; Raih, Mohd Firdaus; Murad, Abdul Munir Abdul

2015-09-01

A cDNA encoding Fe(II) 2-oxoglutarate (2OG) dependent dioxygenases was isolated from psychrophilic yeast, Glaciozyma antarctica PI12. We have successfully amplified 1,029 bp cDNA sequence that encodes 342 amino acid with predicted molecular weight 38 kDa. The prediction protein was analysed using various bioinformatics tools to explore the properties of the protein. Based on a BLAST search analysis, the Fe2OX amino acid sequence showed 61% identity to the sequence of oxoglutarate/iron-dependent oxygenase from Rhodosporidium toruloides NP11. SignalP prediction showed that the Fe2OX protein contains no putative signal peptide, which suggests that this enzyme most probably localised intracellularly.The structure of Fe2OX was predicted by homology modelling using MODELLER9v11. The model with the lowest objective function was selected from hundred models generated using MODELLER9v11. Analysis of the structure revealed the longer loop at Fe2OX from G.antarctica that might be responsible for the flexibility of the structure, which contributes to its adaptation to low temperatures. Fe2OX hold a highly conserved Fe(II) binding HXD/E…H triad motif. The binding site for 2-oxoglutarate was found conserved for Arg280 among reported studies, however the Phe268 was found to be different in Fe2OX.

Compositional Reservoir Simulation of Highly Heterogeneous and Anisotropic Fractured Media in 2D and 3D Unstructured Gridding

NASA Astrophysics Data System (ADS)

Zidane, A.; Firoozabadi, A.

2017-12-01

We present an efficient and accurate numerical model for multicomponent compressible single-phase flow in 2D and 3D fractured media based on higher-order discretization. The numerical model accounts for heterogeneity and anisotropy in unstructured gridding with low mesh dependency. The efficiency of our model is demonstrated by having comparable CPU time between fractured and unfractured media. The fracture cross-flow equilibrium approach (FCFE) is applied on triangular finite elements (FE) in 2D. This allows simulating fractured reservoirs with all possible orientations of fractures as opposed to rectangular FE. In 3D we apply the FCFE approach on the prism FE. The prism FE with FCFE allows simulating realistic fractured domains compared to hexahedron FE. In addition, when using FCFE on triangular and prism FE there is no limitation on the number of intersecting fractures, whereas in rectangular and hexahedron FE the number is limited to 2 in 2D and 3 in 3D. To generate domains with complicated boundaries, we have developed a computer-aided design (CAD) interface in our model. The advances introduced in this work are demonstrated through various examples.

Method for Vibration Response Simulation and Sensor Placement Optimization of a Machine Tool Spindle System with a Bearing Defect

PubMed Central

Cao, Hongrui; Niu, Linkai; He, Zhengjia

2012-01-01

Bearing defects are one of the most important mechanical sources for vibration and noise generation in machine tool spindles. In this study, an integrated finite element (FE) model is proposed to predict the vibration responses of a spindle bearing system with localized bearing defects and then the sensor placement for better detection of bearing faults is optimized. A nonlinear bearing model is developed based on Jones' bearing theory, while the drawbar, shaft and housing are modeled as Timoshenko's beam. The bearing model is then integrated into the FE model of drawbar/shaft/housing by assembling equations of motion. The Newmark time integration method is used to solve the vibration responses numerically. The FE model of the spindle-bearing system was verified by conducting dynamic tests. Then, the localized bearing defects were modeled and vibration responses generated by the outer ring defect were simulated as an illustration. The optimization scheme of the sensor placement was carried out on the test spindle. The results proved that, the optimal sensor placement depends on the vibration modes under different boundary conditions and the transfer path between the excitation and the response. PMID:23012514

Finite Element Analysis of Osteosynthesis Screw Fixation in the Bone Stock: An Appropriate Method for Automatic Screw Modelling

PubMed Central

Wieding, Jan; Souffrant, Robert; Fritsche, Andreas; Mittelmeier, Wolfram; Bader, Rainer

2012-01-01

The use of finite element analysis (FEA) has grown to a more and more important method in the field of biomedical engineering and biomechanics. Although increased computational performance allows new ways to generate more complex biomechanical models, in the area of orthopaedic surgery, solid modelling of screws and drill holes represent a limitation of their use for individual cases and an increase of computational costs. To cope with these requirements, different methods for numerical screw modelling have therefore been investigated to improve its application diversity. Exemplarily, fixation was performed for stabilization of a large segmental femoral bone defect by an osteosynthesis plate. Three different numerical modelling techniques for implant fixation were used in this study, i.e. without screw modelling, screws as solid elements as well as screws as structural elements. The latter one offers the possibility to implement automatically generated screws with variable geometry on arbitrary FE models. Structural screws were parametrically generated by a Python script for the automatic generation in the FE-software Abaqus/CAE on both a tetrahedral and a hexahedral meshed femur. Accuracy of the FE models was confirmed by experimental testing using a composite femur with a segmental defect and an identical osteosynthesis plate for primary stabilisation with titanium screws. Both deflection of the femoral head and the gap alteration were measured with an optical measuring system with an accuracy of approximately 3 µm. For both screw modelling techniques a sufficient correlation of approximately 95% between numerical and experimental analysis was found. Furthermore, using structural elements for screw modelling the computational time could be reduced by 85% using hexahedral elements instead of tetrahedral elements for femur meshing. The automatically generated screw modelling offers a realistic simulation of the osteosynthesis fixation with screws in the adjacent bone stock and can be used for further investigations. PMID:22470474

Analytical validation of an explicit finite element model of a rolling element bearing with a localised line spall

NASA Astrophysics Data System (ADS)

Singh, Sarabjeet; Howard, Carl Q.; Hansen, Colin H.; Köpke, Uwe G.

2018-03-01

In this paper, numerically modelled vibration response of a rolling element bearing with a localised outer raceway line spall is presented. The results were obtained from a finite element (FE) model of the defective bearing solved using an explicit dynamics FE software package, LS-DYNA. Time domain vibration signals of the bearing obtained directly from the FE modelling were processed further to estimate time-frequency and frequency domain results, such as spectrogram and power spectrum, using standard signal processing techniques pertinent to the vibration-based monitoring of rolling element bearings. A logical approach to analyses of the numerically modelled results was developed with an aim to presenting the analytical validation of the modelled results. While the time and frequency domain analyses of the results show that the FE model generates accurate bearing kinematics and defect frequencies, the time-frequency analysis highlights the simulation of distinct low- and high-frequency characteristic vibration signals associated with the unloading and reloading of the rolling elements as they move in and out of the defect, respectively. Favourable agreement of the numerical and analytical results demonstrates the validation of the results from the explicit FE modelling of the bearing.

Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

PubMed

Fitzpatrick, Jessica; Kim, Eunsuk

2015-08-18

Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen reactivity of various types of DNICs has been established. N-bound neutral {Fe(NO)2}(10) DNICs react with O2 to generate low-temperature stable peroxynitrite (ONOO(-)) species, which then carry out nitration chemistry in the presence of phenolic substrates, relevant to tyrosine nitration chemistry. The reaction between S-bound anionic {Fe(NO)2}(9) DNICs and O2 results in the formation of Roussin's red esters (RREs) and thiol oxidation products, chemistry that may be important in biological cysteine oxidation. The N-bound cationic {Fe(NO)2}(9) DNICs can spontaneously release NO, and this property can be utilized in developing a new class of NO-donating agents with anti-inflammatory activity.

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.

Formation of 3-monochloro-1,2-propanediol (3-MCPD) di- and monoesters from tristearoylglycerol (TSG) and the potential catalytic effect of Fe²⁺ and Fe³⁺.

PubMed

Zhang, Zhongfei; Gao, Boyan; Zhang, Xiaowei; Jiang, Yuanrong; Xu, Xuebing; Yu, Liangli Lucy

2015-02-18

This study investigated whether and how triacylglycerol (TAG) may serve as a precursor for 3-monochloro-1,2-propanediol (3-MCPD) fatty acid ester formation using tristearoylglycerol (TSG). TSG was reacted with inorganic chloride compounds including NaCl, KCl, FeCl2, CuCl2, ZnCl2, FeCl3 and dry HCl, or organic chlorine compound lindane at different temperatures. Only FeCl2 and FeCl3 were able to form 3-MCPD esters from TSG. Further electron spin resonance (ESR) determination of TSG, Fe2(SO4)3 and 5,5-dimethylpyrroline-N-oxide (DMPO) reactions revealed potential of Fe ion in promoting free radical generations under the experimental conditions. To further confirm the effect of Fe ion, chelating agent (EDTA-2Na) was added to the model reactions. The results showed for the first time that EDTA-2Na was able to reduce the generation of 3-MCPD esters. In addition, FT-IR examination indicated a possible involvement of a carbonyl group during the reaction. Taking all the observations together, the possible mechanisms, involving the formation of either a cyclic acyloxonium or a glycidol ester radical intermediate, were proposed for generating 3-MCPD fatty acid di- and mono- esters from TAG under a high temperature and low moisture condition, as well as the coformation of glycidol esters. The results from this study may be useful for reducing the level of 3-MCPD esters and related toxicants in the refined edible oils and food products.

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4.

PubMed

Wright, Robert J; Zhang, Wei; Yang, Xinzheng; Fasulo, Meg; Tilley, T Don

2012-01-07

Proposed electrocatalytic proton reduction intermediates of hydrogenase mimics were synthesized, observed, and studied computationally. A new mechanism for H(2) generation appears to involve Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3), the dianions {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)Fe(CO)(2)](2-) (3(2-)), the bridging hydride {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)(μ-H)Fe(CO)(2)]}(-), 3H(-)(bridging), and the terminal hydride 3H(-)(term-stag), {[1,2-S(2)C(6)H(4)][HFe(CO)(3)Fe(CO)(3)]}(-), as intermediates. The dimeric sodium derivative of 3(2-), {[Na(2)(THF)(OEt(2))(3)][3(2-)]}(2) (4) was isolated from reaction of Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3) with excess sodium and was characterized by X-ray crystallography. It possesses a bridging CO and an unsymmetrically bridging dithiolate ligand. Complex 4 reacts with 4 equiv. of triflic or benzoic acid (2 equiv. per Fe center) to generate H(2) and 3 in 75% and 60% yields, respectively. Reaction of 4 with 2 equiv. of benzoic acid generated two hydrides in a 1.7 : 1 ratio (by (1)H NMR spectroscopy). Chemical shift calculations on geometry optimized structures of possible hydride isomers strongly suggest that the main product, 3H(-)(bridging), possesses a bridging hydride ligand, while the minor product is a terminal hydride, 3H(-)(term-stag). Computational studies support a catalytic proton reduction mechanism involving a two-electron reduction of 3 that severs an Fe-S bond to generate a dangling thiolate and an electron rich Fe center. The latter iron center is the initial site of protonation, and this event is followed by protonation at the dangling thiolate to give the thiol thiolate [Fe(2)H(CO)(6)(1,2-SHSC(6)H(4))]. This species then undergoes an intramolecular acid-base reaction to form a dihydrogen complex that loses H(2) and regenerates 3.

Vertically aligned P(VDF-TrFE) core-shell structures on flexible pillar arrays

PubMed Central

Choi, Yoon-Young; Yun, Tae Gwang; Qaiser, Nadeem; Paik, Haemin; Roh, Hee Seok; Hong, Jongin; Hong, Seungbum; Han, Seung Min; No, Kwangsoo

2015-01-01

PVDF and P(VDF-TrFE) nano- and micro- structures have been widely used due to their potential applications in several fields, including sensors, actuators, vital sign transducers, and energy harvesters. In this study, we developed vertically aligned P(VDF-TrFE) core-shell structures using high modulus polyurethane acrylate (PUA) pillars as the support structure to maintain the structural integrity. In addition, we were able to improve the piezoelectric effect by 1.85 times from 40 ± 2 to 74 ± 2 pm/V when compared to the thin film counterpart, which contributes to the more efficient current generation under a given stress, by making an effective use of the P(VDF-TrFE) thin top layer as well as the side walls. We attribute the enhancement of piezoelectric effects to the contributions from the shell component and the strain confinement effect, which was supported by our modeling results. We envision that these organic-based P(VDF-TrFE) core-shell structures will be used widely as 3D sensors and power generators because they are optimized for current generations by utilizing all surface areas, including the side walls of core-shell structures. PMID:26040539

Vertically aligned P(VDF-TrFE) core-shell structures on flexible pillar arrays

DOE PAGES

Choi, Yoon-Young; Yun, Tae Gwang; Qaiser, Nadeem; ...

2015-06-04

PVDF and P(VDF-TrFE) nano- and micro- structures are widely used due to their potential applications in several fields, including sensors, actuators, vital sign transducers, and energy harvesters. In this study, we developed vertically aligned P(VDF-TrFE) core-shell structures using high modulus polyurethane acrylate (PUA) pillars as the support structure to maintain the structural integrity. In addition, we were able to improve the piezoelectric effect by 1.85 times from 40 ± 2 to 74 ± 2 pm/V when compared to the thin film counterpart, which contributes to the more efficient current generation under a given stress, by making an effective use ofmore » the P(VDF-TrFE) thin top layer as well as the side walls. We attribute the enhancement of piezoelectric effects to the contributions from the shell component and the strain confinement effect, which was supported by our modeling results. We envision that these organic-based P(VDF-TrFE) core-shell structures will be used widely as 3D sensors and power generators because they are optimized for current generations by utilizing all surface areas, including the side walls of core-shell structures.« less

Refractory Abundances of Terrestrial Planets and Their Stars: Testing [Si/Fe] Correlations with TESS and PLATO

NASA Astrophysics Data System (ADS)

Wolfgang, Angie; Fortney, Jonathan

2018-01-01

In standard models for planet formation, solid material in protoplanetary disks coagulate and collide to form rocky bodies. It therefore seems reasonable to assume that their chemical composition will follow the abundances of refractory elements, such as Si and Fe, in the host star, which has also accreted material from the disk. Backed by planet formation simulations which validate this assumption, planetary internal structure models have begun to use stellar abundances to break degeneracies in low-mass planet compositions inferred only from mass and radius. Inconveniently, our own Solar System contradicts this approach, as its terrestrial bodies exhibit a range of rock/iron ratios and the Sun's [Si/Fe] ratio is offset from the mean planetary [Si/Fe]. In this work, we explore what number and quality of observations we need to empirically measure the exoplanet-star [Si/Fe] correlation, given future transit missions, RV follow-up, and stellar characterization. Specifically, we generate synthetic datasets of terrestrial planet masses and radii and host star abundances assuming that the planets’ bulk [Si/Fe] ratio exactly tracks that of their host stars. We assign measurement uncertainties corresponding to expected precisions for TESS, PLATO, Gaia, and future RV instrumentation, and then invert the problem to infer the planet-star [Si/Fe] correlation given these observational constraints. Comparing the result to the generated truth, we find that 1% precision on the planet radii is needed to test whether [Si/Fe] ratios are correlated between exoplanet and host star. On the other hand, lower precisions can test for systematic offsets between planet and star [Si/Fe], which can constrain the importance of giant impacts for extrasolar terrestrial planet formation.

Fluorinated Dodecaphenylporphyrins: Synthetic and Electrochemical Studies Including the First Evidence of Intramolecular Electron Transfer Between an Fe(II) Porphyrin -Anion Radical and an Fe(I) Porphyrin

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

D'Souza, F.; Forsyth, T.P.; Fukuzumi, S.

1998-10-19

Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (FXDPPS) were synthesized as model compounds for studying electronic effects in nonplan~ porphyrins, and detailed electrochemical studies of the chloroiron(HI) complexes of these compounds were undertaken. The series of porphyrins, represented as FeDPPCl and as FeFXDPPCl where x = 4, 8 (two isomers), 12, 20,28 or 36, could be reversibly oxidized by two electrons in dichloromethane to give n-cation radicals and n-dications. All of the compounds investigated could also be reduced by three electrons in benzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compoundmore » FeDPPC1, whereas the FeFXDPPCl complexes generally exhibited irreversible first and second reductions which were coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss of the chloride ion after generation of Fe FXDPPC1. The second chemical reaction involved a novel intramolecular electron transfer between the initially generated Fe(H) porphyrin n-anion radical and the final Fe(I) porphyrin reduction product. In pyridine, three reversible one electron reductions were observed with the second reduction affording stable Fe(II) porphyrin o - anion radicals for ail of the complexes investigated.« less

A Fe(II)/citrate/UV/PMS process for carbamazepine degradation at a very low Fe(II)/PMS ratio and neutral pH: The mechanisms.

PubMed

Ling, Li; Zhang, Dapeng; Fan, Chihhao; Shang, Chii

2017-11-01

A novel Fe(II)/citrate/UV/PMS process for degrading a model micropollutant, carbamazepine (CBZ), at a low Fe(II)/PMS ratio and neutral pH has been proposed in this study, and the mechanisms of radical generation in the system was explored. With a UV dose of 302.4 mJ/cm 2 , an initial pH of 7, and CBZ, PMS, Fe(II) and citrate at initial concentrations of 10, 100, 12 and 26 μM, respectively, the CBZ degradation efficiency reached 71% in 20 min in the Fe(II)/citrate/UV/PMS process, which was 4.7 times higher than that in either the citrate/UV/PMS or Fe(II)/citrate/PMS process. The enhanced CBZ degradation in the Fe(II)/citrate/UV/PMS process was mainly attributed to the continuous activation of PMS by the UV-catalyzed regenerated Fe(II) from a Fe(III)-citrate complex, [Fe 3 O(cit) 3 H 3 ] 2- , which not only maintained Fe(III) soluble at neutral pH, but also increased 6.6 and 2.6 times of its molar absorbance and quantum yield as compared to those of ionic Fe(III), respectively. In the Fe(II)/citrate/UV/PMS process, the SO 4 •- produced from the fast reaction between PMS and the initially-added Fe(II) contributed 11% of CBZ degradation. The PMS activation by the UV radiation and regenerated Fe(II) contributed additional 14% and 46% of CBZ removal, respectively. The low iron and citrate doses and the fast radical generation at neutral pH make the Fe(II)/citrate/UV/PMS process suitable for degrading recalcitrant organic compounds in potable water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

PubMed

Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

2014-06-01

Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. Copyright © 2014 Elsevier Inc. All rights reserved.

The thermal evolution of Mercury's Fe-Si core

NASA Astrophysics Data System (ADS)

Knibbe, Jurriën Sebastiaan; van Westrenen, Wim

2018-01-01

We have studied the thermal and magnetic field evolution of planet Mercury with a core of Fe-Si alloy to assess whether an Fe-Si core matches its present-day partially molten state, Mercury's magnetic field strength, and the observed ancient crustal magnetization. The main advantages of an Fe-Si core, opposed to a previously assumed Fe-S core, are that a Si-bearing core is consistent with the highly reduced nature of Mercury and that no compositional convection is generated upon core solidification, in agreement with magnetic field indications of a stable layer at the top of Mercury's core. This study also present the first implementation of a conductive temperature profile in the core where heat fluxes are sub-adiabatic in a global thermal evolution model. We show that heat migrates from the deep core to the outer part of the core as soon as heat fluxes at the outer core become sub-adiabatic. As a result, the deep core cools throughout Mercury's evolution independent of the temperature evolution at the core-mantle boundary, causing an early start of inner core solidification and magnetic field generation. The conductive layer at the outer core suppresses the rate of core growth after temperature differences between the deep and shallow core are relaxed, such that a magnetic field can be generated until the present. Also, the outer core and mantle operate at higher temperatures than previously thought, which prolongs mantle melting and mantle convection. The results indicate that S is not a necessary ingredient of Mercury's core, bringing bulk compositional models of Mercury more in line with reduced meteorite analogues.

High particulate iron(II) content in glacially sourced dusts enhances productivity of a model diatom

PubMed Central

Shoenfelt, Elizabeth M.; Sun, Jing; Winckler, Gisela; Kaplan, Michael R.; Borunda, Alejandra L.; Farrell, Kayla R.; Moreno, Patricio I.; Gaiero, Diego M.; Recasens, Cristina; Sambrotto, Raymond N.; Bostick, Benjamin C.

2017-01-01

Little is known about the bioavailability of iron (Fe) in natural dusts and the impact of dust mineralogy on Fe utilization by photosynthetic organisms. Variation in the supply of bioavailable Fe to the ocean has the potential to influence the global carbon cycle by modulating primary production in the Southern Ocean. Much of the dust deposited across the Southern Ocean is sourced from South America, particularly Patagonia, where the waxing and waning of past and present glaciers generate fresh glaciogenic material that contrasts with aged and chemically weathered nonglaciogenic sediments. We show that these two potential sources of modern-day dust are mineralogically distinct, where glaciogenic dust sources contain mostly Fe(II)-rich primary silicate minerals, and nearby nonglaciogenic dust sources contain mostly Fe(III)-rich oxyhydroxide and Fe(III) silicate weathering products. In laboratory culture experiments, Phaeodactylum tricornutum, a well-studied coastal model diatom, grows more rapidly, and with higher photosynthetic efficiency, with input of glaciogenic particulates compared to that of nonglaciogenic particulates due to these differences in Fe mineralogy. Monod nutrient accessibility models fit to our data suggest that particulate Fe(II) content, rather than abiotic solubility, controls the Fe bioavailability in our Fe fertilization experiments. Thus, it is possible for this diatom to access particulate Fe in dusts by another mechanism besides uptake of unchelated Fe (Fe′) dissolved from particles into the bulk solution. If this capability is widespread in the Southern Ocean, then dusts deposited to the Southern Ocean in cold glacial periods are likely more bioavailable than those deposited in warm interglacial periods. PMID:28691098

A Simple Kinetic Model for the Growth of Fe2B Layers on AISI 1026 Steel During the Powder-pack Boriding

NASA Astrophysics Data System (ADS)

Flores-Rentería, M. A.; Ortiz-Domínguez, M.; Keddam, M.; Damián-Mejía, O.; Elias-Espinosa, M.; Flores-González, M. A.; Medina-Moreno, S. A.; Cruz-Avilés, A.; Villanueva-Ibañez, M.

2015-02-01

This work focused on the determination of boron diffusion coefficient through the Fe2B layers on AISI 1026 steel using a mathematical model. The suggested model solves the mass balance equation at the (Fe2B/substrate) interface. This thermochemical treatment was carried out in the temperature range of 1123-1273 K for a treatment time ranging from 2 to 8 h. The generated boride layers were characterized by different experimental techniques such as light optical microscopy, scanning electron microscopy, XRD analysis and the Daimler-Benz Rockwell-C indentation technique. As a result, the boron activation energy for AISI 1026 steel was estimated as 178.4 kJ/mol. Furthermore, this kinetic model was validated by comparing the experimental Fe2B layer thickness with the predicted one at a temperature of 1253 K for 5 h of treatment. A contour diagram relating the layer thickness to the boriding parameters was proposed to be used in practical applications.

Ferrous and ferric ion generation during iron electrocoagulation.

PubMed

Lakshmanan, Divagar; Clifford, Dennis A; Samanta, Gautam

2009-05-15

Our research on arsenate removal by iron electrocoagulation (EC) produced highly variable results, which appeared to be due to Fe2+ generation without subsequent oxidation to Fe3+. Because the environmental technology literature is contradictory with regard to the generation of ferric or ferrous ions during EC, the objective of this research was to establish the iron species generated during EC with iron anodes. Experimental results demonstrated that Fe2+, not Fe3+, was produced at the iron anode. Theoretical current efficiency was attained based on Fe2+ production with a clean iron rod, regardless of current, dissolved-oxygen (DO) level, or pH (6.5-8.5). The Fe2+ remaining after generation and mixing decreased with increasing pH and DO concentration due to rapid oxidation to Fe3+. At pH 8.5, Fe2+ was completely oxidized, which resulted in the desired Fe(OH)3(s)/ FeOOH(s), whereas, at pH 6.5 and 7.5, incomplete oxidation was observed, resulting in a mixture of soluble Fe2+ and insoluble Fe(OH)3(s)/FeOOH(s). When compared with Fe2+ chemical coagulation, a transient pH increase during EC led to faster Fe2+ oxidation. In summary, for EC in the pH 6.5-7.5 range and at low DO conditions, there is a likelihood of soluble Fe2+ species passing through a subsequentfiltration process resulting in secondary contamination and inefficient contaminant removals.

Real-Time Kinetic Probes Support Monothiol Glutaredoxins As Intermediate Carriers in Fe-S Cluster Biosynthetic Pathways.

PubMed

Vranish, James N; Das, Deepika; Barondeau, David P

2016-11-18

Iron-sulfur (Fe-S) clusters are protein cofactors that are required for many essential cellular functions. Fe-S clusters are synthesized and inserted into target proteins by an elaborate biosynthetic process. The insensitivity of most Fe-S assembly and transfer assays requires high concentrations for components and places major limits on reaction complexity. Recently, fluorophore labels were shown to be effective at reporting cluster content for Fe-S proteins. Here, the incorporation of this labeling approach allowed the design and interrogation of complex Fe-S cluster biosynthetic reactions that mimic in vivo conditions. A bacterial Fe-S assembly complex, composed of the cysteine desulfurase IscS and scaffold protein IscU, was used to generate [2Fe-2S] clusters for transfer to mixtures of putative intermediate carrier and acceptor proteins. The focus of this study was to test whether the monothiol glutaredoxin, Grx4, functions as an obligate [2Fe-2S] carrier protein in the Fe-S cluster distribution network. Interestingly, [2Fe-2S] clusters generated by the IscS-IscU complex transferred to Grx4 at rates comparable to previous assays using uncomplexed IscU as a cluster source in chaperone-assisted transfer reactions. Further, we provide evidence that [2Fe-2S]-Grx4 delivers clusters to multiple classes of Fe-S targets via direct ligand exchange in a process that is both dynamic and reversible. Global fits of cluster transfer kinetics support a model in which Grx4 outcompetes terminal target proteins for IscU-bound [2Fe-2S] clusters and functions as an intermediate cluster carrier. Overall, these studies demonstrate the power of chemically conjugated fluorophore reporters for unraveling mechanistic details of biological metal cofactor assembly and distribution networks.

Mesh morphing for finite element analysis of implant positioning in cementless total hip replacements.

PubMed

Bah, Mamadou T; Nair, Prasanth B; Browne, Martin

2009-12-01

Finite element (FE) analysis of the effect of implant positioning on the performance of cementless total hip replacements (THRs) requires the generation of multiple meshes to account for positioning variability. This process can be labour intensive and time consuming as CAD operations are needed each time a specific orientation is to be analysed. In the present work, a mesh morphing technique is developed to automate the model generation process. The volume mesh of a baseline femur with the implant in a nominal position is deformed as the prosthesis location is varied. A virtual deformation field, obtained by solving a linear elasticity problem with appropriate boundary conditions, is applied. The effectiveness of the technique is evaluated using two metrics: the percentages of morphed elements exceeding an aspect ratio of 20 and an angle of 165 degrees between the adjacent edges of each tetrahedron. Results show that for 100 different implant positions, the first and second metrics never exceed 3% and 3.5%, respectively. To further validate the proposed technique, FE contact analyses are conducted using three selected morphed models to predict the strain distribution in the bone and the implant micromotion under joint and muscle loading. The entire bone strain distribution is well captured and both percentages of bone volume with strain exceeding 0.7% and bone average strains are accurately computed. The results generated from the morphed mesh models correlate well with those for models generated from scratch, increasing confidence in the methodology. This morphing technique forms an accurate and efficient basis for FE based implant orientation and stability analysis of cementless hip replacements.

Creating physically-based three-dimensional microstructures: Bridging phase-field and crystal plasticity models.

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

Lim, Hojun; Owen, Steven J.; Abdeljawad, Fadi F.

In order to better incorporate microstructures in continuum scale models, we use a novel finite element (FE) meshing technique to generate three-dimensional polycrystalline aggregates from a phase field grain growth model of grain microstructures. The proposed meshing technique creates hexahedral FE meshes that capture smooth interfaces between adjacent grains. Three dimensional realizations of grain microstructures from the phase field model are used in crystal plasticity-finite element (CP-FE) simulations of polycrystalline a -iron. We show that the interface conformal meshes significantly reduce artificial stress localizations in voxelated meshes that exhibit the so-called "wedding cake" interfaces. This framework provides a direct linkmore » between two mesoscale models - phase field and crystal plasticity - and for the first time allows mechanics simulations of polycrystalline materials using three-dimensional hexahedral finite element meshes with realistic topological features.« less

Modeling Verwey transition temperature of Fe3O4 nanocrystals

NASA Astrophysics Data System (ADS)

Jiang, Xiao bao; Xiao, Bei bei; Yang, Hong yu; Gu, Xiao yan; Sheng, Hong chao; Zhang, Xing hua

2016-11-01

The Verwey transition in nanoscale is an important physical property for Fe3O4 nanocrystals and has attracted extensive attention in recent years. In this work, an analytic thermodynamic model without any adjusting parameters is developed to estimate the size and shape effects on modulating the Verwey transition temperature of Fe3O4 nanocrystals. The results show that the Verwey transition temperature reduces with increasing shape parameter λ or decreasing size D. A good agreement between the prediction and the experimental data verified our physical insight that the Verwey transition of Fe3O4 can be directly related to the atomic thermal vibration. The results presented in this work will be of benefit to the understanding of the microscopic mechanism of the Verwey transition and the design of future generation switching and memory devices.

Fe-Distribution and Hydrogen Generation During Serpentinization

NASA Astrophysics Data System (ADS)

Klein, F.; Bach, W.; Jöns, N.; McCollom, T.; Berquó, T.; Moskowitz, B.

2009-04-01

Serpentinization of peridotite generates large amounts of dihydrogen (H2,aq), indicated by the presence of Ni-Fe alloys and low-sulfur-fugacity sulfides, e. g. awaruite and pentlandite, in serpentinites. Hydrogen is produced when ferrous iron in olivine is oxidized by water to ferric iron in secondary magnetite and serpentine. This process is strongly dependent on bulk rock composition, water-to-rock ratio and temperature. These relations were examined in thermodynamic reaction path models (using the EQ3/6 computer code) with dunitic and harzburgitic rock compositions. The model results were compared with electron microprobe analyses, bulk magnetization measurements, and Mößbauer spectroscopy of partially to fully serpentinized dunites and harzburgites from Ocean Drilling Program Leg 209, Hole 1274A, Mid-Atlantic Ridge 15 °N. These samples have mesh rims that reveal a distinct in-to-out zoning, starting with brucite (Mg# 80) at the interface with olivine, then a zone of serpentine (Mg# 95) + brucite ± magnetite, and finally serpentine + magnetite in the outermost mesh rim. The composition of co-existing serpentine and brucite in pseudomorphic mesh rims is virtually constant in most samples from 32 to 147 meters below seafloor, suggesting similar alteration conditions of olivine downhole. Bulk magnetization measurements of microdrilled mesh rims in combination with thin section petrography revealed a positive correlation of magnetite content with extent of serpentinization. Where relic olivine is present, the magnetite content is significantly lower then in fully serpentinized rocks. In these domains with sparse magnetite, Mößbauer spectra revealed Fe3+/‘ Fe values between 0.30 and 0.48 for paramagnetic minerals in the mesh rims (i. e., secondary hydrous phases). In heavily to completely serpentinized rocks with abundant magnetite, Fe3+/‘ Fe values of the paramagnetic phases are consistently higher and range from 0.53 to 0.68. In the EQ3/6 runs, a serpentine solid solution model that includes greenalite and hisingerite (Fe2Si2O5(OH)4) was used in investigating the distribution of iron between serpentine and magnetite and its oxidation state in serpentine. Our model computations predict that above 330 °C and water activities near unity, the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen is significantly obstructed by the dearth of silica. At these temperatures, hydrogen fugacities are too low for awaruite and pentlandite to be stable. When temperatures drop below 320-330 °C, brucite becomes stable and hydrogen generation is facilitated, because the reaction of olivine to serpentine, magnetite and brucite requires no external silica. The MgO-FeO-Fe2O3-SiO2-H2O and Fe-Ni-Co-O-S phase relations observed in the mesh rims suggest that serpentine and brucite from Hole 1274A likely formed at temperatures between 150 and 250 °C and water-to-rock ratios (w/r) between 5 and 0.1. However, formation of awaruite must have taken place during main stage serpentinization at temperatures between 200-250 °C and w/r < 1, when alteration conditions were sufficiently reducing. Likewise, the model predicts the Fe3+/‘ Fe ratios of mesh-rim serpentine/brucite observed in incompletely serpentinized rocks of serpentine (0.3 to 0.5) at low w/r ratios and T < 250 °C. The calculation results furthermore indicate that elevated Fe3+/‘ Fe ratios (0.5 to 0.7) measured in fully serpentinized rocks appear to correspond to higher w/r ratios and less reducing conditions. Our study indicates that unprecedented details about the reaction sequences during serpentinization may be obtained from merging careful petrographic, magnetic, and spectroscopic analyses with comprehensive thermodynamic modeling.

Discrepancies in anthropometric parameters between different models affect intervertebral rotations when loading finite element models with muscle forces from inverse static analyses.

PubMed

Zhu, Rui; Rohlmann, Antonius

2014-06-01

In only a few published finite element (FE) simulations have muscle forces been applied to the spine. Recently, muscle forces determined using an inverse static (IS) model of the spine were transferred to a spinal FE model, and the effect of methodical parameters was investigated. However, the sensitivity of anthropometric differences between FE and IS models, such as body height and spinal orientation, was not considered. The aim of this sensitivity study was to determine the influence of those differences on the intervertebral rotations (IVRs) following the transfer of muscle forces from an IS model to a FE model. Muscle forces were estimated for 20° flexion and 10° extension of the upper body using an inverse static musculoskeletal model. These forces were subsequently transferred to a nonlinear FE model of the spino-pelvic complex, which includes 243 muscle fascicles. Deviations of body height (±10 cm), spinal orientation in the sagittal plane (±10°), and body weight (±10 kg) between both models were intentionally generated, and their influences on IVRs were determined. The changes in each factor relative to their corresponding reference value of the IS model were calculated. Deviations in body height, spinal orientation, and body weight resulted in maximum changes in the IVR of 19.2%, 26% and 4.2%, respectively, relative to T12-S1 IVR. When transferring muscle forces from an IS to a FE model, it is crucial that both models have the same spinal orientation and height. Additionally, the body weight should be equal in both models.

A microscopic solution to the magnetic detwinning mystery in EuFe2As2

NASA Astrophysics Data System (ADS)

Maiwald, J.; Mazin, I. I.; Nandi, S.; Xiao, Y.; Gegenwart, P.

One of the greatest recent advances in studying nematic phenomena in Fe-based superconductors was the mechanical detwinning of the 122-family compounds. Unfortunately, these techniques generate considerable stress in the investigated samples, which contaminates the results. Recently, we observed that a minuscule magnetic field of the order of 0.1 T irreversibly and persistently detwins EuFe2As2, opening an entirely new avenue for addressing nematicity. However, further development was hindered by the absence of a microscopic theory explaining this magnetic detwinning. In fact, Eu2+ has zero orbital moment and does not couple to the lattice, and its exchange coupling with the Fe sublattice cancels by symmetry. Moreover, further increase of the field to 1 T leads to a reorientation of Fe domains, while even larger fields 10 T reorient the domains once again. We will present a new microscopic model, based on a sizable biquadratic coupling between the Fe 3 d and Eu 4 f moments. This model quantitatively explains our old and new magnetization and neutron diffraction data, thus removing the veil of mystery and finally opening the door to full-scale research into magnetic detwinning and nematicity in Fe-based superconductors.

A downloadable meshed human canine tooth model with PDL and bone for finite element simulations.

PubMed

Boryor, Andrew; Hohmann, Ansgar; Geiger, Martin; Wolfram, Uwe; Sander, Christian; Sander, Franz Günter

2009-09-01

The aim of this study is to relieve scientists from the complex and time-consuming task of model generation by providing a model of a canine tooth and its periradicular tissues for Finite Element Method (FEM) simulations. This was achieved with diverse commercial software, based on a micro-computed tomography of the specimen. The Finite Element (FE) Model consists of enamel, dentin, nerve (innervation), periodontal ligament (PDL), and the surrounding cortical bone with trabecular structure. The area and volume meshes are of a very high quality in order to represent the model in a detailed form. Material properties are to be set individually by every user. The tooth model is provided for Abaqus, Ansys, HyperMesh, Nastran and as STL files, in an ASCII format for free download. This can help reduce the cost and effort of generating a tooth model for some research institutions, and may encourage other research groups to provide their high quality models for other researchers. By providing FE models, research results, especially FEM simulations, could be easily verified by others.

The Use of a Vehicle Acceleration Exposure Limit Model and a Finite Element Crash Test Dummy Model to Evaluate the Risk of Injuries During Orion Crew Module Landings

NASA Technical Reports Server (NTRS)

Lawrence, Charles; Fasanella, Edwin L.; Tabiei, Ala; Brinkley, James W.; Shemwell, David M.

2008-01-01

A review of astronaut whole body impact tolerance is discussed for land or water landings of the next generation manned space capsule named Orion. LS-DYNA simulations of Orion capsule landings are performed to produce a low, moderate, and high probability of injury. The paper evaluates finite element (FE) seat and occupant simulations for assessing injury risk for the Orion crew and compares these simulations to whole body injury models commonly referred to as the Brinkley criteria. The FE seat and crash dummy models allow for varying the occupant restraint systems, cushion materials, side constraints, flailing of limbs, and detailed seat/occupant interactions to minimize landing injuries to the crew. The FE crash test dummies used in conjunction with the Brinkley criteria provides a useful set of tools for predicting potential crew injuries during vehicle landings.

Minerals Masquerading As Enzymes: Abiotic Oxidation Of Soil Organic Matter In An Iron-Rich Humid Tropical Forest Soil

NASA Astrophysics Data System (ADS)

Hall, S. J.; Silver, W. L.

2010-12-01

Oxidative reactions play an important role in decomposing soil organic matter fractions that resist hydrolytic degradation, and fundamentally affect the cycling of recalcitrant soil carbon across ecosystems. Microbial extracellular oxidative enzymes (e.g. lignin peroxidases and laccases) have been assumed to provide a dominant role in catalyzing soil organic matter oxidation, while other potential oxidative mechanisms remain poorly explored. Here, we show that abiotic reactions mediated by the oxidation of ferrous iron (Fe(II)) could explain high potential oxidation rates in humid tropical forest soils, which often contain high concentrations of Fe(II) and experience rapid redox fluctuations between anaerobic and aerobic conditions. These abiotic reactions could provide an additional mechanism to explain high rates of decomposition in these ecosystems, despite frequent oxygen deficits. We sampled humid tropical forest soils in Puerto Rico, USA from various topographic positions, ranging from well-drained ridges to riparian valleys that experience broad fluctuations in redox potential. We measured oxidative activity by adding the model humic compound L-DOPA to soil slurries, followed by colorimetric measurements of the supernatant solution over time. Dilute hydrogen peroxide was added to a subset of slurries to measure peroxidative activity. We found that oxidative and peroxidative activity correlated positively with soil Fe(II) concentrations, counter to prevailing theory that low redox potential should suppress oxidative enzymes. Boiling or autoclaving sub-samples of soil slurries to denature any enzymes present typically increased peroxidative activity and did not eliminate oxidative activity, further suggesting the importance of an abiotic mechanism. We found substantial differences in the oxidation products of the L-DOPA substrate generated by our soil slurries in comparison with oxidation products generated by a purified enzyme (mushroom tyrosinase). Tyrosinase generated a red compound (dopachrome) that is the target analyte of the traditional L-DOPA oxidative enzyme assay, whereas our soil slurries generated purple melanin-like compounds that were likely generated by more extensive oxidation. To investigate the importance of Fe(II) for L-DOPA oxidation, we added realistic concentrations of Fe(II) (equivalent to 10 - 500 μg Fe g-1 soil) to an L-DOPA buffer solution under oxic conditions, and found rates of L-DOPA oxidation comparable to those from soil slurries. Molecular oxygen and Fe(II) are known to generate strong oxidants via Fenton reactions. We decreased L-DOPA oxidation rates in soil slurries by adding catalase and superoxide-dismutase enzymes to scavenge reactive oxygen species, suggesting that a free-radical mechanism contributed to L-DOPA oxidation. We obtained similar results using another humic model compound, tetramethylbenzidine (TMB). Although abiotic oxidative reactions involving iron have been employed to degrade anthropogenic organic contaminants, this study is among the first to demonstrate their potential importance for oxidizing organic matter in natural ecosystems. In soils rich in Fe(II), abiotic reactions could complement, or even obviate, the role of microbial oxidative enzymes in degrading recalcitrant organic compounds.

Experimental modeling of the interaction of subducted carbonates and sulfur with mantle silicates

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Sobolev, N. V.

2016-09-01

Experimental studies in the system Fe,Ni-olivine-carbonate-S ( P = 6.3 GPa, T = 1050-1550°C, t = 40-60 h) aimed at modeling of the interaction of subducted carbonates and sulfur with rocks of the silicate mantle and at investigation of the likely mechanism of the formation of mantle sulfides were performed. It is shown that an association of olivine + orthopyroxene + magnesite + pyrite coexisting with a sulfur melt/fluid with dissolved Fe, Ni, and O is formed at T ≤ 1250°C. An association of low-Fe olivine, orthopyroxene, and magnesite and two immiscible melts of the carbonate and S-Fe-Ni-O compositions are formed at T ≥ 1350°C. It is shown that the reduced S-bearing fluids may transform silicates and carbonates, extract metals from the solid-phase matrix, and provide conditions for generation of sulfide melts.

Oxoiron(IV) complexes as synthons for the assembly of heterobimetallic centers such as the Fe/Mn active site of Class Ic ribonucleotide reductases.

PubMed

Zhou, Ang; Crossland, Patrick M; Draksharapu, Apparao; Jasniewski, Andrew J; Kleespies, Scott T; Que, Lawrence

2018-01-01

Nonheme oxoiron(IV) complexes can serve as synthons for generating heterobimetallic oxo-bridged dimetal complexes by reaction with divalent metal complexes. The formation of Fe III -O-Cr III and Fe III -O-Mn III complexes is described herein. The latter complexes may serve as models for the Fe III -X-Mn III active sites of an emerging class of Fe/Mn enzymes represented by the Class 1c ribonucleotide reductase from Chlamydia trachomatis and the R2-like ligand-binding oxidase (R2lox) found in Mycobacterium tuberculosis. These synthetic complexes have been characterized by UV-Vis, resonance Raman, and X-ray absorption spectroscopy, as well as electrospray mass spectrometry. The Fe III -O-Cr III complexes exhibit a three-band UV-Vis pattern that differs from the simpler features associated with Fe III -O-Fe III complexes. The positions of these features are modulated by the nature of the supporting polydentate ligand on the iron center, and their bands intensify dramatically in two examples upon the binding of an axial cyanate or thiocyanate ligand trans to the oxo bridge. In contrast, the Fe III -O-Mn III complexes resemble Fe III -O-Fe III complexes more closely. Resonance Raman characterization of the Fe III -O-M III complexes reveals an 18 O-sensitive vibration in the range of 760-890 cm -1 . This feature has been assigned to the asymmetric Fe III -O-M III stretching mode and correlates reasonably with the Fe-O bond distance determined by EXAFS analysis. The likely binding of an acetate as a bridging ligand to the Fe III -O-Mn III complex 12 lays the foundation for further efforts to model the heterobimetallic active sites of Fe/Mn enzymes.

Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases.

PubMed

Song, Li-Cheng; Cao, Meng; Wang, Yong-Xiang

2015-04-21

The homodinuclear complexes [Ni(RNPyS4)]2 (; RNPyS4 = 2,6-bis(2-mercaptophenylthiomethyl)-4-R-pyridine; R = H, MeO, Cl, Br, i-Pr) were found to be prepared by reactions of the in situ generated Li2[Ni(1,2-S2C6H4)2] with 2,6-bis[(tosyloxy)methyl]pyridine and its substituted derivatives 2,6-bis[(tosyloxy)methyl]-4-R-pyridine. Further reactions of with Fe3(CO)12 gave both heterotrinuclear complexes NiFe2(RNPyS4)(CO)5 () and mononuclear complexes Fe(RNPyS4)(CO) (), unexpectedly. Interestingly, complexes and could be regarded as models for the active sites of [NiFe]- and [Fe]-hydrogenases, respectively. All the prepared complexes were characterized by elemental analysis, spectroscopy, and particularly for some of them, by X-ray crystallography. In addition, the electrochemical properties of and as well as the electrocatalytic H2 production catalyzed by and were investigated by CV techniques.

Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

NASA Astrophysics Data System (ADS)

Zhang, Peng; Yuan, Songhu

2017-12-01

Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe(II)-citrate- oxidation. Most soluble Fe3+ that is produced from pyrite oxidation hydrolyzes to Fe(III) hydroxide. Kinetic models that were developed according to the proposed mechanisms identified the relative importance of each reaction for radOH production. Using the kinetic model, the oxidation efficiencies of the redox-active substances that react with radOH at different reaction-rate constants were estimated in the presence of 1 mM citrate. This study presents on the overlooked role of LMWOAs in enhancing radOH production from pyrite oxidation by O2 in pyrite-rich circumneutral environments, such as marine and estuarine sediments and salt marshes.

Carbon-enhanced metal-poor stars: relics from the dark ages

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

Cooke, Ryan J.; Madau, Piero, E-mail: rcooke@ucolick.org

2014-08-20

We use detailed nucleosynthesis calculations and a realistic prescription for the environment of the first stars to explore the first episodes of chemical enrichment that occurred during the dark ages. Based on these calculations, we propose a novel explanation for the increased prevalence of carbon-enhanced metal-poor (CEMP) stars with decreasing Fe abundance: the observed chemistry for the most metal-poor Galactic halo stars is the result of an intimate link between the explosions of the first stars and their host minihalo's ability to retain its gas. Specifically, high-energy supernovae produce a near solar ratio of C/Fe, but are effective in evacuatingmore » the gas from their host minihalo, thereby suppressing the formation of a second generation of stars. On the other hand, minihalos that host low-energy supernovae are able to retain their gas and form a second stellar generation, but, as a result, the second stars are born with a supersolar ratio of C/Fe. Our models are able to accurately reproduce the observed distributions of [C/Fe] and [Fe/H], as well as the fraction of CEMP stars relative to non-CEMP stars as a function of [Fe/H] without any free parameters. We propose that the present lack of chemical evidence for very massive stars (≳ 140 M {sub ☉}) that ended their lives as a highly energetic pair-instability supernova does not imply that such stars were rare or did not exist; the chemical products of these very massive first stars may have been evacuated from their host minihalos and were never incorporated into subsequent generations of stars. Finally, our models suggest that the most Fe-poor stars currently known may have seen the enrichment from a small multiple of metal-free stars, and need not have been exclusively enriched by a solitary first star. These calculations also add further support to the possibility that some of the surviving dwarf satellite galaxies of the Milky Way are the relics of the first galaxies.« less

Biomechanical behavior of cavity configuration on micropush-out test: a finite-element-study.

PubMed

Cekic-Nagas, Isil; Shinya, Akikazu; Ergun, Gulfem; Vallittu, Pekka K; Lassila, Lippo V J

2011-01-01

The objective of this study was to simulate the micropush-out bond strength test from a biomechanical point of view. For this purpose, stress analysis using finite element (FE) method was performed. Three different occlusal cavity shapes were simulated in disc specimens (model A: 1.5 mm cervical, 2 mm occlusal diameter; model B: 1.5 mm cervical, 1.75 mm occlusal diameter; model C: 1.5 mm cervical, 1.5 mm occlusal diameter). Quarter sizes of 3D FE specimen models of 4.0 x 4.0 x 1.25 mm3 were constructed. In order to avoid quantitative differences in the stress value in the models, models were derived from a single mapping mesh pattern that generated 47.182 elements and 66.853 nodes. The materials that were used were resin composite (Filtek Z250, 3M ESPE), bonding agent (Adper Scotchbond Multi-Purpose, 3M ESPE) and dentin as an isotropic material. Loading conditions consisted of subjecting a press of 4 MPa to the top of the resin composite discs. The postprocessing files allowed the calculation of the maximum principal stress, minimum principal stress and displacement within the disc specimens and stresses at the bonding layer. FE model construction and analysis were performed on PC workstation (Precision Work Station 670, Dell Inc.) using FE analysis program (ANSYS 10 Sp, ANSYS Inc.). Compressive stress concentrations were observed equally in the bottom interface edge of dentin. Tensile stresses were observed on the top area of dentin and at the half of lower side of composite under the loading point in all of the FE models. The FE model revealed differences in displacement and stress between different cavity shaped disc specimens. As the slope of the cavity was increased, the maximum displacement, compressive and tensile stresses also increased.

Fluid-structure interaction study of transcatheter aortic valve dynamics using smoothed particle hydrodynamics

PubMed Central

Mao, Wenbin; Li, Kewei; Sun, Wei

2016-01-01

Computational modeling of heart valve dynamics incorporating both fluid dynamics and valve structural responses has been challenging. In this study, we developed a novel fully-coupled fluid-structure interaction (FSI) model using smoothed particle hydrodynamics (SPH). A previously developed nonlinear finite element (FE) model of transcatheter aortic valves (TAV) was utilized to couple with SPH to simulate valve leaflet dynamics throughout the entire cardiac cycle. Comparative simulations were performed to investigate the impact of using FE-only models versus FSI models, as well as an isotropic versus an anisotropic leaflet material model in TAV simulations. From the results, substantial differences in leaflet kinematics between FE-only and FSI models were observed, and the FSI model could capture the realistic leaflet dynamic deformation due to its more accurate spatial and temporal loading conditions imposed on the leaflets. The stress and the strain distributions were similar between the FE and FSI simulations. However, the peak stresses were different due to the water hammer effect induced by the flow inertia in the FSI model during the closing phase, which led to 13%–28% lower peak stresses in the FE-only model compared to that of the FSI model. The simulation results also indicated that tissue anisotropy had a minor impact on hemodynamics of the valve. However, a lower tissue stiffness in the radial direction of the leaflets could reduce the leaflet peak stress caused by the water hammer effect. It is hoped that the developed FSI models can serve as an effective tool to better assess valve dynamics and optimize next generation TAV designs. PMID:27844463

Fluid-Structure Interaction Study of Transcatheter Aortic Valve Dynamics Using Smoothed Particle Hydrodynamics.

PubMed

Mao, Wenbin; Li, Kewei; Sun, Wei

2016-12-01

Computational modeling of heart valve dynamics incorporating both fluid dynamics and valve structural responses has been challenging. In this study, we developed a novel fully-coupled fluid-structure interaction (FSI) model using smoothed particle hydrodynamics (SPH). A previously developed nonlinear finite element (FE) model of transcatheter aortic valves (TAV) was utilized to couple with SPH to simulate valve leaflet dynamics throughout the entire cardiac cycle. Comparative simulations were performed to investigate the impact of using FE-only models vs. FSI models, as well as an isotropic vs. an anisotropic leaflet material model in TAV simulations. From the results, substantial differences in leaflet kinematics between FE-only and FSI models were observed, and the FSI model could capture the realistic leaflet dynamic deformation due to its more accurate spatial and temporal loading conditions imposed on the leaflets. The stress and the strain distributions were similar between the FE and FSI simulations. However, the peak stresses were different due to the water hammer effect induced by the fluid inertia in the FSI model during the closing phase, which led to 13-28% lower peak stresses in the FE-only model compared to that of the FSI model. The simulation results also indicated that tissue anisotropy had a minor impact on hemodynamics of the valve. However, a lower tissue stiffness in the radial direction of the leaflets could reduce the leaflet peak stress caused by the water hammer effect. It is hoped that the developed FSI models can serve as an effective tool to better assess valve dynamics and optimize next generation TAV designs.

A nano-disperse ferritin-core mimetic that efficiently corrects anemia without luminal iron redox activity

PubMed Central

Powell, Jonathan J.; Bruggraber, Sylvaine F.A.; Faria, Nuno; Poots, Lynsey K.; Hondow, Nicole; Pennycook, Timothy J.; Latunde-Dada, Gladys O.; Simpson, Robert J.; Brown, Andy P.; Pereira, Dora I.A.

2014-01-01

The 2-5 nm Fe(III) oxo-hydroxide core of ferritin is less ordered and readily bioavailable compared to its pure synthetic analogue, ferrihydrite. We report the facile synthesis of tartrate-modified, nano-disperse ferrihydrite of small primary particle size, but with enlarged or strained lattice structure (~ 2.7 Å for the main Bragg peak versus 2.6 Å for synthetic ferrihydrite). Analysis indicated that co-precipitation conditions can be achieved for tartrate inclusion into the developing ferrihydrite particles, retarding both growth and crystallization and favoring stabilization of the cross-linked polymeric structure. In murine models, gastrointestinal uptake was independent of luminal Fe(III) reduction to Fe(II) and, yet, absorption was equivalent to that of ferrous sulphate, efficiently correcting the induced anemia. This process may model dietary Fe(III) absorption and potentially provide a side effect-free form of cheap supplemental iron. From the Clinical Editor Small size tartrate-modified, nano-disperse ferrihydrite was used for efficient gastrointestinal delivery of soluble Fe(III) without the risk for free radical generation in murine models. This method may provide a potentially side effect-free form iron supplementation. PMID:24394211

Mössbauer, EPR, and Modeling Study of Iron Trafficking and Regulation in Δccc1 and CCC1-up Saccharomyces cerevisiae

PubMed Central

2015-01-01

Strains lacking and overexpressing the vacuolar iron (Fe) importer CCC1 were characterized using Mössbauer and EPR spectroscopies. Vacuolar Fe import is impeded in Δccc1 cells and enhanced in CCC1-up cells, causing vacuolar Fe in these strains to decline and accumulate, respectively, relative to WT cells. Cytosolic Fe levels should behave oppositely. The Fe content of Δccc1 cells grown under low-Fe conditions was similar to that in WT cells. Most Fe was mitochondrial with some nonheme high spin (NHHS) FeII present. Δccc1 cells grown with increasing Fe concentration in the medium contained less total Fe, less vacuolar HS FeIII, and more NHHS FeII than in comparable WT cells. As the Fe concentration in the growth medium increased, the concentration of HS FeIII in Δccc1 cells increased to just 60% of WT levels, while NHHS FeII increased to twice WT levels, suggesting that the NHHS FeII was cytosolic. Δccc1 cells suffered more oxidative damage than WT cells, suggesting that the accumulated NHHS FeII promoted Fenton chemistry. The Fe concentration in CCC1-up cells was higher than in WT cells; the extra Fe was present as NHHS FeII and FeIII and as FeIII oxyhydroxide nanoparticles. These cells contained less mitochondrial Fe and exhibited less ROS damage than Δccc1 cells. CCC1-up cells were adenine-deficient on minimal medium; supplementing with adenine caused a decline of NHHS FeII suggesting that some of the NHHS FeII that accumulated in these cells was associated with adenine deficiency rather than the overexpression of CCC1. A mathematical model was developed that simulated changes in Fe distributions. Simulations suggested that only a modest proportion of the observed NHHS FeII in both strains was the cytosolic form of Fe that is sensed by the Fe import regulatory system. The remainder is probably generated by the reduction of the vacuolar NHHS FeIII species. PMID:24785783

Mössbauer, EPR, and modeling study of iron trafficking and regulation in Δccc1 and CCC1-up Saccharomyces cerevisiae.

PubMed

Cockrell, Allison; McCormick, Sean P; Moore, Michael J; Chakrabarti, Mrinmoy; Lindahl, Paul A

2014-05-13

Strains lacking and overexpressing the vacuolar iron (Fe) importer CCC1 were characterized using Mössbauer and EPR spectroscopies. Vacuolar Fe import is impeded in Δccc1 cells and enhanced in CCC1-up cells, causing vacuolar Fe in these strains to decline and accumulate, respectively, relative to WT cells. Cytosolic Fe levels should behave oppositely. The Fe content of Δccc1 cells grown under low-Fe conditions was similar to that in WT cells. Most Fe was mitochondrial with some nonheme high spin (NHHS) Fe(II) present. Δccc1 cells grown with increasing Fe concentration in the medium contained less total Fe, less vacuolar HS Fe(III), and more NHHS Fe(II) than in comparable WT cells. As the Fe concentration in the growth medium increased, the concentration of HS Fe(III) in Δccc1 cells increased to just 60% of WT levels, while NHHS Fe(II) increased to twice WT levels, suggesting that the NHHS Fe(II) was cytosolic. Δccc1 cells suffered more oxidative damage than WT cells, suggesting that the accumulated NHHS Fe(II) promoted Fenton chemistry. The Fe concentration in CCC1-up cells was higher than in WT cells; the extra Fe was present as NHHS Fe(II) and Fe(III) and as Fe(III) oxyhydroxide nanoparticles. These cells contained less mitochondrial Fe and exhibited less ROS damage than Δccc1 cells. CCC1-up cells were adenine-deficient on minimal medium; supplementing with adenine caused a decline of NHHS Fe(II) suggesting that some of the NHHS Fe(II) that accumulated in these cells was associated with adenine deficiency rather than the overexpression of CCC1. A mathematical model was developed that simulated changes in Fe distributions. Simulations suggested that only a modest proportion of the observed NHHS Fe(II) in both strains was the cytosolic form of Fe that is sensed by the Fe import regulatory system. The remainder is probably generated by the reduction of the vacuolar NHHS Fe(III) species.

Experiments, constitutive modeling and FE simulations of the impact behavior of Molybdenum

NASA Astrophysics Data System (ADS)

Kleiser, Geremy; Revil-Baudard, Benoit

For polycrystalline high-purity molybdenum the feasibility of a Taylor test is questionable because the very large tensile stresses generated at impact would result in disintegration of the specimen. We report an experimental investigation and new model to account simultaneously for the experimentally observed anisotropy, tension-compression asymmetry and strain-rate sensitivity of this material. To ensure high-fidelity predictions, a fully-implicit algorithm was used for implementing the new model in the FE code ABAQUS. Based on model predictions, the impact velocity range was established for which specimens may be recovered. Taylor impact tests in this range (140-165 m/s) were successfully conducted for different specimen taken along the rolling direction (RD), the transverse direction and 45o to the RD. Comparison between the measured profiles of impact specimens and FE model predictions show excellent agreement. Furthermore, simulations were performed to gain understanding of the dynamic event: time evolution of the pressure, the extent of plastic deformation, distribution of plastic strain rates, and transition to quasi-stable deformation occurs.

Knowledge-Based Planning Model for Courses of Action Generation,

DTIC Science & Technology

1986-04-07

AO-AIS 608 KNOWLEDGE-BASED PLANNING MODEL FOR COURSES OF ACTION mJI OENERATION(U) ARMY MAR COLL CARLISLE BARRACKS PA USI FE D R COLLINS ET AL. 97APR...agencies. This document may not be released for open publication until it has been cleared by the appropriate military service or government agency. 00 DTIC...I ELECTE KNOWLEDGE-BASED PLANNING MODEL C AUG 5~ FOR COURSES OF ACTION GENERATION DD BY COLONEL D. R. COLLINS LIEUTENANT COLONEL(P) T. A. BAUCUM

3D micro-crack propagation simulation at enamel/adhesive interface using FE submodeling and element death techniques.

PubMed

Liu, Heng-Liang; Lin, Chun-Li; Sun, Ming-Tsung; Chang, Yen-Hsiang

2010-06-01

This study investigates micro-crack propagation at the enamel/adhesive interface using finite element (FE) submodeling and element death techniques. A three-dimensional (3D) FE macro-model of the enamel/adhesive/ceramic subjected to shear bond testing was generated and analyzed. A 3D micro-model with interfacial bonding structure was constructed at the upper enamel/adhesive interface where the stress concentration was found from the macro-model results. The morphology of this interfacial bonding structure (i.e., resin tag) was assigned based on resin tag geometry and enamel rod arrangement from a scanning electron microscopy micrograph. The boundary conditions for the micro-model were determined from the macro-model results. A custom iterative code combined with the element death technique was used to calculate the micro-crack propagation. Parallel experiments were performed to validate this FE simulation. The stress concentration within the adhesive occurred mainly at the upper corner near the enamel/adhesive interface and the resin tag base. A simulated fracture path was found at the resin tag base along the enamel/adhesive interface. A morphological observation of the fracture patterns obtained from in vitro testing corresponded with the simulation results. This study shows that the FE submodeling and element death techniques could be used to simulate the 3D micro-stress pattern and the crack propagation noted at the enamel/adhesive interface.

Development of digital phantoms based on a finite element model to simulate low-attenuation areas in CT imaging for pulmonary emphysema quantification.

PubMed

Diciotti, Stefano; Nobis, Alessandro; Ciulli, Stefano; Landini, Nicholas; Mascalchi, Mario; Sverzellati, Nicola; Innocenti, Bernardo

2017-09-01

To develop an innovative finite element (FE) model of lung parenchyma which simulates pulmonary emphysema on CT imaging. The model is aimed to generate a set of digital phantoms of low-attenuation areas (LAA) images with different grades of emphysema severity. Four individual parameter configurations simulating different grades of emphysema severity were utilized to generate 40 FE models using ten randomizations for each setting. We compared two measures of emphysema severity (relative area (RA) and the exponent D of the cumulative distribution function of LAA clusters size) between the simulated LAA images and those computed directly on the models output (considered as reference). The LAA images obtained from our model output can simulate CT-LAA images in subjects with different grades of emphysema severity. Both RA and D computed on simulated LAA images were underestimated as compared to those calculated on the models output, suggesting that measurements in CT imaging may not be accurate in the assessment of real emphysema extent. Our model is able to mimic the cluster size distribution of LAA on CT imaging of subjects with pulmonary emphysema. The model could be useful to generate standard test images and to design physical phantoms of LAA images for the assessment of the accuracy of indexes for the radiologic quantitation of emphysema.

A method to generate conformal finite-element meshes from 3D measurements of microstructurally small fatigue-crack propagation [A method to generate conformal finite-element meshes from 3D measurements of microstructurally small fatigue-crack propagation: 3D Meshes of Microstructurally Small Crack Growth

DOE PAGES

Spear, Ashley D.; Hochhalter, Jacob D.; Cerrone, Albert R.; ...

2016-04-27

In an effort to reproduce computationally the observed evolution of microstructurally small fatigue cracks (MSFCs), a method is presented for generating conformal, finite-element (FE), volume meshes from 3D measurements of MSFC propagation. The resulting volume meshes contain traction-free surfaces that conform to incrementally measured 3D crack shapes. Grain morphologies measured using near-field high-energy X-ray diffraction microscopy are also represented within the FE volume meshes. Proof-of-concept simulations are performed to demonstrate the utility of the mesh-generation method. The proof-of-concept simulations employ a crystal-plasticity constitutive model and are performed using the conformal FE meshes corresponding to successive crack-growth increments. Although the simulationsmore » for each crack increment are currently independent of one another, they need not be, and transfer of material-state information among successive crack-increment meshes is discussed. The mesh-generation method was developed using post-mortem measurements, yet it is general enough that it can be applied to in-situ measurements of 3D MSFC propagation.« less

A method to generate conformal finite-element meshes from 3D measurements of microstructurally small fatigue-crack propagation [A method to generate conformal finite-element meshes from 3D measurements of microstructurally small fatigue-crack propagation: 3D Meshes of Microstructurally Small Crack Growth

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

Spear, Ashley D.; Hochhalter, Jacob D.; Cerrone, Albert R.

In an effort to reproduce computationally the observed evolution of microstructurally small fatigue cracks (MSFCs), a method is presented for generating conformal, finite-element (FE), volume meshes from 3D measurements of MSFC propagation. The resulting volume meshes contain traction-free surfaces that conform to incrementally measured 3D crack shapes. Grain morphologies measured using near-field high-energy X-ray diffraction microscopy are also represented within the FE volume meshes. Proof-of-concept simulations are performed to demonstrate the utility of the mesh-generation method. The proof-of-concept simulations employ a crystal-plasticity constitutive model and are performed using the conformal FE meshes corresponding to successive crack-growth increments. Although the simulationsmore » for each crack increment are currently independent of one another, they need not be, and transfer of material-state information among successive crack-increment meshes is discussed. The mesh-generation method was developed using post-mortem measurements, yet it is general enough that it can be applied to in-situ measurements of 3D MSFC propagation.« less

Three-dimensional thermal finite element modeling of lithium-ion battery in thermal abuse application

NASA Astrophysics Data System (ADS)

Guo, Guifang; Long, Bo; Cheng, Bo; Zhou, Shiqiong; Xu, Peng; Cao, Binggang

In order to better understand the thermal abuse behavior of high capacities and large power lithium-ion batteries for electric vehicle application, a three-dimensional thermal model has been developed for analyzing the temperature distribution under abuse conditions. The model takes into account the effects of heat generation, internal conduction and convection, and external heat dissipation to predict the temperature distribution in a battery. Three-dimensional model also considers the geometrical features to simulate oven test, which are significant in larger cells for electric vehicle application. The model predictions are compared to oven test results for VLP 50/62/100S-Fe (3.2 V/55 Ah) LiFePO 4/graphite cells and shown to be in great agreement.

Iron(III) solubility and speciation in aqueous solutions. experimental study and modelling: part 1. hematite solubility from 60 to 300°C in NaOH-NaCl solutions and thermodynamic properties of Fe(OH) 4 -(aq)

NASA Astrophysics Data System (ADS)

Diakonov, Igor I.; Schott, Jacques; Martin, Francois; Harrichourry, Jean-Claude; Escalier, Jocelyne

1999-08-01

The solubility of natural and synthetic hematite (α-Fe 2O 3) was measured in NaOH-NaCl solutions (0.007 ≤ m(NaOH) ≤ 2.0) between 60 and 300°C at saturated water vapour pressure and under excess oxygen. Solubility constants determined in the present study and by Yishan et al. (1986) at 300°C were combined with the thermodynamic properties of hematite (Hemingway, 1990) and water (SUPCRT92, Johnson et al., 1992) to generate within the framework of the revised Helgeson-Kirkham-Flowers (HKF) model the standard partial molal thermodynamic properties at 25°C and 1 bar, and the revised HKF equations of state parameters of Fe(OH) 4 -. The extrapolated value for the Gibbs energy of formation for Fe(OH) 4 - at 25°C is -201.97 kcal/mol. Thermodynamic calculations show that Fe(OH) 4 - exhibits a chemical behaviour different from that of Ga(OH) 4 - and Al(OH) 4 -.

Contact (kallikrein/kinin) system activation in whole human blood induced by low concentrations of α-Fe2O3 nanoparticles.

PubMed

Ekdahl, Kristina N; Davoodpour, Padideh; Ekstrand-Hammarström, Barbro; Fromell, Karin; Hamad, Osama A; Hong, Jaan; Bucht, Anders; Mohlin, Camilla; Seisenbaeva, Gulaim A; Kessler, Vadim G; Nilsson, Bo

2018-04-01

Iron-oxide nanoparticles (NPs) generated by environmental events are likely to represent health problems. α-Fe 2 O 3 NPs were synthesized, characterized and tested in a model for toxicity utilizing human whole blood without added anticoagulant. MALDI-TOF of the corona was performed and activation markers for plasma cascade systems (complement, contact and coagulation systems), platelet consumption and release of growth factors, MPO, and chemokine/cytokines from blood cells were analyzed. The coronas formed on the pristine α-Fe 2 O 3 NPs contained contact system proteins and they induced massive activation of the contact (kinin/kallikrein) system, as well as thrombin generation, platelet activation, and release of two pro-angiogeneic growth factors: platelet-derived growth factor and vascular endothelial growth factor, whereas complement activation was unaffected. The α-Fe 2 O 3 NPs exhibited a noticeable toxicity, with kinin/kallikrein activation, which may be associated with hypotension and long-term angiogenesis in vivo, with implications for cancer, arteriosclerosis and pulmonary disease. Copyright © 2017 Elsevier Inc. All rights reserved.

Finite element analysis of gradient z-coil induced eddy currents in a permanent MRI magnet.

PubMed

Li, Xia; Xia, Ling; Chen, Wufan; Liu, Feng; Crozier, Stuart; Xie, Dexin

2011-01-01

In permanent magnetic resonance imaging (MRI) systems, pulsed gradient fields induce strong eddy currents in the conducting structures of the magnet body. The gradient field for image encoding is perturbed by these eddy currents leading to MR image distortions. This paper presents a comprehensive finite element (FE) analysis of the eddy current generation in the magnet conductors. In the proposed FE model, the hysteretic characteristics of ferromagnetic materials are considered and a scalar Preisach hysteresis model is employed. The developed FE model was applied to study gradient z-coil induced eddy currents in a 0.5 T permanent MRI device. The simulation results demonstrate that the approach could be effectively used to investigate eddy current problems involving ferromagnetic materials. With the knowledge gained from this eddy current model, our next step is to design a passive magnet structure and active gradient coils to reduce the eddy current effects. Copyright © 2010 Elsevier Inc. All rights reserved.

From single muscle fiber to whole muscle mechanics: a finite element model of a muscle bundle with fast and slow fibers.

PubMed

Marcucci, Lorenzo; Reggiani, Carlo; Natali, Arturo N; Pavan, Piero G

2017-12-01

Muscles exhibit highly complex, multi-scale architecture with thousands of muscle fibers, each with different properties, interacting with each other and surrounding connective structures. Consequently, the results of single-fiber experiments are scarcely linked to the macroscopic or whole muscle behavior. This is especially true for human muscles where it would be important to understand of how skeletal muscles disorders affect patients' life. In this work, we developed a mathematical model to study how fast and slow muscle fibers, well characterized in single-fiber experiments, work and generate together force and displacement in muscle bundles. We characterized the parameters of a Hill-type model, using experimental data on fast and slow single human muscle fibers, and comparing experimental data with numerical simulations obtained from finite element (FE) models of single fibers. Then, we developed a FE model of a bundle of 19 fibers, based on an immunohistochemically stained cross section of human diaphragm and including the corresponding properties of each slow or fast fiber. Simulations of isotonic contractions of the bundle model allowed the generation of its apparent force-velocity relationship. Although close to the average of the force-velocity curves of fast and slow fibers, the bundle curve deviates substantially toward the fast fibers at low loads. We believe that the present model and the characterization of the force-velocity curve of a fiber bundle represents the starting point to link the single-fiber properties to those of whole muscle with FE application in phenomenological models of human muscles.

Finite element modeling of a 3D coupled foot-boot model.

PubMed

Qiu, Tian-Xia; Teo, Ee-Chon; Yan, Ya-Bo; Lei, Wei

2011-12-01

Increasingly, musculoskeletal models of the human body are used as powerful tools to study biological structures. The lower limb, and in particular the foot, is of interest because it is the primary physical interaction between the body and the environment during locomotion. The goal of this paper is to adopt the finite element (FE) modeling and analysis approaches to create a state-of-the-art 3D coupled foot-boot model for future studies on biomechanical investigation of stress injury mechanism, foot wear design and parachute landing fall simulation. In the modeling process, the foot-ankle model with lower leg was developed based on Computed Tomography (CT) images using ScanIP, Surfacer and ANSYS. Then, the boot was represented by assembling the FE models of upper, insole, midsole and outsole built based on the FE model of the foot-ankle, and finally the coupled foot-boot model was generated by putting together the models of the lower limb and boot. In this study, the FE model of foot and ankle was validated during balance standing. There was a good agreement in the overall patterns of predicted and measured plantar pressure distribution published in literature. The coupled foot-boot model will be fully validated in the subsequent works under both static and dynamic loading conditions for further studies on injuries investigation in military and sports, foot wear design and characteristics of parachute landing impact in military. Copyright © 2011 IPEM. Published by Elsevier Ltd. All rights reserved.

Iron pentacarbonyl detection limits in the cigarette smoke matrix using FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Parrish, Milton E.; Plunkett, Susan E.; Harward, Charles N.

2005-11-01

Endogenous metals present in tobacco from agricultural practices have been purported to generate metal carbonyls in cigarette smoke. Transition metal catalysts, such as iron oxide, have been investigated for the reduction of carbon monoxide (CO) in cigarette smoke. These studies motivated the development of an analytical method to determine if iron pentacarbonyl [Fe(CO) 5] is present in mainstream smoke from cigarette models having cigarette paper made with iron oxide. An FT-IR puff-by-puff method was developed and the detection limit was determined using two primary reference spectra from different sources to estimate the amount of Fe(CO) 5 present in a high-pressure steel cylinder of CO. We do not detect Fe(CO) 5 in a single 35 mL puff from reference cigarettes or from those cigarette models having cigarette paper made with iron oxide, with a 30-ppbV limit of detection (LOD). Also, it was shown that a filter containing activated carbon would remove Fe(CO) 5.

A subsurface Fe-silicate weathering microbiome

NASA Astrophysics Data System (ADS)

Napieralski, S. A.; Buss, H. L.; Roden, E. E.

2017-12-01

Traditional models of microbially mediated weathering of primary Fe-bearing minerals often invoke organic ligands (e.g. siderophores) used for nutrient acquisition. However, it is well known that the oxidation of Fe(II) governs the overall rate of Fe-silicate mineral dissolution. Recent work has demonstrated the ability of lithtrophic iron oxidizing bacteria (FeOB) to grow via the oxidation of structural Fe(II) in biotite as a source of metabolic energy with evidence suggesting a direct enzymatic attack on the mineral surface. This process necessitates the involvement of dedicated outer membrane proteins that interact with insoluble mineral phases in a process known as extracellular electron transfer (EET). To investigate the potential role FeOB in a terrestrial subsurface weathering system, samples were obtained from the bedrock-saprolite interface (785 cm depth) within the Rio Icacos Watershed of the Luquillo Mountains in Puerto Rico. Prior geochemical evidence suggests the flux of Fe(II) from the weathering bedrock supports a robust lithotrophic microbial community at depth. Current work confirms the activity of microorganism in situ, with a marked increase in ATP near the bedrock-saprolite interface. Regolith recovered from the interface was used as inoculum to establish enrichment cultures with powderized Fe(II)-bearing minerals serving as the sole energy source. Monitoring of the Fe(II)/Fe(total) ratio and ATP generation suggests growth of microorganisms coupled to the oxidation of mineral bound Fe(II). Analysis of 16S rRNA gene and shotgun metagenomic libraries from in situ and enrichment culture samples lends further support to FeOB involvement in the weathering process. Multiple metagenomic bins related to known FeOB, including Betaproteobacteria genera, contain homologs to model EET systems, including Cyc2 and MtoAB. Our approach combining geochemistry and metagenomics with ongoing microbiological and genomic characterization of novel isolates obtained from enrichment cultures provides insight into the role of FeOB in Fe(II)-mineral alteration as well as furthering our understanding of the biotic reactions contributing the globally important biogeochemical phenomenon of chemical weathering.

A Framework to Learn Physics from Atomically Resolved Images

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

Vlcek, L.; Maksov, A.; Pan, M.

Here, we present a generalized framework for physics extraction, i.e., knowledge, from atomically resolved images, and show its utility by applying it to a model system of segregation of chalcogen atoms in an FeSe 0.45Te 0.55 superconductor system. We emphasize that the framework can be used for any imaging data for which a generative physical model exists. Consider that a generative physical model can produce a very large number of configurations, not all of which are observable. By applying a microscope function to a sub-set of this generated data, we form a simulated dataset on which statistics can be computed.

Micro Finite Element models of the vertebral body: Validation of local displacement predictions.

PubMed

Costa, Maria Cristiana; Tozzi, Gianluca; Cristofolini, Luca; Danesi, Valentina; Viceconti, Marco; Dall'Ara, Enrico

2017-01-01

The estimation of local and structural mechanical properties of bones with micro Finite Element (microFE) models based on Micro Computed Tomography images depends on the quality bone geometry is captured, reconstructed and modelled. The aim of this study was to validate microFE models predictions of local displacements for vertebral bodies and to evaluate the effect of the elastic tissue modulus on model's predictions of axial forces. Four porcine thoracic vertebrae were axially compressed in situ, in a step-wise fashion and scanned at approximately 39μm resolution in preloaded and loaded conditions. A global digital volume correlation (DVC) approach was used to compute the full-field displacements. Homogeneous, isotropic and linear elastic microFE models were generated with boundary conditions assigned from the interpolated displacement field measured from the DVC. Measured and predicted local displacements were compared for the cortical and trabecular compartments in the middle of the specimens. Models were run with two different tissue moduli defined from microindentation data (12.0GPa) and a back-calculation procedure (4.6GPa). The predicted sum of axial reaction forces was compared to the experimental values for each specimen. MicroFE models predicted more than 87% of the variation in the displacement measurements (R2 = 0.87-0.99). However, model predictions of axial forces were largely overestimated (80-369%) for a tissue modulus of 12.0GPa, whereas differences in the range 10-80% were found for a back-calculated tissue modulus. The specimen with the lowest density showed a large number of elements strained beyond yield and the highest predictive errors. This study shows that the simplest microFE models can accurately predict quantitatively the local displacements and qualitatively the strain distribution within the vertebral body, independently from the considered bone types.

Finite element analysis of the high strain rate testing of polymeric materials

NASA Astrophysics Data System (ADS)

Gorwade, C. V.; Alghamdi, A. S.; Ashcroft, I. A.; Silberschmidt, V. V.; Song, M.

2012-08-01

Advanced polymer materials are finding an increasing range of industrial and defence applications. Ultra-high molecular weight polymers (UHMWPE) are already used in lightweight body armour because of their good impact resistance with light weight. However, a broader use of such materials is limited by the complexity of the manufacturing processes and the lack of experimental data on their behaviour and failure evolution under high-strain rate loading conditions. The current study deals with an investigation of the internal heat generation during tensile of UHMWPE. A 3D finite element (FE) model of the tensile test is developed and validated the with experimental work. An elastic-plastic material model is used with adiabatic heat generation. The temperature and stresses obtained with FE analysis are found to be in a good agreement with the experimental results. The model can be used as a simple and cost effective tool to predict the thermo-mechanical behaviour of UHMWPE part under various loading conditions.

YSZ-based sensor using Cr-Fe-based spinel-oxide electrodes for selective detection of CO.

PubMed

Anggraini, Sri Ayu; Fujio, Yuki; Ikeda, Hiroshi; Miura, Norio

2017-08-22

A selective carbon monoxide (CO) sensor was developed by the use of both of CuCrFeO 4 and CoCrFeO 4 as the sensing electrode (SE) for yttria-stabilized zirconia (YSZ)-based potentiometric sensor. The sensing-characteristic examinations of the YSZ-based sensors using each of spinel oxides as the single-SE sensor showed that CuCrFeO 4 -SE had the ability to detect CO, hydrocarbons and NO x gases, while CoCrFeO 4 -SE was sensitive to hydrocarbons and NO x gases. Thus, when both SEs were paired as a combined-SEs sensor, the resulting sensor could generate a selective response to CO at 450 °C under humid conditions. The sensor was also capable of detecting CO in the concentration range of 20-700 ppm. Its sensing mechanism that was examined via polarization-curve measurements was confirmed to be based on mixed-potential model. The CO response generated by the combined-SEs sensor was unaffected by the change of water vapor concentration in the range of 1.3-11.5 vol% H 2 O. Additionally, the sensing performance was stable during 13 days tested. Copyright © 2017 Elsevier B.V. All rights reserved.

Orion Crew Member Injury Predictions during Land and Water Landings

NASA Technical Reports Server (NTRS)

Lawrence, Charles; Littell, Justin D.; Fasanella, Edwin L.; Tabiei, Ala

2008-01-01

A review of astronaut whole body impact tolerance is discussed for land or water landings of the next generation manned space capsule named Orion. LS-DYNA simulations of Orion capsule landings are performed to produce a low, moderate, and high probability of injury. The paper evaluates finite element (FE) seat and occupant simulations for assessing injury risk for the Orion crew and compares these simulations to whole body injury models commonly referred to as the Brinkley criteria. The FE seat and crash dummy models allow for varying the occupant restraint systems, cushion materials, side constraints, flailing of limbs, and detailed seat/occupant interactions to minimize landing injuries to the crew. The FE crash test dummies used in conjunction with the Brinkley criteria provides a useful set of tools for predicting potential crew injuries during vehicle landings.

Experimental and Computational Investigation of High Entropy Alloys for Elevated-Temperature Applications

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

Liaw, Peter; Zhang, Fan; Zhang, Chuan

2016-07-30

To create and design novel structural materials with enhanced creep-resistance, fundamental studies have been conducted on high-entropy alloys (HEAs), using (1) thermodynamic calculations, (2) mechanical tests, (3) neutron diffraction, (4) characterization techniques, and (5) crystal-plasticity finite-element modeling (CPFEM), to explore future candidates for next-generation power plants. All the constituent binary and ternary systems of the Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems were thermodynamically modeled within the whole composition range. Comparisons between the calculated phase diagrams and literature data are in good agreement. Seven types of HEAs were fabricated from Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems. The Al xCrCuFeMnNi HEAs have disordered [face-centered cubic (FCC)more » + body-centered cubic (BCC)] crystal structures, not FCC or BCC single structure. Excessive alloying of the Al element results in the change of both microstructural and mechanical properties in Al xCoCrFeNi HEAs. There are mainly three structural features in Al xCoCrFeNi: (1) the morphology, (2) the volume fractions of the constitute phases, and (3) existing temperatures of all six phases. After homogenization, the Al 0.3CoCrFeNi material is a pure FCC solid solution. After aging at 700 °C for 500 hours, the optimal microstructure combinations, the FCC matrix, needle-like B2 phase within grains, and granular σ phase along grain boundary, is achieved for Al 0.3CoCrFeNi. The cold-rolling process is utilized to reduce the grain size of Al 0.1CoCrFeNi and Al 0.3CoCrFeNi. The chemical elemental partitioning of FCC, BCC, B2, and σphases at different temperatures, before and after mechanical tests, in Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems are quantitatively characterized by both synchrotron X-ray diffraction, neutron diffraction with levitation, scanning electron microscopy (SEM), advanced atom probe tomography (APT), and transmission electron microscopy (TEM). In-situ neutron diffraction experiments were conducted to study the strengthening effect of B2 phase on tensile properties of Al 0.3CoCrFeNi HEAs directly. The results shows the creep behavior of Al 0.3CoCrFeNi is superior to conventional alloys, and the heat treatment introduces secondary B2 phase into the FCC matrix, which increase the yielding strength, decrease the ductility, diminish the serrated flow during compression tests at high temperatures. In summary, the outcomes of the development of the HEAs with creep resistance include: (1) Suitable candidates, for the application to boilers and steam and gas turbines at temperatures above 760 °C and a stress of 35 MPa. (2) Fundamental understanding on the precipitate stability and deformation mechanisms of both single-phase and precipitate-strengthened alloys at room and elevated temperatures, and (3) The demonstration of an integrated approach, coupling modeling [thermodynamic calculations and crystal-plasticity finite-element modeling (CPFEM)] and focused experiments, to identify HEAs that outperform conventional alloys for high-temperature applications, which will be applicable for the discovery and development of other high-temperature materials in the power-generating industry.« less

Channel scaling and field-effect mobility extraction in amorphous InZnO thin film transistors

NASA Astrophysics Data System (ADS)

Lee, Sunghwan; Song, Yang; Park, Hongsik; Zaslavsky, A.; Paine, D. C.

2017-09-01

Amorphous oxide semiconductors (AOSs) based on indium oxides are of great interest for next generation ultra-high definition displays that require much smaller pixel driving elements. We describe the scaling behavior in amorphous InZnO thin film transistors (TFTs) with a significant decrease in the extracted field-effect mobility μFE with channel length L (from 39.3 to 9.9 cm2/V·s as L is reduced from 50 to 5 μm). Transmission line model measurements reveal that channel scaling leads to a significant μFE underestimation due to contact resistance (RC) at the metallization/channel interface. Therefore, we suggest a method of extracting correct μFE when the TFT performance is significantly affected by RC. The corrected μFE values are higher (45.4 cm2/V·s) and nearly independent of L. The results show the critical effect of contact resistance on μFE measurements and suggest strategies to determine accurate μFE when a TFT channel is scaled.

High energy irradiations simulating cosmic-ray-induced planetary gamma ray production. I - Fe target

NASA Technical Reports Server (NTRS)

Metzger, A. E.; Parker, R. H.; Yellin, J.

1986-01-01

Two thick Fe targets were bombarded by a series of 6 GeV proton irradiations for the purpose of simulating the cosmic ray bombardment of planetary objects in space. Gamma ray energy spectra were obtained with a germanium solid state detector during the bombardment, and 46 of the gamma ray lines were ascribed to the Fe targets. A comparison between observed and predicted values showed good agreement for Fe lines from neutron inelastic scattering and spallation reactions, and less satisfactory agreement for neutron capture reactions, the latter attributed to the difference in composition between the Fe target and the mean lunar abundance used in the modeling. Through an analysis of the irradiation results together with continuum data obtained in lunar orbit, it was found that 100 hours of measurement with a current instrument should generate a spectrum containing approximately 20 lines due to Fe alone, with a 2-sigma sensitivity for detection of about 0.2 percent.

Multigrid finite element method in stress analysis of three-dimensional elastic bodies of heterogeneous structure

NASA Astrophysics Data System (ADS)

Matveev, A. D.

2016-11-01

To calculate the three-dimensional elastic body of heterogeneous structure under static loading, a method of multigrid finite element is provided, when implemented on the basis of algorithms of finite element method (FEM), using homogeneous and composite threedimensional multigrid finite elements (MFE). Peculiarities and differences of MFE from the currently available finite elements (FE) are to develop composite MFE (without increasing their dimensions), arbitrarily small basic partition of composite solids consisting of single-grid homogeneous FE of the first order can be used, i.e. in fact, to use micro approach in finite element form. These small partitions allow one to take into account in MFE, i.e. in the basic discrete models of composite solids, complex heterogeneous and microscopically inhomogeneous structure, shape, the complex nature of the loading and fixation and describe arbitrarily closely the stress and stain state by the equations of three-dimensional elastic theory without any additional simplifying hypotheses. When building the m grid FE, m of nested grids is used. The fine grid is generated by a basic partition of MFE, the other m —1 large grids are applied to reduce MFE dimensionality, when m is increased, MFE dimensionality becomes smaller. The procedures of developing MFE of rectangular parallelepiped, irregular shape, plate and beam types are given. MFE generate the small dimensional discrete models and numerical solutions with a high accuracy. An example of calculating the laminated plate, using three-dimensional 3-grid FE and the reference discrete model is given, with that having 2.2 milliards of FEM nodal unknowns.

Development of an anti-ferret CD4 monoclonal antibody for the characterisation of ferret T lymphocytes.

PubMed

Layton, Daniel S; Xiao, Xiaowen; Bentley, John D; Lu, Louis; Stewart, Cameron R; Bean, Andrew G D; Adams, Timothy E

2017-05-01

The ferret is an established animal model for a number of human respiratory viral infections, such as influenza virus and more recently, Ebola virus. However, a paucity of immunological reagents has hampered the study of cellular immune responses. Here we describe the development and characterisation of a novel monoclonal antibody (mAb) against the ferret CD4 antigen and the characterisation of ferret CD4 T lymphocytes. Recombinant production and purification of the ferret CD4 ectodomain soluble protein allowed hybridoma generation and the generation of a mAb (FeCD4) showing strong binding to ferret CD4 protein and lymphoid cells by flow cytometry. FeCD4 bound to its cognate antigen post-fixation with paraformaldehyde (PFA) which is routinely used to inactivate highly pathogenic viruses. We have also used FeCD4 in conjunction with other immune cell markers to characterise ferret T cells in both primary and secondary lymphoid organs. In summary, we have developed an important reagent for the study of cellular immunological responses in the ferret model of infectious disease. Copyright © 2017 Elsevier B.V. All rights reserved.

Simplified versus geometrically accurate models of forefoot anatomy to predict plantar pressures: A finite element study.

PubMed

Telfer, Scott; Erdemir, Ahmet; Woodburn, James; Cavanagh, Peter R

2016-01-25

Integration of patient-specific biomechanical measurements into the design of therapeutic footwear has been shown to improve clinical outcomes in patients with diabetic foot disease. The addition of numerical simulations intended to optimise intervention design may help to build on these advances, however at present the time and labour required to generate and run personalised models of foot anatomy restrict their routine clinical utility. In this study we developed second-generation personalised simple finite element (FE) models of the forefoot with varying geometric fidelities. Plantar pressure predictions from barefoot, shod, and shod with insole simulations using simplified models were compared to those obtained from CT-based FE models incorporating more detailed representations of bone and tissue geometry. A simplified model including representations of metatarsals based on simple geometric shapes, embedded within a contoured soft tissue block with outer geometry acquired from a 3D surface scan was found to provide pressure predictions closest to the more complex model, with mean differences of 13.3kPa (SD 13.4), 12.52kPa (SD 11.9) and 9.6kPa (SD 9.3) for barefoot, shod, and insole conditions respectively. The simplified model design could be produced in <1h compared to >3h in the case of the more detailed model, and solved on average 24% faster. FE models of the forefoot based on simplified geometric representations of the metatarsal bones and soft tissue surface geometry from 3D surface scans may potentially provide a simulation approach with improved clinical utility, however further validity testing around a range of therapeutic footwear types is required. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Di/mono-nuclear iron(I)/(II) complexes as functional models for the 2Fe2S subunit and distal Fe moiety of the active site of [FeFe] hydrogenases: protonations, molecular structures and electrochemical properties.

PubMed

Gao, Shang; Fan, Jiangli; Sun, Shiguo; Song, Fengling; Peng, Xiaojun; Duan, Qian; Jiang, Dayong; Liang, Qingcheng

2012-10-21

Di/mono-nuclear iron(I)/(II) complexes containing conjugated and electron-withdrawing S-to-S linkers, [{(μ-S)(2)(C(4)N(2)H(2))}Fe(2)(CO)(6)] (1), [{(μ-S)(2)(C(4)N(2)H(2))}Fe(2)(CO)(5)(PMe(3))] (1P), and [{(μ-S)(2)(C(4)N(2)H(2))}Fe(CO)(2)(PMe(3))(2)] (2) were prepared as biomimetic models for the 2Fe2S subunit and distal Fe moiety of the active site of [FeFe] hydrogenases. The N atoms in the heterocyclic pyrazines of 1 and 2 were protonated in the presence of proton acid to generate one and two hydrides, [1(NH)](+) CF(3)SO(3)(-), [2(NH)](+) CF(3)SO(3)(-), and [2(NH)(2)](2+) (CF(3)SO(3)(-))(2), respectively. The protonation processes were evidenced by in situ IR and NMR spectroscopy. The molecular structures of the protonated species [1(NH)](+) CF(3)SO(3)(-) and [2(NH)(2)](2+) (CF(3)SO(3)(-))(2) together with their originating complexes and , and the mono-PMe(3) substituted diiron complex were identified by X-ray crystallography. The IR and single-crystal analysis data all suggested that the electron-withdrawing bridge, pyrazine, led to decreased electron density at the Fe centers of the model complexes, which was consistent with the electrochemical studies. The cyclic voltammograms indicated that complex exhibited a low primary reduction potential at -1.17 V vs. Fc-Fc(+) with a 270 mV positive shift compared with that of the benzene-1,2-dithiolate (bdt) bridged analogue [(μ-bdt)Fe(2)(CO)(6)]. Under the weak acid conditions, complexes 1 and 2 could electrochemically catalyze the proton reduction. More interestingly, the mononuclear ferrous complex 2 showed two catalytic peaks during the formation of hydrogen, confirming its potential as a catalyst for hydrogen production.

Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

NASA Astrophysics Data System (ADS)

Sanibondi, Paolo

2015-09-01

Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

Reference values of fractional excretion of exhaled nitric oxide among non-smokers and current smokers.

PubMed

Torén, Kjell; Murgia, Nicola; Schiöler, Linus; Bake, Björn; Olin, Anna-Carin

2017-08-25

Fractional exhaled nitric oxide (FE NO ) is used to assess of airway inflammation; diagnose asthma and monitor adherence to advised therapy. Reliable and accurate reference values for FE NO are needed for both non-smoking and current smoking adults in the clinical setting. The present study was performed to establish reference adult FE NO values among never-smokers, former smokers and current smokers. FE NO was measured in 5265 subjects aged 25-75 years in a general-population study, using a chemiluminescence (Niox ™) analyser according to the guidelines of the American Thoracic Society and the European Respiratory Society. Atopy was based on the presence of immunoglobulin E (IgE) antibodies to common inhalant allergens (measured using Phadiatop® test). Spirometry without bronchodilation was performed and forced vital capacity (FVC), forced expired volume in 1 s (FEV 1 ) and the ratio of FEV 1 to FVC values were obtained. After excluding subjects with asthma, chronic bronchitis, spirometric airway obstruction and current cold, 3378 subjects remained. Equations for predictions of FE NO values were modelled using nonparametric regression models. FE NO levels were similar in never-smokers and former smokers, and these two groups were therefore merged into a group termed "non-smokers". Reference equations, including the 5th and 95th percentiles, were generated for female and male non-smokers, based on age, height and atopy. Regression models for current smokers were unstable. Hence, the proposed reference values for current smokers are based on the univariate distribution of FE NO and fixed cut-off limits. Reference values for FE NO among respiratory healthy non-smokers should be outlined stratified for gender using individual reference values. For current smokers separate cut-off limits are proposed.

Facile fabrication of superparamagnetic graphene/polyaniline/Fe3O4 nanocomposites for fast magnetic separation and efficient removal of dye.

PubMed

Mu, Bin; Tang, Jie; Zhang, Long; Wang, Aiqin

2017-07-13

Using graphene as adsorbent for removal of pollutants from polluted water is commonly recognized to be costly because the graphene is usually produced by a very complex process. Herein, a simple and eco-friendly method was employed to fabricate efficient superparamagnetic graphene/polyaniline/Fe 3 O 4 nanocomposites for removal of dyes. The exfoliation of graphite as nanosheets and the functionalization of nanosheets with polyaniline and Fe 3 O 4 nanoparticles were simultaneously achieved via a one-pot reaction process combining the intercalation polymerization of aniline and the co-precipitation of the residual Fe 3+ and the generated Fe 2+ . The obtained graphene/polyaniline/Fe 3 O 4 nanocomposites exhibited excellent adsorption performance for Congo red, even in the presence of Brilliant green. The adsorption kinetics and adsorption isotherms were well fitted with pseudo second-order kinetic model and Langmuir isotherm model, respectively. In a word, this method is simple and industrially feasible, which provides a new approach to fabricate highly efficient graphene-based adsorbents on large scale for removal of dyes. In addition, it also can be used to exfoliate other two-dimensional materials, such as boron nitride, carbon nitride and MoS 2 for a range of possible applications.

Constraining Thermal Histories by Monte Carlo Simulation of Mg-Fe Isotopic Profiles in Olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Dauphas, N.

2016-12-01

In thermochronology, random time-temperature (t-T) paths are generated and used as inputs to model fission track data. This random search method is used to identify a range of acceptable thermal histories that can describe the data. We have extended this modeling approach to magmatic systems. This approach utilizes both the chemical and stable isotope profiles measured in crystals as model constraints. Specifically, the isotopic profiles are used to determine the relative contribution of crystal growth vs. diffusion in generating chemical profiles, and to detect changes in melt composition. With this information, tighter constraints can be placed on the thermal evolution of magmatic bodies. We use an olivine phenocryst from the Kilauea Iki lava lake, HI, to demonstrate proof of concept. We treat this sample as one with little geologic context, then compare our modeling results to the known thermal history experienced by that sample. To complete forward modeling, we use MELTS to estimate the boundary condition, initial and quench temperatures. We also assume a simple relationship between crystal growth and cooling rate. Another important parameter is the isotopic effect for diffusion (i.e., the relative diffusivity of the light vs. heavy isotope of an element). The isotopic effects for Mg and Fe diffusion in olivine have been estimated based on natural samples; experiments to better constrain these parameters are underway. We find that 40% of the random t-T paths can be used to fit the Mg-Fe chemical profiles. However, only a few can be used to simultaneously fit the Mg-Fe isotopic profiles. These few t-T paths are close to the independently determined t-T history of the sample. This modeling approach can be further extended other igneous and metamorphic systems where data exist for diffusion rates, crystal growth rates, and isotopic effects for diffusion.

A pulsed eddy current probe for inspection of support plates from within Alloy-800 steam generator tubes

NASA Astrophysics Data System (ADS)

Krause, T. W.; Babbar, V. K.; Underhill, P. R.

2014-02-01

Support plate degradation and fouling in nuclear steam generators (SGs) can lead to SG tube corrosion and loss of efficiency. Inspection and monitoring of these conditions can be integrated with preventive maintenance programs, thereby advancing station-life management processes. A prototype pulsed eddy current (PEC) probe, targeting inspection issues associated with SG tubes in SS410 tube support plate structures, has been developed using commercial finite element (FE) software. FE modeling was used to identify appropriate driver and pickup coil configurations for optimum sensitivity to changes in gap and offset for Alloy-800 SG tubes passing through 25 mm thick SS410 support plates. Experimental measurements using a probe that was manufactured based on the modeled configuration, were used to confirm the sensitivity of differential PEC signals to changes in relative position of the tube within the tube support plate holes. Models investigated the effect of shift and tilt of tube with respect to hole centers. Near hole centers and for small shifts, modeled signal amplitudes from the differentially connected coil pairs were observed to change linearly with tube shift. This was in agreement with experimentally measured TEC coil response. The work paves the way for development of a system targeting the inspection and evaluation of support plate structures in steam generators.

Dimeric Fe (II, III) complex of quinoneoxime as functional model of PAP enzyme: Mössbauer, magneto-structural and DNA cleavage studies

NASA Astrophysics Data System (ADS)

Salunke-Gawali, Sunita; Ahmed, Khursheed; Varret, François; Linares, Jorge; Zaware, Santosh; Date, Sadgopal; Rane, Sandhya

2008-07-01

Purple acid phosphatase, ( PAP), is known to contain dinuclear Fe2 + 2, + 3 site with characteristic Fe + 3 ← Tyr ligand to metal charge transfer in coordination. Phthiocoloxime (3-methyl-2-hydroxy-1,4-naphthoquinone-1-oxime) ligand L, mimics (His/Tyr) ligation with controlled and unique charge transfers resulting in valence tautomeric coordination with mixed valent diiron site in model compound Fe-1: [μ-OH-Fe2 + 2, + 3 ( o-NQCH3ox) ( o-NSQCH3ox)2 (CAT) H2O]. Fe-2: [Fe + 3( o-NQCH3ox) ( p-NQCH3ox)2]2 a molecularly associated dimer of phthiocoloxime synthesized for comparison of charge transfer. 57Fe Mössbauer studies was used to quantitize unusual valences due to ligand in dimeric Fe-1 and Fe-2 complexes which are supported by EPR and SQUID studies. 57Fe Mössbauer spectra for Fe-1 at 300 K indicates the presence of two quadrupole split asymmetric doublets due to the differences in local coordination geometries of [Fe + 3]A and [Fe + 2]B sites. The hyperfine interaction parameters are δ A = 0.152, (Δ E Q)A = 0.598 mm/s with overlapping doublet at δ B = 0.410 and (Δ E Q)B = 0.468 mm/s. Due to molecular association tendency of ligand, dimer Fe-2 possesses 100% Fe + 3(h.s.) hexacoordinated configuration with isomer shift δ = 0.408 mm/s. Slightly distorted octahedral symmetry created by NQCH3ox ligand surrounding Fe + 3(h.s.) state generates small field gradient indicated by quadrupole split Δ E Q = 0.213 mm/s. Decrease of isomer shifts together with variation of quadrupole splits with temperature in Fe-1 dimer compared to Fe-2 is result of charge transfers in [Fe2 + 2, + 3 SQ] complexes. EPR spectrum of Fe-1 shows two strong signals at g 1 = 4.17 and g 2 = 2.01 indicative of S = 3/2 spin state with an intermediate spin of Fe + 3(h.s.) configuration. SQUID data of χ _m^{corr} .T were best fitted by using HDVV spin pair model S = 2, 3/2 resulting in antiferromagnetic exchange ( J = -13.5 cm - 1 with an agreement factor of R = 1.89 × 10 - 5). The lower J value of antiferromagnetic exchange leads to Fe+3μ-(OH) Fe + 2 bridging in Fe-1 dimer instead of μ-oxo bridge. The intermolecular association through H-bonds may lead to weakly coupled antiferromagnetic interaction between two Fe-2 molecules having Fe + 3(h.s.) centers. Using S = 5/2, 5/2 spin pair model we obtained best-fitted parameters such as J = -12.4 cm - 1, g = 2.3 with R = 3.58 × 10 - 5. Synthetic strategy results in non-equivalent iron sites in Fe-1 dimer analogues to PAP enzyme hence its reconstitution results in pUC-19 DNA cleavage activity, as physiological functionality of APase. It is compared with nuclease activity of Fe-2 RAPase.

A voxel-based finite element model for the prediction of bladder deformation

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

Chai Xiangfei; Herk, Marcel van; Hulshof, Maarten C. C. M.

2012-01-15

Purpose: A finite element (FE) bladder model was previously developed to predict bladder deformation caused by bladder filling change. However, two factors prevent a wide application of FE models: (1) the labor required to construct a FE model with high quality mesh and (2) long computation time needed to construct the FE model and solve the FE equations. In this work, we address these issues by constructing a low-resolution voxel-based FE bladder model directly from the binary segmentation images and compare the accuracy and computational efficiency of the voxel-based model used to simulate bladder deformation with those of a classicalmore » FE model with a tetrahedral mesh. Methods: For ten healthy volunteers, a series of MRI scans of the pelvic region was recorded at regular intervals of 10 min over 1 h. For this series of scans, the bladder volume gradually increased while rectal volume remained constant. All pelvic structures were defined from a reference image for each volunteer, including bladder wall, small bowel, prostate (male), uterus (female), rectum, pelvic bone, spine, and the rest of the body. Four separate FE models were constructed from these structures: one with a tetrahedral mesh (used in previous study), one with a uniform hexahedral mesh, one with a nonuniform hexahedral mesh, and one with a low-resolution nonuniform hexahedral mesh. Appropriate material properties were assigned to all structures and uniform pressure was applied to the inner bladder wall to simulate bladder deformation from urine inflow. Performance of the hexahedral meshes was evaluated against the performance of the standard tetrahedral mesh by comparing the accuracy of bladder shape prediction and computational efficiency. Results: FE model with a hexahedral mesh can be quickly and automatically constructed. No substantial differences were observed between the simulation results of the tetrahedral mesh and hexahedral meshes (<1% difference in mean dice similarity coefficient to manual contours and <0.02 cm difference in mean standard deviation of residual errors). The average equation solving time (without manual intervention) for the first two types of hexahedral meshes increased to 2.3 h and 2.6 h compared to the 1.1 h needed for the tetrahedral mesh, however, the low-resolution nonuniform hexahedral mesh dramatically decreased the equation solving time to 3 min without reducing accuracy. Conclusions: Voxel-based mesh generation allows fast, automatic, and robust creation of finite element bladder models directly from binary segmentation images without user intervention. Even the low-resolution voxel-based hexahedral mesh yields comparable accuracy in bladder shape prediction and more than 20 times faster in computational speed compared to the tetrahedral mesh. This approach makes it more feasible and accessible to apply FE method to model bladder deformation in adaptive radiotherapy.« less

Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations

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

Tufano, K.J.; Benner, S.G.; Mayer, K.U.

There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealizedmore » micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in dissolved Fe{sup 2+} on the fate of ferrihydrite during reduction in structured soils.« less

Fast estimation of Colles' fracture load of the distal section of the radius by homogenized finite element analysis based on HR-pQCT.

PubMed

Hosseini, Hadi S; Dünki, Andreas; Fabech, Jonas; Stauber, Martin; Vilayphiou, Nicolas; Pahr, Dieter; Pretterklieber, Michael; Wandel, Jasmin; Rietbergen, Bert van; Zysset, Philippe K

2017-04-01

Fractures of the distal section of the radius (Colles' fractures) occur earlier in life than other osteoporotic fractures. Therefore, they can be interpreted as a warning signal for later, more deleterious fractures of vertebral bodies or the femoral neck. In the past decade, the advent of HR-pQCT allowed a detailed architectural analysis of the distal radius and an automated but time-consuming estimation of its strength with linear micro-finite element (μFE) analysis. Recently, a second generation of HR-pQCT scanner (XtremeCT II, SCANCO Medical, Switzerland) with a resolution beyond 61 μm became available for even more refined biomechanical investigations in vivo. This raises the question how biomechanical outcome variables compare between the original (LR) and the new (HR) scanner resolution. Accordingly, the aim of this work was to validate experimentally a patient-specific homogenized finite element (hFE) analysis of the distal section of the human radius for the fast prediction of Colles' fracture load based on the last generation HR-pQCT. Fourteen pairs of fresh frozen forearms (mean age = 77.5±9) were scanned intact using the high (61 μm) and the low (82 μm) resolution protocols that correspond to the new and original HR-pQCT systems. From each forearm, the 20mm most distal section of the radius were dissected out, scanned with μCT at 16.4 μm and tested experimentally under compression up to failure for assessment of stiffness and ultimate load. Linear and nonlinear hFE models together with linear micro finite element (μFE) models were then generated based on the μCT and HR-pQCT reconstructions to predict the aforementioned mechanical properties of 24 sections. Precision errors of the short term reproducibility of the FE analyses were measured based on the repeated scans of 12 sections. The calculated failure loads correlated strongly with those measured in the experiments: accounting for donor as a random factor, the nonlinear hFE provided a marginal coefficient of determination (R m 2 ) of 0.957 for the high resolution (HR) and 0.948 for the low resolution (LR) protocols, the linear hFE with R m 2 of 0.957 for the HR and 0.947 for the LR protocols. Linear μFE predictions of the ultimate load were similar with an R m 2 of 0.950 for the HR and 0.954 for the LR protocols, respectively. Nonlinear hFE strength computation led to precision errors of 2.2 and 2.3% which were higher than the ones calculated based on the linear hFE (1.6 and 1.9%) and linear μFE (1.2 and 1.6%) for the HR and LR protocols respectively. Computation of the fracture load with nonlinear hFE demanded in average 6h of CPU time which was 3 times faster than with linear μFE, while computation with linear hFE took only a few minutes. This study delivers an extensive experimental and numerical validation for the application of an accurate and fast hFE diagnostic tool to help in identifying individuals who may be at risk of an osteoporotic wrist fracture and to follow up pharmacological and other treatments in such patients. Copyright © 2017 Elsevier Inc. All rights reserved.

On the performance of piezoelectric harvesters loaded by finite width impulses

NASA Astrophysics Data System (ADS)

Doria, A.; Medè, C.; Desideri, D.; Maschio, A.; Codecasa, L.; Moro, F.

2018-02-01

The response of cantilevered piezoelectric harvesters loaded by finite width impulses of base acceleration is studied analytically in the frequency domain in order to identify the parameters that influence the generated voltage. Experimental tests are then performed on harvesters loaded by hammer impacts. The latter are used to confirm analytical results and to validate a linear finite element (FE) model of a unimorph harvester. The FE model is, in turn, used to extend analytical results to more general harvesters (tapered, inverse tapered, triangular) and to more general impulses (heel strike in human gait). From analytical and numerical results design criteria for improving harvester performance are obtained.

Nitrogen monoxide decreases iron uptake from transferrin but does not mobilise iron from prelabelled neoplastic cells.

PubMed

Richardson, D R; Neumannova, V; Ponka, P

1995-05-12

The effect of congeners of nitrogen monoxide (NO) on iron (Fe) uptake from 59Fe-125I-transferrin (Tf) and release of 59Fe from prelabelled cells have been investigated in SK-MEL-28 human melanoma cells, human K562 cells and mouse MDW-4 cells. These studies have been initiated as it has been suggested that the tumoricidal effects of NO may be mediated by its acting to release Fe from cells (Hibbs et al., 1984 Biochem. Biophys. Res. Commun. 123, 716-723; Hibbs et al., 1988 Biochem. Biophys. Res. Commun. 157, 87-94). The nitrosonium ion (NO+) generator, sodium nitroprusside (SNP), decreased 59Fe uptake by melanoma cells to 57% of the control without decreasing 125I-Tf uptake after a 4-h incubation with 59Fe-125-Tf (1.25 microM). Longer incubations up to 24 h decreased 59Fe uptake and also 125I-Tf uptake. Two breakdown products of SNP, ferricyanide and cyanide, had no effect on 59Fe uptake. In addition, photolysis of the SNP solution prevented the inhibition of 59Fe uptake, suggesting that NO was the active agent. Two nitric oxide (NO.) producing agents, 3-morpholinosydnonimine (SIN), and S-nitroso-N-acetylpenicillamine (SNAP), also decreased 59Fe uptake from 59Fe-125I-Tf. Superoxide dismutase increased the efficacy of SIN, and the NO-scavenger, oxyhaemoglobin, prevented the inhibition of 59Fe uptake mediated by SNAP, again suggesting that NO was the active agent. Furthermore, dialysis studies demonstrated that none of the NO-generating agents could remove 59Fe from 59Fe-125I-Tf, suggesting that the decrease in cellular Fe uptake observed was not due to NO releasing Fe from the Fe-binding sites of Tf. Despite the ability of NO-producing agents at inhibiting 59Fe uptake by cells, they could not remove significant amounts of 59Fe from melanoma cells prelabelled with either 59Fe-citrate or 59Fe-125I-Tf. Similar data were obtained using K562 and MDW-4 cells. Interestingly, the NO+ generating agent, SNP, had no effect on [3H]thymidine uptake. However, when SNP was converted to an NO. generator by the addition of 1 mM ascorbate, its effect was similar to the NO. generator, SNAP, markedly reducing [3H]thymidine incorporation to 33% of the control value. The addition of unlabelled diferric Tf (0.625 microM) to SNAP ameliorated its inhibitory effect on cellular [3H]thymidine uptake, suggesting that the interaction of NO. with Fe was of importance in the inhibition observed. The results are discussed in the context of the cytostatic potential of NO via its binding to Fe.

Incorporating physically-based microstructures in materials modeling: Bridging phase field and crystal plasticity frameworks

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

Lim, Hojun; Abdeljawad, Fadi; Owen, Steven J.

Here, the mechanical properties of materials systems are highly influenced by various features at the microstructural level. The ability to capture these heterogeneities and incorporate them into continuum-scale frameworks of the deformation behavior is considered a key step in the development of complex non-local models of failure. In this study, we present a modeling framework that incorporates physically-based realizations of polycrystalline aggregates from a phase field (PF) model into a crystal plasticity finite element (CP-FE) framework. Simulated annealing via the PF model yields ensembles of materials microstructures with various grain sizes and shapes. With the aid of a novel FEmore » meshing technique, FE discretizations of these microstructures are generated, where several key features, such as conformity to interfaces, and triple junction angles, are preserved. The discretizations are then used in the CP-FE framework to simulate the mechanical response of polycrystalline α-iron. It is shown that the conformal discretization across interfaces reduces artificial stress localization commonly observed in non-conformal FE discretizations. The work presented herein is a first step towards incorporating physically-based microstructures in lieu of the overly simplified representations that are commonly used. In broader terms, the proposed framework provides future avenues to explore bridging models of materials processes, e.g. additive manufacturing and microstructure evolution of multi-phase multi-component systems, into continuum-scale frameworks of the mechanical properties.« less

Incorporating physically-based microstructures in materials modeling: Bridging phase field and crystal plasticity frameworks

DOE PAGES

Lim, Hojun; Abdeljawad, Fadi; Owen, Steven J.; ...

2016-04-25

Here, the mechanical properties of materials systems are highly influenced by various features at the microstructural level. The ability to capture these heterogeneities and incorporate them into continuum-scale frameworks of the deformation behavior is considered a key step in the development of complex non-local models of failure. In this study, we present a modeling framework that incorporates physically-based realizations of polycrystalline aggregates from a phase field (PF) model into a crystal plasticity finite element (CP-FE) framework. Simulated annealing via the PF model yields ensembles of materials microstructures with various grain sizes and shapes. With the aid of a novel FEmore » meshing technique, FE discretizations of these microstructures are generated, where several key features, such as conformity to interfaces, and triple junction angles, are preserved. The discretizations are then used in the CP-FE framework to simulate the mechanical response of polycrystalline α-iron. It is shown that the conformal discretization across interfaces reduces artificial stress localization commonly observed in non-conformal FE discretizations. The work presented herein is a first step towards incorporating physically-based microstructures in lieu of the overly simplified representations that are commonly used. In broader terms, the proposed framework provides future avenues to explore bridging models of materials processes, e.g. additive manufacturing and microstructure evolution of multi-phase multi-component systems, into continuum-scale frameworks of the mechanical properties.« less

Influence of crack opening and incident wave angle on second harmonic generation of Lamb waves

NASA Astrophysics Data System (ADS)

Yang, Yi; Ng, Ching-Tai; Kotousov, Andrei

2018-05-01

Techniques utilising second harmonic generation (SHG) have proven their great potential in detecting contact-type damage. However, the gap between the practical applications and laboratory studies is still quite large. The current work is aimed to bridge this gap by investigating the effects of the applied load and incident wave angle on the detectability of fatigue cracks at various lengths. Both effects are critical for practical implementations of these techniques. The present experimental study supported by three-dimensional (3D) finite element (FE) modelling has demonstrated that the applied load, which changes the crack opening and, subsequently, the contact nonlinearity, significantly affects the amplitude of the second harmonic generated by the fundamental symmetric mode (S0) of Lamb wave. This amplitude is also dependent on the length of the fatigue crack as well as the incident wave angle. The experimental and FE results correlate well, so the modelling approach can be implemented for practical design of damage monitoring systems as well as for the evaluation of the severity of the fatigue cracks.

2D Analytical Model for the Directivity Prediction of Ultrasonic Contact Type Transducers in the Generation of Guided Waves.

PubMed

Tiwari, Kumar Anubhav; Raisutis, Renaldas; Mazeika, Liudas; Samaitis, Vykintas

2018-03-26

In this paper, a novel 2D analytical model based on the Huygens's principle of wave propagation is proposed in order to predict the directivity patterns of contact type ultrasonic transducers in the generation of guided waves (GWs). The developed model is able to estimate the directivity patterns at any distance, at any excitation frequency and for any configuration and shape of the transducers with prior information of phase dispersive characteristics of the guided wave modes and the behavior of transducer. This, in turn, facilitates to choose the appropriate transducer or arrays of transducers, suitable guided wave modes and excitation frequency for the nondestructive testing (NDT) and structural health monitoring (SHM) applications. The model is demonstrated for P1-type macro-fiber composite (MFC) transducer glued on a 2 mm thick aluminum (Al) alloy plate. The directivity patterns of MFC transducer in the generation of fundamental guided Lamb modes (the S0 and A0) and shear horizontal mode (the SH0) are successfully obtained at 80 kHz, 5-period excitation signal. The results are verified using 3D finite element (FE) modelling and experimental investigation. The results obtained using the proposed model shows the good agreement with those obtained using numerical simulations and experimental analysis. The calculation time using the analytical model was significantly shorter as compared to the time spent in experimental analysis and FE numerical modelling.

Kinetic Study on the Removal of Iron from Gold Mine Tailings by Citric Acid

NASA Astrophysics Data System (ADS)

Mashifana, T.; Mavimbela, N.; Sithole, N.

2018-03-01

The Gold mining generates large volumes of tailings, with consequent disposal and environmental problems. Iron tends to react with sulphur to form pyrite and pyrrhotite which then react with rain water forming acid rain. The study focuses on the removal of iron (Fe) from Gold Mine tailings; Fe was leached using citric acid as a leaching reagent. Three parameters which have an effect on the removal of Fe from the gold mine tailings, namely; temperature (25 °C and 50 °C), reagent concentration (0.25 M, 0.5 M, 0.75 M and 1 M) and solid loading ratio (20 %, 30 % and 40 %) were investigated. It was found that the recovery of Fe from gold mine tailings increased with increasing temperature and reagent concentration, but decreased with increasing solid loading ratio. The optimum conditions for the recovery of Fe from gold mine tailings was found to be at a temperature of 50 ºC, reagent concentration of 1 M and solid loading of 20 %. Three linear kinetic models were investigated and Prout-Tompkins kinetic model was the best fit yielding linear graphs with the highest R2 values.

Statistical Optimization of Reactive Plasma Cladding to Synthesize a WC-Reinforced Fe-Based Alloy Coating

NASA Astrophysics Data System (ADS)

Wang, Miqi; Zhou, Zehua; Wu, Lintao; Ding, Ying; Xu, Feilong; Wang, Zehua

2018-04-01

A new compound Fe-W-C powder for reactive plasma cladding was fabricated by precursor carbonization process using sucrose as a precursor. The application of quadratic general rotary unitized design was highlighted to develop a mathematical model to predict and accomplish the desired surface hardness of plasma-cladded coating. The microstructure and microhardness of the coating with optimal parameters were also investigated. According to the developed empirical model, the optimal process parameters were determined as follows: 1.4 for C/W atomic ratio, 20 wt.% for W content, 130 A for scanning current and 100 mm/min (1.67 mm/s) for scanning rate. The confidence level of the model was 99% according to the results of the F-test and lack-of-fit test. Microstructural study showed that the dendritic structure was comprised of a mechanical mixture of α-Fe and carbides, while the interdendritic structure was a eutectic of α-Fe and carbides in the composite coating with optimal parameters. WC phase generation can be confirmed from the XRD pattern. Due to good preparation parameters, the average microhardness of cladded coating can reach 1120 HV0.1, which was four times the substrate microhardness.

Synthesis of superior fast charging-discharging nano-LiFePO4/C from nano-FePO4 generated using a confined area impinging jet reactor approach.

PubMed

Liu, Xiao-min; Yan, Pen; Xie, Yin-Yin; Yang, Hui; Shen, Xiao-dong; Ma, Zi-Feng

2013-06-14

LiFePO4/C nanocomposites with excellent electrochemical performance is synthesized from nano-FePO4, generated by a novel method using a confined area impinging jet reactor (CIJR). When discharged at 80 C (13.6 Ag(-1)), the LiFePO4/C delivers a discharge capacity of 95 mA h g(-1), an energy density of 227 W h kg(-1) and a power density of 34 kW kg(-1).

Development and analysis of a finite element model to simulate pulmonary emphysema in CT imaging.

PubMed

Diciotti, Stefano; Nobis, Alessandro; Ciulli, Stefano; Landini, Nicholas; Mascalchi, Mario; Sverzellati, Nicola; Innocenti, Bernardo

2015-01-01

In CT imaging, pulmonary emphysema appears as lung regions with Low-Attenuation Areas (LAA). In this study we propose a finite element (FE) model of lung parenchyma, based on a 2-D grid of beam elements, which simulates pulmonary emphysema related to smoking in CT imaging. Simulated LAA images were generated through space sampling of the model output. We employed two measurements of emphysema extent: Relative Area (RA) and the exponent D of the cumulative distribution function of LAA clusters size. The model has been used to compare RA and D computed on the simulated LAA images with those computed on the models output. Different mesh element sizes and various model parameters, simulating different physiological/pathological conditions, have been considered and analyzed. A proper mesh element size has been determined as the best trade-off between reliable results and reasonable computational cost. Both RA and D computed on simulated LAA images were underestimated with respect to those calculated on the models output. Such underestimations were larger for RA (≈ -44 ÷ -26%) as compared to those for D (≈ -16 ÷ -2%). Our FE model could be useful to generate standard test images and to design realistic physical phantoms of LAA images for the assessment of the accuracy of descriptors for quantifying emphysema in CT imaging.

Dissociative Recombination of FeO(+) with Electrons: Implications for Plasma Layers in the Ionosphere.

PubMed

Bones, D L; Plane, J M C; Feng, W

2016-03-10

The dissociative recombination (DR) of FeO(+) ions with electrons has been studied in a flowing afterglow reactor. FeO(+) was generated by the pulsed laser ablation of a solid Fe target, and then entrained in an Ar(+) ion/electron plasma where the absolute electron density was measured using a Langmuir probe. A kinetic model describing gas-phase chemistry and diffusion to the reactor walls was fitted to the experimental data, yielding a DR rate coefficient at 298 K of k(FeO(+) + e(-)) = (5.5 ± 1.0) × 10(-7) cm(3) molecule(-1) s(-1), where the quoted uncertainty is at the 2σ level. Fe(+) ions in the lower thermosphere are oxidized by O3 to FeO(+), and this DR reaction is shown to provide a more important route for neutralizing Fe(+) below 110 km than the radiative/dielectronic recombination of Fe(+) with electrons. The experimental system was first validated by measuring two other DR reaction rate coefficients: k(O2(+) + e(-)) = (2.0 ± 0.4) × 10(-7) and k(N2O(+) + e(-)) = (3.3 ± 0.8) × 10(-7) cm(3) molecule(-1) s(-1), which are in good agreement with the recent literature.

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

The influence of irrigation-induced water table fluctuation on iron redistribution and arsenic immobilization within the unsaturation zone.

PubMed

Chi, Zeyong; Xie, Xianjun; Pi, Kunfu; Wang, Yanxin; Li, Junxia; Qian, Kun

2018-05-08

Given the long-term potential risk of arsenic (As)-contaminated agricultural soil to public health, the redistribution of iron (Fe) and immobilization of As within the unsaturation zone during irrigation and consequent water table fluctuations were studied via a column experiment and corresponding geochemical modeling. Experimental results show that As and Fe accumulated significantly at the top of the column during irrigation. A tremendous increase in As and Fe accumulation rates exists after water table recovery. It was deduced that Fe(II) and As(III) were oxidized directly by O 2 at the period of low water table. But the production of hydroxyl radical (OH) was promoted at the period of high water table due to the oxidation of adsorbed Fe(II). The generated OH further accelerate the oxidation of Fe(II) and As(III). Moreover, the combination of As and Fe is more stronger at the top of the column due to the transformation of combined states of As from surface complexation into surface precipitation with the growth of Fe(III) minerals. This study details the processes and mechanisms of As and Fe immobilization within the unsaturation zone during different irrigation periods and accordingly provides some insights to mitigate As accumulation in topsoil. Copyright © 2018 Elsevier B.V. All rights reserved.

Iron bioavailability studies of the first generation of iron-biofortified beans released in Rwanda

USDA-ARS?s Scientific Manuscript database

This paper represents a series of in vitro Fe bioavailability experiments, Fe content analysis and polyphenolic profile of the first generation of Fe biofortified beans (Phaseolus vulgaris) selected for human trials in Rwanda and released to farmers of that region. The objective of the present stud...

Improve regional distribution and source apportionment of PM2.5 trace elements in China using inventory-observation constrained emission factors.

PubMed

Ying, Qi; Feng, Miao; Song, Danlin; Wu, Li; Hu, Jianlin; Zhang, Hongliang; Kleeman, Michael J; Li, Xinghua

2018-05-15

Contributions to 15 trace elements in airborne particulate matter with aerodynamic diameters <2.5μm (PM 2.5 ) in China from five major source sectors (industrial sources, residential sources, transportation, power generation and windblown dust) were determined using a source-oriented Community Multiscale Air Quality (CMAQ) model. Using emission factors in the composite speciation profiles from US EPA's SPECIATE database for the five sources leads to relatively poor model performance at an urban site in Beijing. Improved predictions of the trace elements are obtained by using adjusted emission factors derived from a robust multilinear regression of the CMAQ predicted primary source contributions and observation at the urban site. Good correlations between predictions and observations are obtained for most elements studied with R>0.5, except for crustal elements Al, Si and Ca, particularly in spring. Predicted annual and seasonal average concentrations of Mn, Fe, Zn and Pb in Nanjing and Chengdu are also consistently improved using the adjusted emission factors. Annual average concentration of Fe is as high as 2.0μgm -3 with large contributions from power generation and transportation. Annual average concentration of Pb reaches 300-500ngm -3 in vast areas, mainly from residential activities, transportation and power generation. The impact of high concentrations of Fe on secondary sulfate formation and Pb on human health should be evaluated carefully in future studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Inferring Properties of Ancient Cyanobacteria from Biogeochemical Activity and Genomes of Siderophilic Cyanobacteria

NASA Technical Reports Server (NTRS)

McKay, David S.; Brown, I. I.; Tringe, S. G.; Thomas-Keprta, K. E.; Bryant, D. A.; Sarkisova, S. S.; Malley, K.; Sosa, O.; Klatt, C. G.; McKay, D. S.

2010-01-01

Interrelationships between life and the planetary system could have simultaneously left landmarks in genomes of microbes and physicochemical signatures in the lithosphere. Verifying the links between genomic features in living organisms and the mineralized signatures generated by these organisms will help to reveal traces of life on Earth and beyond. Among contemporary environments, iron-depositing hot springs (IDHS) may represent one of the most appropriate natural models [1] for insights into ancient life since organisms may have originated on Earth and probably Mars in association with hydrothermal activity [2,3]. IDHS also seem to be appropriate models for studying certain biogeochemical processes that could have taken place in the late Archean and,-or early Paleoproterozoic eras [4, 5]. It has been suggested that inorganic polyphosphate (PPi), in chains of tens to hundreds of phosphate residues linked by high-energy bonds, is environmentally ubiquitous and abundant [6]. Cyanobacteria (CB) react to increased heavy metal concentrations and UV by enhanced generation of PPi bodies (PPB) [7], which are believed to be signatures of life [8]. However, the role of PPi in oxygenic prokaryotes for the suppression of oxidative stress induced by high Fe is poorly studied. Here we present preliminary results of a new mechanism of Fe mineralization in oxygenic prokaryotes, the effect of Fe on the generation of PPi bodies in CB, as well as preliminary analysis of the diversity and phylogeny of proteins involved in the prevention of oxidative stress in phototrophs inhabiting IDHS.

Morphing the feature-based multi-blocks of normative/healthy vertebral geometries to scoliosis vertebral geometries: development of personalized finite element models.

PubMed

Hadagali, Prasannaah; Peters, James R; Balasubramanian, Sriram

2018-03-01

Personalized Finite Element (FE) models and hexahedral elements are preferred for biomechanical investigations. Feature-based multi-block methods are used to develop anatomically accurate personalized FE models with hexahedral mesh. It is tedious to manually construct multi-blocks for large number of geometries on an individual basis to develop personalized FE models. Mesh-morphing method mitigates the aforementioned tediousness in meshing personalized geometries every time, but leads to element warping and loss of geometrical data. Such issues increase in magnitude when normative spine FE model is morphed to scoliosis-affected spinal geometry. The only way to bypass the issue of hex-mesh distortion or loss of geometry as a result of morphing is to rely on manually constructing the multi-blocks for scoliosis-affected spine geometry of each individual, which is time intensive. A method to semi-automate the construction of multi-blocks on the geometry of scoliosis vertebrae from the existing multi-blocks of normative vertebrae is demonstrated in this paper. High-quality hexahedral elements were generated on the scoliosis vertebrae from the morphed multi-blocks of normative vertebrae. Time taken was 3 months to construct the multi-blocks for normative spine and less than a day for scoliosis. Efforts taken to construct multi-blocks on personalized scoliosis spinal geometries are significantly reduced by morphing existing multi-blocks.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid

PubMed Central

ZHANG, Xiang; GU, Xiaogang; LU, Shuguang; MIAO, Zhouwei; XU, Minhui; FU, Xiaori; DANISH, Muhammad; Brusseau, Mark L.; QIU, Zhaofu; SUI, Qian

2017-01-01

Trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H2O2 generation. The generation of HO• and O2−• in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly o direct oxidation by HO•, while O2−• strengthened the generation of HO• by promoting Fe(III) transformation in the CP/Fe(III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl−, HCO3−, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl− production suggested that TCE degradation in the CP/Fe(III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater. PMID:28959499

Anisotropic Resistivity Forward Modelling Using Automatic Generated Higher-order Finite Element Codes

NASA Astrophysics Data System (ADS)

Wang, W.; Liu, J.

2016-12-01

Forward modelling is the general way to obtain responses of geoelectrical structures. Field investigators might find it useful for planning surveys and choosing optimal electrode configurations with respect to their targets. During the past few decades much effort has been put into the development of numerical forward codes, such as integral equation method, finite difference method and finite element method. Nowadays, most researchers prefer the finite element method (FEM) for its flexible meshing scheme, which can handle models with complex geometry. Resistivity Modelling with commercial sofewares such as ANSYS and COMSOL is convenient, but like working with a black box. Modifying the existed codes or developing new codes is somehow a long period. We present a new way to obtain resistivity forward modelling codes quickly, which is based on the commercial sofeware FEPG (Finite element Program Generator). Just with several demanding scripts, FEPG could generate FORTRAN program framework which can easily be altered to adjust our targets. By supposing the electric potential is quadratic in each element of a two-layer model, we obtain quite accurate results with errors less than 1%, while more than 5% errors could appear by linear FE codes. The anisotropic half-space model is supposed to concern vertical distributed fractures. The measured apparent resistivities along the fractures are bigger than results from its orthogonal direction, which are opposite of the true resistivities. Interpretation could be misunderstood if this anisotropic paradox is ignored. The technique we used can obtain scientific codes in a short time. The generated powerful FORTRAN codes could reach accurate results by higher-order assumption and can handle anisotropy to make better interpretations. The method we used could be expand easily to other domain where FE codes are needed.

Quantum yield measurements of light-induced H₂ generation in a photosystem I-[FeFe]-H₂ase nanoconstruct.

PubMed

Applegate, Amanda M; Lubner, Carolyn E; Knörzer, Philipp; Happe, Thomas; Golbeck, John H

2016-01-01

The quantum yield for light-induced H2 generation was measured for a previously optimized bio-hybrid cytochrome c 6-crosslinked PSI(C13G)-1,8-octanedithiol-[FeFe]-H2ase(C97G) (PSI-H2ase) nanoconstruct. The theoretical quantum yield for the PSI-H2ase nanoconstruct is 0.50 molecules of H2 per photon absorbed, which equates to a requirement of two photons per H2 generated. Illumination of the PSI-H2ase nanoconstruct with visible light between 400 and 700 nm resulted in an average quantum yield of 0.10-0.15 molecules of H2 per photon absorbed, which equates to a requirement of 6.7-10 photons per H2 generated. A possible reason for the difference between the theoretical and experimental quantum yield is the occurrence of non-productive PSI(C13G)-1,8-octanedithiol-PSIC13G (PSI-PSI) conjugates, which would absorb light without generating H2. Assuming the thiol-Fe coupling is equally efficient at producing PSI-PSI conjugates as well as in producing PSI-H2ase nanoconstructs, the theoretical quantum yield would decrease to 0.167 molecules of H2 per photon absorbed, which equates to 6 photons per H2 generated. This value is close to the range of measured values in the current study. A strategy that purifies the PSI-H2ase nanoconstructs from the unproductive PSI-PSI conjugates or that incorporates different chemistries on the PSI and [FeFe]-H2ase enzyme sites could potentially allow the PSI-H2ase nanoconstruct to approach the expected theoretical quantum yield for light-induced H2 generation.

A Physically Motivated and Empirically Calibrated Method to Measure the Effective Temperature, Metallicity, and Ti Abundance of M Dwarfs

NASA Astrophysics Data System (ADS)

Veyette, Mark J.; Muirhead, Philip S.; Mann, Andrew W.; Brewer, John M.; Allard, France; Homeier, Derek

2017-12-01

The ability to perform detailed chemical analysis of Sun-like F-, G-, and K-type stars is a powerful tool with many applications, including studying the chemical evolution of the Galaxy and constraining planet formation theories. Unfortunately, complications in modeling cooler stellar atmospheres hinders similar analyses of M dwarf stars. Empirically calibrated methods to measure M dwarf metallicity from moderate-resolution spectra are currently limited to measuring overall metallicity and rely on astrophysical abundance correlations in stellar populations. We present a new, empirical calibration of synthetic M dwarf spectra that can be used to infer effective temperature, Fe abundance, and Ti abundance. We obtained high-resolution (R ˜ 25,000), Y-band (˜1 μm) spectra of 29 M dwarfs with NIRSPEC on Keck II. Using the PHOENIX stellar atmosphere modeling code (version 15.5), we generated a grid of synthetic spectra covering a range of temperatures, metallicities, and alpha-enhancements. From our observed and synthetic spectra, we measured the equivalent widths of multiple Fe I and Ti I lines and a temperature-sensitive index based on the FeH band head. We used abundances measured from widely separated solar-type companions to empirically calibrate transformations to the observed indices and equivalent widths that force agreement with the models. Our calibration achieves precisions in T eff, [Fe/H], and [Ti/Fe] of 60 K, 0.1 dex, and 0.05 dex, respectively, and is calibrated for 3200 K < T eff < 4100 K, -0.7 < [Fe/H] < +0.3, and -0.05 < [Ti/Fe] < +0.3. This work is a step toward detailed chemical analysis of M dwarfs at a precision similar to what has been achieved for FGK stars.

Isochrones for old (>5 Gyr) stars and stellar populations. I. Models for –2.4 ≤ [Fe/H] ≤+0.6, 0.25 ≤ Y ≤ 0.33, and –0.4 ≤ [α/Fe] ≤+0.4

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

VandenBerg, Don A.; Bergbusch, Peter A.; Ferguson, Jason W.

2014-10-10

Canonical grids of stellar evolutionary sequences have been computed for the helium mass-fraction abundances Y = 0.25, 0.29, and 0.33, and for iron abundances that vary from –2.4 to +0.4 (in 0.2 dex increments) when [α/Fe] =+0.4, or for the ranges –2.0 ≤ [Fe/H] ≤+0.6, –1.8 ≤ [Fe/H] ≤+0.6 when [α/Fe] =0.0 and –0.4, respectively. The grids, which consist of tracks for masses from 0.12 M{sub ⊙} to 1.1-1.5 M{sub ⊙} (depending on the metallicity) are based on up-to-date physics, including the gravitational settling of helium (but not metals diffusion). Interpolation software is provided to generate isochrones for arbitrary agesmore » between ≈5 and 15 Gyr and any values of Y, [α/Fe], and [Fe/H] within the aformentioned ranges. Comparisons of isochrones with published color-magnitude diagrams (CMDs) for the open clusters M67 ([Fe/H] ≈0.0) and NGC 6791 ([Fe/H] ≈0.3) and for four of the metal-poor globular clusters (47 Tuc, M3, M5, and M92) indicate that the models for the observed metallicities do a reasonably good job of reproducing the locations and slopes of the cluster main sequences and giant branches. The same conclusion is reached from a consideration of plots of nearby subdwarfs that have accurate Hipparcos parallaxes and metallicities in the range –2.0 ≲ [Fe/H] ≲ –1.0 on various CMDs and on the (log T {sub eff}, M{sub V} ) diagram. A relatively hot temperature scale similar to that derived in recent calibrations of the infrared flux method is favored by both the isochrones and the adopted color transformations, which are based on the latest MARCS model atmospheres.« less

Central Elemental Abundance Ratios In the Perseus Cluster: Resonant Scattering or SN Ia Enrichment?

NASA Technical Reports Server (NTRS)

Dupke, Renato A.; Arnaud, Keith; White, Nicholas E. (Technical Monitor)

2001-01-01

We have determined abundance ratios in the core of the Perseus Cluster for several elements. These ratios indicate a central dominance of Type 1a supernova (SN Ia) ejects similar to that found for A496, A2199 and A3571. Simultaneous analysis of ASCA spectra from SIS1, GIS2, and GIS3 shows that the ratio of Ni to Fe abundances is approx. 3.4 +/- 1.1 times solar within the central 4'. This ratio is consistent with (and more precise than) that observed in other clusters whose central regions are dominated by SN Ia ejecta. Such a large Ni overabundance is predicted by "convective deflagration" explosion models for SNe Ia such as W7 but is inconsistent with delayed detonation models. We note that with current instrumentation the Ni K(alpha) line is confused with Fe K(beta) and that the Ni overabundance we observe has been interpreted by others as an anomalously large ratio of Fe K(beta) to Fe K(alpha) caused by resonant scattering in the Fe K(alpha) line. We argue that a central enhancement of SN Ia ejecta and hence a high ratio of Ni to Fe abundances are naturally explained by scenarios that include the generation of chemical gradients by suppressed SN Ia winds or ram pressure stripping of cluster galaxies. It is not necessary to suppose that the intracluster gas is optically thick to resonant scattering of the Fe K(alpha) line.

Generation of magnetic skyrmion bubbles by inhomogeneous spin Hall currents

DOE PAGES

Heinonen, Olle; Jiang, Wanjun; Somaily, Hamoud; ...

2016-03-07

Recent experiments have shown that magnetic skyrmion bubbles can be generated and injected at room temperature in thin films. In this study, we demonstrate, using micromagnetic modeling, that such skyrmions can be generated by an inhomogeneous spin Hall torque in the presence of Dzyaloshinskii-Moriya interactions (DMIs). In the experimental Ta-Co 20Fe 60B 20 thin films, the DMI is rather small; nevertheless, the skyrmion bubbles are stable, or at least metastable on observational time scales.

FeO and H-2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1983-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting Earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

FeO and H2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1984-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would resuit in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

Thermally Generated Spin Signals in a Nondegenerate Silicon Spin Valve

NASA Astrophysics Data System (ADS)

Yamashita, Naoto; Ando, Yuichiro; Koike, Hayato; Miwa, Shinji; Suzuki, Yoshishige; Shiraishi, Masashi

2018-05-01

Thermally generated spin signals are observed in a nondegenerate Si spin valve. The spin-dependent Seebeck effect is used for thermal spin-signal generation. A thermal gradient of about 200 mK at the interface of Fe and Si enables the generation of a spin voltage of 8 μ V at room temperature. A simple expansion of the conventional spin-drift-diffusion model that takes into account the spin-dependent Seebeck effect shows that semiconductor materials are more promising for thermal spin-signal generation comparing than metallic materials, and thus enable efficient heat recycling in semiconductor spin devices.

The Semireduced Mechanism for Nitric Oxide Reduction by Non-Heme Diiron Complexes: Modeling Flavodiiron Nitric Oxide Reductases.

PubMed

White, Corey J; Speelman, Amy L; Kupper, Claudia; Demeshko, Serhiy; Meyer, Franc; Shanahan, James P; Alp, E Ercan; Hu, Michael; Zhao, Jiyong; Lehnert, Nicolai

2018-02-21

Flavodiiron nitric oxide reductases (FNORs) are a subclass of flavodiiron proteins (FDPs) capable of preferential binding and subsequent reduction of NO to N 2 O. FNORs are found in certain pathogenic bacteria, equipping them with resistance to nitrosative stress, generated as a part of the immune defense in humans, and allowing them to proliferate. Here, we report the spectroscopic characterization and detailed reactivity studies of the diiron dinitrosyl model complex [Fe 2 (BPMP)(OPr)(NO) 2 ](OTf) 2 for the FNOR active site that is capable of reducing NO to N 2 O [Zheng et al., J. Am. Chem. Soc. 2013, 135, 4902-4905]. Using UV-vis spectroscopy, cyclic voltammetry, and spectro-electrochemistry, we show that one reductive equivalent is in fact sufficient for the quantitative generation of N 2 O, following a semireduced reaction mechanism. This reaction is very efficient and produces N 2 O with a first-order rate constant k > 10 2 s -1 . Further isotope labeling studies confirm an intramolecular N-N coupling mechanism, consistent with the rapid time scale of the reduction and a very low barrier for N-N bond formation. Accordingly, the reaction proceeds at -80 °C, allowing for the direct observation of the mixed-valent product of the reaction. At higher temperatures, the initial reaction product is unstable and decays, ultimately generating the diferrous complex [Fe 2 (BPMP)(OPr) 2 ](OTf) and an unidentified ferric product. These results combined offer deep insight into the mechanism of NO reduction by the relevant model complex [Fe 2 (BPMP)(OPr)(NO) 2 ] 2+ and provide direct evidence that the semireduced mechanism would constitute a highly efficient pathway to accomplish NO reduction to N 2 O in FNORs and in synthetic catalysts.

Arterial thrombosis is accelerated in mice deficient in histidine-rich glycoprotein

PubMed Central

Vu, Trang T.; Zhou, Ji; Leslie, Beverly A.; Stafford, Alan R.; Fredenburgh, James C.; Ni, Ran; Qiao, Shengjun; Vaezzadeh, Nima; Jahnen-Dechent, Willi; Monia, Brett P.; Gross, Peter L.; Weitz, Jeffrey I.

2015-01-01

Factor (F) XII, a key component of the contact system, triggers clotting via the intrinsic pathway, and is implicated in propagating thrombosis. Although nucleic acids are potent activators, it is unclear how the contact system is regulated to prevent uncontrolled clotting. Previously, we showed that histidine-rich glycoprotein (HRG) binds FXIIa and attenuates its capacity to trigger coagulation. To investigate the role of HRG as a regulator of the intrinsic pathway, we compared RNA- and DNA-induced thrombin generation in plasma from HRG-deficient and wild-type mice. Thrombin generation was enhanced in plasma from HRG-deficient mice, and accelerated clotting was restored to normal with HRG reconstitution. Although blood loss after tail tip amputation was similar in HRG-deficient and wild-type mice, carotid artery occlusion after FeCl3 injury was accelerated in HRG-deficient mice, and HRG administration abrogated this effect. To confirm that HRG modulates the contact system, we used DNase, RNase, and antisense oligonucleotides to characterize the FeCl3 model. Whereas DNase or FVII knockdown had no effect, carotid occlusion was abrogated with RNase or FXII knockdown, confirming that FeCl3-induced thrombosis is triggered by RNA in a FXII-dependent fashion. Therefore, in a nucleic acid–driven model, HRG inhibits thrombosis by modulating the intrinsic pathway of coagulation. PMID:25691157

Development of a Tabletop Model for the Generation of Amorphous/ Microcrystalline Metal Powders

DTIC Science & Technology

1980-04-30

Voltage Characteristics for Wetting (si) and Non-wetting (AZ 4.5% Cu ) EHD Spray 2-57 28 Schematic of the Process of Electrohydrodynamic Droplet...Microscope Image of a Deposit , Fine Powders and "Matrix" Film of Fe-Ni-B-P Metallic Glass Alloy Produced by the EHD Technique 3-9 45 Selected Area...Transmission Electron Microscope Image of a Deposit , Fine Powders and "Matrix" Film of Fe-Ni-B-P Metallic Glass Alloy Produced by the EHD Technique 3-11 xi

Manufacturing of diamond windows for synchrotron radiation

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

Schildkamp, W.; Nikitina, L.

2012-09-15

A new diamond window construction is presented and explicit manufacturing details are given. This window will increase the power dissipation by about a factor of 4 over present day state of the art windows to absorb 600 W of power. This power will be generated by in-vacuum undulators with the storage ring ALBA operating at a design current of 400 mA. Extensive finite element (FE) calculations are included to predict the windows behavior accompanied by explanations for the chosen boundary conditions. A simple linear model was used to cross-check the FE calculations.

[NiFeSe]-hydrogenase chemistry.

PubMed

Wombwell, Claire; Caputo, Christine A; Reisner, Erwin

2015-11-17

The development of technology for the inexpensive generation of the renewable energy vector H2 through water splitting is of immediate economic, ecological, and humanitarian interest. Recent interest in hydrogenases has been fueled by their exceptionally high catalytic rates for H2 production at a marginal overpotential, which is presently only matched by the nonscalable noble metal platinum. The mechanistic understanding of hydrogenase function guides the design of synthetic catalysts, and selection of a suitable hydrogenase enables direct applications in electro- and photocatalysis. [FeFe]-hydrogenases display excellent H2 evolution activity, but they are irreversibly damaged upon exposure to O2, which currently prevents their use in full water splitting systems. O2-tolerant [NiFe]-hydrogenases are known, but they are typically strongly biased toward H2 oxidation, while H2 production by [NiFe]-hydrogenases is often product (H2) inhibited. [NiFeSe]-hydrogenases are a subclass of [NiFe]-hydrogenases with a selenocysteine residue coordinated to the active site nickel center in place of a cysteine. They exhibit a combination of unique properties that are highly advantageous for applications in water splitting compared with other hydrogenases. They display a high H2 evolution rate with marginal inhibition by H2 and tolerance to O2. [NiFeSe]-hydrogenases are therefore one of the most active molecular H2 evolution catalysts applicable in water splitting. Herein, we summarize our recent progress in exploring the unique chemistry of [NiFeSe]-hydrogenases through biomimetic model chemistry and the chemistry with [NiFeSe]-hydrogenases in semiartificial photosynthetic systems. We gain perspective from the structural, spectroscopic, and electrochemical properties of the [NiFeSe]-hydrogenases and compare them with the chemistry of synthetic models of this hydrogenase active site. Our synthetic models give insight into the effects on the electronic properties and reactivity of the active site upon the introduction of selenium. We have utilized the exceptional properties of the [NiFeSe]-hydrogenase from Desulfomicrobium baculatum in a number of photocatalytic H2 production schemes, which are benchmark systems in terms of single site activity, tolerance toward O2, and in vitro water splitting with biological molecules. Each system comprises a light-harvesting component, which allows for light-driven electron transfer to the hydrogenase in order for it to catalyze H2 production. A system with [NiFeSe]-hydrogenase on a dye-sensitized TiO2 nanoparticle gives an enzyme-semiconductor hybrid for visible light-driven generation of H2 with an enzyme-based turnover frequency of 50 s(-1). A stable and inexpensive polymeric carbon nitride as a photosensitizer in combination with the [NiFeSe]-hydrogenase shows good activity for more than 2 days. Light-driven H2 evolution with the enzyme and an organic dye under high O2 levels demonstrates the excellent robustness and feasibility of water splitting with a hydrogenase-based scheme. This has led, most recently, to the development of a light-driven full water splitting system with a [NiFeSe]-hydrogenase wired to the water oxidation enzyme photosystem II in a photoelectrochemical cell. In contrast to the other systems, this photoelectrochemical system does not rely on a sacrificial electron donor and allowed us to establish the long sought after light-driven water splitting with an isolated hydrogenase.

Paracetamol degradation intermediates and toxicity during photo-Fenton treatment using different iron species.

PubMed

Trovó, Alam G; Pupo Nogueira, Raquel F; Agüera, Ana; Fernandez-Alba, Amadeo R; Malato, Sixto

2012-10-15

The photo-Fenton degradation of paracetamol (PCT) was evaluated using FeSO(4) and the iron complex potassium ferrioxalate (FeOx) as iron source under simulated solar light. The efficiency of the degradation process was evaluated considering the decay of PCT and total organic carbon concentration and the generation of carboxylic acids, ammonium and nitrate, expressed as total nitrogen. The results showed that the degradation was favored in the presence of FeSO(4) in relation to FeOx. The higher concentration of hydroxylated intermediates generated in the presence of FeSO(4) in relation to FeOx probably enhanced the reduction of Fe(III) to Fe(II) improving the degradation efficiency. The degradation products were determined using liquid chromatography electrospray time-of-flight mass spectrometry. Although at different concentrations, the same intermediates were generated using either FeSO(4) or FeOx, which were mainly products of hydroxylation reactions and acetamide. The toxicity of the sample for Vibrio fischeri and Daphnia magna decreased from 100% to less than 40% during photo-Fenton treatment in the presence of both iron species, except for D. magna in the presence of FeOx due to the toxicity of oxalate to this organism. The considerable decrease of the sample toxicity during photo-Fenton treatment using FeSO(4) indicates a safe application of the process for the removal of this pharmaceutical. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fast nitrate and fluoride adsorption and magnetic separation from water on α-Fe2O3 and Fe3O4 dispersed on Douglas fir biochar.

PubMed

Bombuwala Dewage, Narada; Liyanage, Achala S; Pittman, Charles U; Mohan, Dinesh; Mlsna, Todd

2018-05-02

α-Fe 2 O 3 and Fe 3 O 4 dispersed on high surface area (663 m 2 /g) Douglas fir biochar (BC) was prepared for fast nitrate and fluoride ion removal from water using magnetic separations. This biochar, made originally at 900 °C, was impregnated with FeCl 3 and converted by pyrolysis at 600 °C to magnetic (494 m 2 /g) biochar (MBC). MBC and its precursor BC were characterized using SEM, SEM-EDX, STEM, S BET , PZC measurements, XRD analysis, and XPS. Dispersed α-Fe 2 O 3 and Fe 3 O 4 particles caused magnetization and generated most adsorption sites, causing more nitrate and fluoride uptake than BC. Both nitrate and fluoride adsorption on MBC remained high over a pH range from 2 to 10. Sorption was evaluated from 298 to 318 K using the Langmuir and Freundlich isotherm models. Langmuir adsorption capacities were 15 mg/g for nitrate and 9 mg/g for fluoride, higher capacities than those reported for other biochar and iron oxide adsorbents. Published by Elsevier Ltd.

DETECTION OF PHOSPHORUS, SULPHUR, AND ZINC IN THE CARBON-ENHANCED METAL-POOR STAR BD+44 493

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

Roederer, Ian U.; Placco, Vinicius M.; Beers, Timothy C., E-mail: iur@umich.edu

2016-06-20

The carbon-enhanced metal-poor star BD+44°493 ([Fe/H] = −3.9) has been proposed as a candidate second-generation star enriched by metals from a single Pop III star. We report the first detections of P and S and the second detection of Zn in any extremely metal-poor carbon-enhanced star, using new spectra of BD+44°493 collected by the Cosmic Origins Spectrograph on the Hubble Space Telescope . We derive [P/Fe] = −0.34 ± 0.21, [S/Fe] = +0.07 ± 0.41, and [Zn/Fe] = −0.10 ± 0.24. We increase by 10-fold the number of Si i lines detected in BD+44°493, yielding [Si/Fe] = +0.15 ± 0.22.more » The [S/Fe] and [Zn/Fe] ratios exclude the hypothesis that the abundance pattern in BD+44°493 results from depletion of refractory elements onto dust grains. Comparison with zero-metallicity supernova (SN) models suggests that the stellar progenitor that enriched BD+44°493 was massive and ejected much less than 0.07 M {sub ⊙} of {sup 56}Ni, characteristic of a faint SN.« less

Human frataxin is an allosteric switch that activates the Fe-S cluster biosynthetic complex.

PubMed

Tsai, Chi-Lin; Barondeau, David P

2010-11-02

Cellular depletion of the human protein frataxin is correlated with the neurodegenerative disease Friedreich's ataxia and results in the inactivation of Fe-S cluster proteins. Most researchers agree that frataxin functions in the biogenesis of Fe-S clusters, but its precise role in this process is unclear. Here we provide in vitro evidence that human frataxin binds to a Nfs1, Isd11, and Isu2 complex to generate the four-component core machinery for Fe-S cluster biosynthesis. Frataxin binding dramatically changes the K(M) for cysteine from 0.59 to 0.011 mM and the catalytic efficiency (k(cat)/K(M)) of the cysteine desulfurase from 25 to 7900 M⁻¹s⁻¹. Oxidizing conditions diminish the levels of both complex formation and frataxin-based activation, whereas ferrous iron further stimulates cysteine desulfurase activity. Together, these results indicate human frataxin functions with Fe(2+) as an allosteric activator that triggers sulfur delivery and Fe-S cluster assembly. We propose a model in which cellular frataxin levels regulate human Fe-S cluster biosynthesis that has implications for mitochondrial dysfunction, oxidative stress response, and both neurodegenerative and cardiovascular disease.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Location Distribution Optimization of Photographing Sites for Indoor Panorama Modeling

NASA Astrophysics Data System (ADS)

Zhang, S.; Wu, J.; Zhang, Y.; Zhang, X.; Xin, Z.; Liu, J.

2017-09-01

Generally, panoramas image modeling is costly and time-consuming because of photographing continuously to capture enough photos along the routes, especially in complicated indoor environment. Thus, difficulty follows for a wider applications of panoramic image modeling for business. It is indispensable to make a feasible arrangement of panorama sites locations because the locations influence the clarity, coverage and the amount of panoramic images under the condition of certain device. This paper is aim to propose a standard procedure to generate the specific location and total amount of panorama sites in indoor panoramas modeling. Firstly, establish the functional relationship between one panorama site and its objectives. Then, apply the relationship to panorama sites network. We propose the Distance Clarity function (FC and Fe) manifesting the mathematical relationship between panoramas and objectives distance or obstacle distance. The Distance Buffer function (FB) is modified from traditional buffer method to generate the coverage of panorama site. Secondly, transverse every point in possible area to locate possible panorama site, calculate the clarity and coverage synthetically. Finally select as little points as possible to satiate clarity requirement preferentially and then the coverage requirement. In the experiments, detailed parameters of camera lens are given. Still, more experiments parameters need trying out given that relationship between clarity and distance is device dependent. In short, through the function FC, Fe and FB, locations of panorama sites can be generated automatically and accurately.

Water adsorption on the Fe3O4(111) surface: dissociation and network formation.

PubMed

Zaki, Eman; Mirabella, Francesca; Ivars-Barceló, Francisco; Seifert, Jan; Carey, Spencer; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Li, Xiaoke; Paier, Joachim; Sauer, Joachim

2018-06-13

We monitored adsorption of water on a well-defined Fe3O4(111) film surface at different temperatures as a function of coverage using infrared reflection-absorption spectroscopy, temperature programmed desorption, and single crystal adsorption calorimetry. Additionally, density functional theory was employed using a Fe3O4(111)-(2 × 2) slab model to generate 15 energy minimum structures for various coverages. Corresponding vibrational properties of the adsorbed water species were also computed. The results show that water molecules readily dissociate on regular surface Fetet1-O ion pairs to form "monomers", i.e., terminal Fe-OH and surface OH groups. Further water molecules adsorb on the hydroxyl covered surface non-dissociatively and form "dimers" and larger oligomers, which ultimately assemble into an ordered (2 × 2) hydrogen-bonded network structure with increasing coverage prior to the formation of a solid water film.

Multiferroicity in the generic easy-plane triangular lattice antiferromagnet RbFe(MoO4)2

NASA Astrophysics Data System (ADS)

White, J. S.; Niedermayer, Ch.; Gasparovic, G.; Broholm, C.; Park, J. M. S.; Shapiro, A. Ya.; Demianets, L. A.; Kenzelmann, M.

2013-08-01

RbFe(MoO4)2 is a quasi-two-dimensional (quasi-2D) triangular lattice antiferromagnet (TLA) that displays a zero-field magnetically driven multiferroic phase with a chiral spin structure. By inelastic neutron scattering, we determine quantitatively the spin Hamiltonian. We show that the easy-plane anisotropy is nearly 1/3 of the dominant spin exchange, making RbFe(MoO4)2 an excellent system for studying the physics of the model 2D easy-plane TLA. Our measurements demonstrate magnetic-field-induced fluctuations in this material to stabilize the generic finite-field phases of the 2D XY TLA. We further explain how Dzyaloshinskii-Moriya interactions can generate ferroelectricity only in the zero-field phase. Our conclusion is that multiferroicity in RbFe(MoO4)2, and its absence at high fields, results from the generic properties of the 2D XY TLA.

QUANTIFYING THE CARBON ABUNDANCES IN THE SECONDARY STARS OF SS CYGNI, RU PEGASI, AND GK PERSEI

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

Harrison, Thomas E.; Hamilton, Ryan T., E-mail: tharriso@nmsu.edu, E-mail: rthamilton@sofia.usra.edu

We use a modified version of MOOG to generate large grids of synthetic spectra in an attempt to derive quantitative abundances for three CVs (GK Per, RU Peg, and SS Cyg) by comparing the models to moderate resolution (R ∼ 25,000) K-band spectra obtained with NIRSPEC on Keck. For each of the three systems we find solar, or slightly sub-solar values for [Fe/H], but significant deficits of carbon: for SS Cyg we find [C/Fe] = −0.50, for RU Peg [C/Fe] = −0.75, and for GK Per [C/Fe] = −1.00. We show that it is possible to use lower resolution (Rmore » ∼ 2000) spectra to quantify carbon deficits. We examine realistic veiling scenarios and find that emission from H i or CO cannot reproduce the observations.« less

A parametric model order reduction technique for poroelastic finite element models.

PubMed

Lappano, Ettore; Polanz, Markus; Desmet, Wim; Mundo, Domenico

2017-10-01

This research presents a parametric model order reduction approach for vibro-acoustic problems in the frequency domain of systems containing poroelastic materials (PEM). The method is applied to the Finite Element (FE) discretization of the weak u-p integral formulation based on the Biot-Allard theory and makes use of reduced basis (RB) methods typically employed for parametric problems. The parametric reduction is obtained rewriting the Biot-Allard FE equations for poroelastic materials using an affine representation of the frequency (therefore allowing for RB methods) and projecting the frequency-dependent PEM system on a global reduced order basis generated with the proper orthogonal decomposition instead of standard modal approaches. This has proven to be better suited to describe the nonlinear frequency dependence and the strong coupling introduced by damping. The methodology presented is tested on two three-dimensional systems: in the first experiment, the surface impedance of a PEM layer sample is calculated and compared with results of the literature; in the second, the reduced order model of a multilayer system coupled to an air cavity is assessed and the results are compared to those of the reference FE model.

Investigating the Consistency of Stellar Evolution Models with Globular Cluster Observations via the Red Giant Branch Bump

NASA Astrophysics Data System (ADS)

Joyce, Meridith; Chaboyer, Brian

2016-01-01

Synthetic Red Giant Branch Bump (RGBB) magnitudes are generated with the most recent theoretical stellar evolution models computed with the Dartmouth Stellar Evolution Program (DSEP) code. They are compared to the observational work of Nataf et al. (2013), who present RGBB magnitudes for 72 globular clusters. A DSEP model using a chemical composition with enhanced α capture [α/Fe] =+0.4 and an age of 13 Gyr shows agreement with observations over metallicities ranging from [Fe/H] = 0 to [Fe/H] ≈-1.5, with discrepancy emerging at lower metallicities. A model-independent, density-based outlier detection routine known as the Local Outlying Factor (LOF) algorithm is applied to the observations in order to identify clusters that deviate most in magnitude-metallicity space from the bulk of the observations. Our model's fit is scrutinized with a series of χ^2 routines performed on subsets of the data from which highly anomalous clusters have been selectively removed based on LOF identification. In particular, NGCs 6254, 6681, 6218, and 1904 are tagged recurrently as outliers. The effects of systematic and non-systematic error in metallicity are assessed, and the robustness of observational error bars is investigated.

VTVH-MCD study of the Delta nifB Delta nifZ MoFe protein from Azotobacter vinelandii.

PubMed

Cotton, Marcia S; Rupnik, Kresimir; Broach, Robyn B; Hu, Yilin; Fay, Aaron W; Ribbe, Markus W; Hales, Brian J

2009-04-08

NifZ is a member of a series of proteins associated with the maturation of the nitrogenase MoFe protein. An MCD spectroscopic study was undertaken on the Delta nifB Delta nifZ MoFe protein generated in the absence of both NifZ and NifB (deletion of NifB generates an apo-MoFe protein lacking the FeMo cofactor). Results presented here show that, in the absence of NifZ, only one of the two P-clusters of the MoFe protein is matured to the ultimate [8Fe-7S] structure. The other P-cluster site in the protein contains a [4Fe-4S] cluster pair, representing a P-cluster precursor that is electronically identical to the analogous clusters observed in the Delta nifH MoFe protein. These results suggest that the MoFe protein is synthesized in a stepwise fashion where NifZ is specifically required for the formation of the second P-cluster.

First-principles approach to the dynamic magnetoelectric couplings for the non-reciprocal directional dichroism in BiFeO 3

DOE PAGES

Kezsmarki, I.; Fishman, Randy Scott

2016-04-18

Due to the complicated magnetic and crystallographic structures of BiFeO 3, its magnetoelectric (ME) couplings and microscopic model Hamiltonian remain poorly understood. By employing a firstprinciples approach, we uncover all possibleMEcouplings associated with the spin-current (SC) and exchange-striction (ES) polarizations, and construct an appropriate Hamiltonian for the long-range spin-cycloid in BiFeO 3. First-principles calculations are used to understand the microscopic origins of theMEcouplings.Wefind that inversion symmetries broken by ferroelectric and antiferroelectric distortions induce the SC and the ES polarizations, which cooperatively produce the dynamicME effects in BiFeO 3. A model motivated by first principles reproduces the absorption difference of counter-propagatingmore » light beams called non-reciprocal directional dichroism. The current paper focuses on the spin-driven (SD) polarizations produced by a dynamic electric field, i.e. the dynamic MEcouplings. Due to the inertial properties of Fe, the dynamic SD polarizations differ significantly from the static SD polarizations. Our systematic approach can be generally applied to any multiferroic material, laying the foundation for revealing hiddenMEcouplings on the atomic scale and for exploiting opticalMEeffects in the next generation of technological devices such as optical diodes.« less

Non-local detection of spin dynamics via spin rectification effect in yttrium iron garnet/SiO{sub 2}/NiFe trilayers near simultaneous ferromagnetic resonance

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

Soh, Wee Tee, E-mail: a0046479@u.nus.edu; Ong, C. K.; Peng, Bin

2015-08-15

The spin rectification effect (SRE), a phenomenon that generates dc voltages from ac microwave fields incident onto a conducting ferromagnet, has attracted widespread attention due to its high sensitivity to ferromagnetic resonance (FMR) as well as its relevance to spintronics. Here, we report the non-local detection of yttrium iron garnet (YIG) spin dynamics by measuring SRE voltages from an adjacent conducting NiFe layer up to 200 nm thick. In particular, we detect, within the NiFe layer, SRE voltages stemming from magnetostatic surface spin waves (MSSWs) of the adjacent bulk YIG which are excited by a shorted coaxial probe. These non-localmore » SRE voltages within the NiFe layer that originates from YIG MSSWs are present even in 200 nm-thick NiFe films with a 50 nm thick SiO{sub 2} spacer between NiFe and YIG, thus strongly ruling out the mechanism of spin-pumping induced inverse spin Hall effect in NiFe as the source of these voltages. This long-range influence of YIG dynamics is suggested to be mediated by dynamic fields generated from YIG spin precession near YIG/NiFe interface, which interacts with NiFe spins near the simultaneous resonance of both spins, to generate a non-local SRE voltage within the NiFe layer.« less

Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

NASA Astrophysics Data System (ADS)

Michalkova, Andrea; Kholod, Yana; Kosenkov, Dmytro; Gorb, Leonid; Leszczynski, Jerzy

2011-04-01

The viability of pyrite-pulled metabolism in the 'iron-sulfur world' theory was assessed using a simple model of iron-nickel sulfide (Fe-Ni-S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe-Ni-S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH 3SH and CO on an Fe-Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe-Ni-S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron-nickel sulfide surfaces is discussed.

Optimization and validation of FePro cell labeling method.

PubMed

Janic, Branislava; Rad, Ali M; Jordan, Elaine K; Iskander, A S M; Ali, Md M; Varma, N Ravi S; Frank, Joseph A; Arbab, Ali S

2009-06-11

Current method to magnetically label cells using ferumoxides (Fe)-protamine (Pro) sulfate (FePro) is based on generating FePro complexes in a serum free media that are then incubated overnight with cells for the efficient labeling. However, this labeling technique requires long (>12-16 hours) incubation time and uses relatively high dose of Pro (5-6 microg/ml) that makes large extracellular FePro complexes. These complexes can be difficult to clean with simple cell washes and may create low signal intensity on T2* weighted MRI that is not desirable. The purpose of this study was to revise the current labeling method by using low dose of Pro and adding Fe and Pro directly to the cells before generating any FePro complexes. Human tumor glioma (U251) and human monocytic leukemia cell (THP-1) lines were used as model systems for attached and suspension cell types, respectively and dose dependent (Fe 25 to 100 microg/ml and Pro 0.75 to 3 microg/ml) and time dependent (2 to 48 h) labeling experiments were performed. Labeling efficiency and cell viability of these cells were assessed. Prussian blue staining revealed that more than 95% of cells were labeled. Intracellular iron concentration in U251 cells reached approximately 30-35 pg-iron/cell at 24 h when labeled with 100 microg/ml of Fe and 3 microg/ml of Pro. However, comparable labeling was observed after 4 h across the described FePro concentrations. Similarly, THP-1 cells achieved approximately 10 pg-iron/cell at 48 h when labeled with 100 microg/ml of Fe and 3 microg/ml of Pro. Again, comparable labeling was observed after 4 h for the described FePro concentrations. FePro labeling did not significantly affect cell viability. There was almost no extracellular FePro complexes observed after simple cell washes. To validate and to determine the effectiveness of the revised technique, human T-cells, human hematopoietic stem cells (hHSC), human bone marrow stromal cells (hMSC) and mouse neuronal stem cells (mNSC C17.2) were labeled. Labeling for 4 hours using 100 microg/ml of Fe and 3 microg/ml of Pro resulted in very efficient labeling of these cells, without impairing their viability and functional capability. The new technique with short incubation time using 100 microg/ml of Fe and 3 microg/ml of Pro is effective in labeling cells for cellular MRI.

Micro Finite Element models of the vertebral body: Validation of local displacement predictions

PubMed Central

Costa, Maria Cristiana; Tozzi, Gianluca; Cristofolini, Luca; Danesi, Valentina; Viceconti, Marco

2017-01-01

The estimation of local and structural mechanical properties of bones with micro Finite Element (microFE) models based on Micro Computed Tomography images depends on the quality bone geometry is captured, reconstructed and modelled. The aim of this study was to validate microFE models predictions of local displacements for vertebral bodies and to evaluate the effect of the elastic tissue modulus on model’s predictions of axial forces. Four porcine thoracic vertebrae were axially compressed in situ, in a step-wise fashion and scanned at approximately 39μm resolution in preloaded and loaded conditions. A global digital volume correlation (DVC) approach was used to compute the full-field displacements. Homogeneous, isotropic and linear elastic microFE models were generated with boundary conditions assigned from the interpolated displacement field measured from the DVC. Measured and predicted local displacements were compared for the cortical and trabecular compartments in the middle of the specimens. Models were run with two different tissue moduli defined from microindentation data (12.0GPa) and a back-calculation procedure (4.6GPa). The predicted sum of axial reaction forces was compared to the experimental values for each specimen. MicroFE models predicted more than 87% of the variation in the displacement measurements (R2 = 0.87–0.99). However, model predictions of axial forces were largely overestimated (80–369%) for a tissue modulus of 12.0GPa, whereas differences in the range 10–80% were found for a back-calculated tissue modulus. The specimen with the lowest density showed a large number of elements strained beyond yield and the highest predictive errors. This study shows that the simplest microFE models can accurately predict quantitatively the local displacements and qualitatively the strain distribution within the vertebral body, independently from the considered bone types. PMID:28700618

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

DOE PAGES

Wilker, Molly B.; Utterback, James K.; Greene, Sophie; ...

2017-12-08

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

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

Wilker, Molly B.; Utterback, James K.; Greene, Sophie

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

Iron-mineral accretion from acid mine drainage and its application in passive treatment

PubMed Central

Florence, K.; Sapsford, D.J.; Johnson, D.B.; Kay, C.M.; Wolkersdorfer, C.

2016-01-01

ABSTRACT This study demonstrates substantial removal of iron (Fe) from acid mine drainage (pH ≈3) in a passive vertical flow reactor (VFR) with an equivalent footprint of 154 m2 per L/s mine water and residence times of >23 h. Average Fe removal rate was 67% with a high of 85% over the 10-month trial. The fraction of Fe passing a 0.22 µm filter (referred to here as Fe-filt) was seen to be removed in the VFR even when Fe(II) was absent, indicating that the contribution of microbial Fe(II) oxidation and precipitation was not the dominant removal mechanism in the VFR. Removal rates of Fe-filt in the VFR were up to 70% in residence times as low as 8 h compared with laboratory experiments where much smaller changes in Fe-filt were observed over 60 h. Centrifugation indicated that 80–90% of the influent Fe had particle sizes <35 nm. Together with analyses and geochemical modelling, this suggests that the Fe-filt fraction exists as either truly aqueous (but oversaturated) Fe(III) or nanoparticulate Fe(III) and that this metastability persists. When the water was contacted with VFR sludge, the Fe-filt fraction was destabilized, leading to an appreciably higher removal of this fraction. Heterogeneous precipitation and/or aggregation of nanoparticulate Fe(III) precipitates are considered predominant removal mechanisms. Microbial analyses of the mine water revealed the abundance of extracellular polymeric substance-generating Fe-oxidizing bacterium ‘Ferrovum myxofaciens’, which may aid the removal of iron and explain the unusual appearance and physical properties of the sludge. PMID:26675674

A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts.

PubMed

Ghosh, Pokhraj; Ding, Shengda; Chupik, Rachel B; Quiroz, Manuel; Hsieh, Chung-Hung; Bhuvanesh, Nattami; Hall, Michael B; Darensbourg, Marcetta Y

2017-12-01

Experimental and computational studies address key questions in a structure-function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN 2 S 2 or [(NO)Fe]N 2 S 2 as donors to (η 5 -C 5 H 5 )Fe(CO) + or [Fe(NO) 2 ] +/0 generate a series of four bimetallics, gradually "softened" by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox levels, demonstrating required features of electrocatalysis. Computational modeling of experimental structures and likely transient intermediates that connect the electrochemical events find roles for electron delocalization by NO, as well as Fe-S bond dissociation that produce a terminal thiolate as pendant base well positioned to facilitate proton uptake and transfer. Dihydrogen formation is via proton/hydride coupling by internal S-H + ··· - H-Fe units of the "harder" bimetallic arrangements with more localized electron density, while softer units convert H - ···H - via reductive elimination from two Fe-H deriving from the highly delocalized, doubly reduced [Fe 2 (NO) 3 ] - derivative. Computational studies also account for the inactivity of a Ni 2 Fe complex resulting from entanglement of added H + in a pinched -S δ - ···H + ··· δ - S- arrangement.

Revisiting Coiled Flocculator Performance for Particle Aggregation.

PubMed

2017-09-08

This work summarizes recent studies evaluating the torsion and curvature parameters in the flocculation efficiency using a hydraulic plug-flow flocculator named as Flocs Generator Reactor (FGR). Colloidal Fe(OH)3 and coal particles were used as suspension models and a cationic polyacrylamide was used for the flocculation. The effectiveness of the aggregation process (in the distinct curvature and torsion parameters and hydrodynamic conditions) was evaluated by the settling rate of the Fe(OH)3 flocs and flocs size by photographic analysis. Due to curvature, a secondary flow is induced and the profiles of the flow quantities differ from those for a straight pipe. Results showed that the difference in the flocculator design influences the Fe(OH)3 flocs size and settling rates, reaching values about 13 and 4 mh-1, for the coiled and straight pipes respectively. Coal flocs generation also showed to be dependent on the flocculator design and shear rate. Results showed that turbulent kinetic energy increases due to curvature when the torsion parameter is kept constant (pitch close to zero) enhancing the flocs formation.

Self-report measure of financial exploitation of older adults.

PubMed

Conrad, Kendon J; Iris, Madelyn; Ridings, John W; Langley, Kate; Wilber, Kathleen H

2010-12-01

this study was designed to improve the measurement of financial exploitation (FE) by testing psychometric properties of the older adult financial exploitation measure (OAFEM), a client self-report instrument. rasch item response theory and traditional validation approaches were used. Questionnaires were administered by 22 adult protective services investigators from 7 agencies in Illinois to 227 substantiated abuse clients. Analyses included tests for dimensionality, model fit, and additional construct validation. Results from the OAFEM were also compared with the substantiation decision of abuse and with investigators' assessments of FE using a staff report version. Hypotheses were generated to test hypothesized relationships. the OAFEM, including the original 79-, 54-, and 30-item measures, met stringent Rasch analysis fit and unidimensionality criteria and had high internal consistency and item reliability. The validation results were supportive, while leading to reconsideration of aspects of the hypothesized theoretical hierarchy. Thresholds were suggested to demonstrate levels of severity. the measure is now available to aid in the assessment of FE of older adults by both clinicians and researchers. Theoretical refinements developed using the empirically generated item hierarchy may help to improve assessment and intervention.

Speciation in the Fe(III)-Cl(I)-H2O System at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C)

NASA Astrophysics Data System (ADS)

Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.

2018-02-01

This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).

Data Analysis for Rotationally Resolved Spectra: A Simulated Annealing Approach

DTIC Science & Technology

1992-05-29

Table V. Expe rimental Data PSA was used to analyze high resolution infrared spectra of 2- fluoroethanol (2FE) and difluoroethane (DFE). Although the...does not inhere in the model used to calculate spectra, so the match to the experimental spectrum is not ideal. 8. PSA optimization of Difluoroethane ...A) The experimental spectrum of Difluoroethane . B) The spectrum generated from the starting state given to PSA. C) The spectrum generated from the

THE ROLE OF THERMOHALINE MIXING IN INTERMEDIATE- AND LOW-METALLICITY GLOBULAR CLUSTERS

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

Angelou, George C.; Stancliffe, Richard J.; Church, Ross P.

It is now widely accepted that globular cluster red giant branch (RGB) stars owe their strange abundance patterns to a combination of pollution from progenitor stars and in situ extra mixing. In this hybrid theory a first generation of stars imprints abundance patterns into the gas from which a second generation forms. The hybrid theory suggests that extra mixing is operating in both populations and we use the variation of [C/Fe] with luminosity to examine how efficient this mixing is. We investigate the observed RGBs of M3, M13, M92, M15, and NGC 5466 as a means to test a theorymore » of thermohaline mixing. The second parameter pair M3 and M13 are of intermediate metallicity and our models are able to account for the evolution of carbon along the RGB in both clusters, although in order to fit the most carbon-depleted main-sequence stars in M13 we require a model whose initial [C/Fe] abundance leads to a carbon abundance lower than is observed. Furthermore, our results suggest that stars in M13 formed with some primary nitrogen (higher C+N+O than stars in M3). In the metal-poor regime only NGC 5466 can be tentatively explained by thermohaline mixing operating in multiple populations. We find thermohaline mixing unable to model the depletion of [C/Fe] with magnitude in M92 and M15. It appears as if extra mixing is occurring before the luminosity function bump in these clusters. To reconcile the data with the models would require first dredge-up to be deeper than found in extant models.« less

Mitochondrial Iron-Sulfur Cluster Activity and Cytosolic Iron Regulate Iron Traffic in Saccharomyces cerevisiae.

PubMed

Wofford, Joshua D; Lindahl, Paul A

2015-11-06

An ordinary differential equation-based mathematical model was developed to describe trafficking and regulation of iron in growing fermenting budding yeast. Accordingly, environmental iron enters the cytosol and moves into mitochondria and vacuoles. Dilution caused by increasing cell volume is included. Four sites are regulated, including those in which iron is imported into the cytosol, mitochondria, and vacuoles, and the site at which vacuolar Fe(II) is oxidized to Fe(III). The objective of this study was to determine whether cytosolic iron (Fecyt) and/or a putative sulfur-based product of iron-sulfur cluster (ISC) activity was/were being sensed in regulation. The model assumes that the matrix of healthy mitochondria is anaerobic, and that in ISC mutants, O2 diffuses into the matrix where it reacts with nonheme high spin Fe(II) ions, oxidizing them to nanoparticles and generating reactive oxygen species. This reactivity causes a further decline in ISC/heme biosynthesis, which ultimately gives rise to the diseased state. The ordinary differential equations that define this model were numerically integrated, and concentrations of each component were plotted versus the concentration of iron in the growth medium and versus the rate of ISC/heme biosynthesis. Model parameters were optimized by fitting simulations to literature data. The model variant that assumed that both Fecyt and ISC biosynthesis activity were sensed in regulation mimicked observed behavior best. Such "dual sensing" probably arises in real cells because regulation involves assembly of an ISC on a cytosolic protein using Fecyt and a sulfur species generated in mitochondria during ISC biosynthesis and exported into the cytosol. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Random lattice structures. Modelling, manufacture and FEA of their mechanical response

NASA Astrophysics Data System (ADS)

Maliaris, G.; Sarafis, I. T.; Lazaridis, T.; Varoutoglou, A.; Tsakataras, G.

2016-11-01

The implementation of lightweight structures in various applications, especially in Aerospace/ Automotive industries and Orthopaedics, has become a necessity due to their exceptional mechanical properties with respect to reduced weight. In this work we present a Voronoi tessellation based algorithm, which has been developed for modelling stochastic lattice structures. With the proposed algorithm, is possible to generate CAD geometry with controllable structural parameters, such as porosity, cell number and strut thickness. The digital structures were transformed into physical objects through the combination of 3D printing technics and investment casting. This process was applied to check the mechanical behaviour of generated digital models. Until now, the only way to materialize such structures into physical objects, was feasible through 3D printing methods such as Selective Laser Sintering/ Melting (SLS/ SLM). Investment casting possesses numerous advantages against SLS or SLA, with the major one being the material variety. On the other hand, several trials are required in order to calibrate the process parameters to have successful castings, which is the major drawback of investment casting. The manufactured specimens were subjected to compression tests, where their mechanical response was registered in the form of compressive load - displacement curves. Also, a finite element model was developed, using the specimens’ CAD data and compression test parameters. The FE assisted calculation of specimen plastic deformation is identical with the one of the physical object, which validates the conclusions drawn from the simulation results. As it was observed, strut contact is initiated when specimen deformation is approximately 5mm. Although FE calculated compressive force follows the same trend for the first 3mm of compression, then diverges because of the elasto-plastic FE model type definition and the occurred remeshing steps.

Mn(ii) mediated degradation of artemisinin based on Fe3O4@MnSiO3-FA nanospheres for cancer therapy in vivo

NASA Astrophysics Data System (ADS)

Chen, Jian; Zhang, Weijie; Zhang, Min; Guo, Zhen; Wang, Haibao; He, Mengni; Xu, Pengping; Zhou, Jiajia; Liu, Zhenbang; Chen, Qianwang

2015-07-01

Artemisinin (ART) is a natural drug with potent anticancer activities related with Fe2+ mediated cleavage of the endoperoxide bridge in ART. Herein, we reported that Mn2+ could substitute for Fe2+ to react with ART and generate toxic products, inducing a much higher anticancer efficiency. On this basis, we prepared pH-responsive Fe3O4@MnSiO3-FA nanospheres which can efficiently deliver hydrophobic ART into tumors in mice models. Mn2+ was released in acidic tumor environments and intracellular lysosomes, interacting with ART to kill cancer cells. The ART-loaded nanocarriers could suppress tumor growth more efficiently than free ART, which could be further illustrated by magnetic resonance imaging (MRI). Histological analysis revealed that the drug delivery system had no obvious effect on the major organs of mice. ART has been reported to have lower toxicity than chemotherapeutics. The ART-loaded nanocarriers are promising to be used in improving the survival of chemotherapy patients, providing a novel method for clinical tumor therapy.Artemisinin (ART) is a natural drug with potent anticancer activities related with Fe2+ mediated cleavage of the endoperoxide bridge in ART. Herein, we reported that Mn2+ could substitute for Fe2+ to react with ART and generate toxic products, inducing a much higher anticancer efficiency. On this basis, we prepared pH-responsive Fe3O4@MnSiO3-FA nanospheres which can efficiently deliver hydrophobic ART into tumors in mice models. Mn2+ was released in acidic tumor environments and intracellular lysosomes, interacting with ART to kill cancer cells. The ART-loaded nanocarriers could suppress tumor growth more efficiently than free ART, which could be further illustrated by magnetic resonance imaging (MRI). Histological analysis revealed that the drug delivery system had no obvious effect on the major organs of mice. ART has been reported to have lower toxicity than chemotherapeutics. The ART-loaded nanocarriers are promising to be used in improving the survival of chemotherapy patients, providing a novel method for clinical tumor therapy. Electronic supplementary information (ESI) available: Iron mediated degradation mechanism for artemisinin, mechanism of alkylation of iron(ii)-heme or iron(ii)/heme dimethylester by artemisinin, mechanism of alkylation of the heme model MnIITPP by artemisinin, schematic illustration of the synthesis of ART-loaded Fe3O4@MnSiO3-FA nanospheres, further characterization such as XRD and EDX patterns, N2 adsorption and desorption isotherm and BJH pore distribution, FT-IR spectra, UV-vis spectra, DLS and parallel test results of flow cytometric detection are given in Fig. S1-S13, Fe2+ or Mn2+ release from Fe3O4@MnSiO3 nanospheres in PBS at different pHs is given in Table S1. See DOI: 10.1039/c5nr02402a

Predictive Toxicology of cobalt ferrite nanoparticles: comparative in-vitro study of different cellular models using methods of knowledge discovery from data

PubMed Central

2013-01-01

Background Cobalt-ferrite nanoparticles (Co-Fe NPs) are attractive for nanotechnology-based therapies. Thus, exploring their effect on viability of seven different cell lines representing different organs of the human body is highly important. Methods The toxicological effects of Co-Fe NPs were studied by in-vitro exposure of A549 and NCIH441 cell-lines (lung), precision-cut lung slices from rat, HepG2 cell-line (liver), MDCK cell-line (kidney), Caco-2 TC7 cell-line (intestine), TK6 (lymphoblasts) and primary mouse dendritic-cells. Toxicity was examined following exposure to Co-Fe NPs in the concentration range of 0.05 -1.2 mM for 24 and 72 h, using Alamar blue, MTT and neutral red assays. Changes in oxidative stress were determined by a dichlorodihydrofluorescein diacetate based assay. Data analysis and predictive modeling of the obtained data sets were executed by employing methods of Knowledge Discovery from Data with emphasis on a decision tree model (J48). Results Different dose–response curves of cell viability were obtained for each of the seven cell lines upon exposure to Co-Fe NPs. Increase of oxidative stress was induced by Co-Fe NPs and found to be dependent on the cell type. A high linear correlation (R2=0.97) was found between the toxicity of Co-Fe NPs and the extent of ROS generation following their exposure to Co-Fe NPs. The algorithm we applied to model the observed toxicity belongs to a type of supervised classifier. The decision tree model yielded the following order with decrease of the ranking parameter: NP concentrations (as the most influencing parameter), cell type (possessing the following hierarchy of cell sensitivity towards viability decrease: TK6 > Lung slices > NCIH441 > Caco-2 = MDCK > A549 > HepG2 = Dendritic) and time of exposure, where the highest-ranking parameter (NP concentration) provides the highest information gain with respect to toxicity. The validity of the chosen decision tree model J48 was established by yielding a higher accuracy than that of the well-known “naive bayes” classifier. Conclusions The observed correlation between the oxidative stress, caused by the presence of the Co-Fe NPs, with the hierarchy of sensitivity of the different cell types towards toxicity, suggests that oxidative stress is one possible mechanism for the toxicity of Co-Fe NPs. PMID:23895432

Application of UV-irradiated Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton systems to degrade model and natural occurring naphthenic acids.

PubMed

Zhang, Ying; Chelme-Ayala, Pamela; Klamerth, Nikolaus; Gamal El-Din, Mohamed

2017-07-01

Naphthenic acids (NAs) are a highly complex mixture of organic compounds naturally present in bitumen and identified as the primary toxic constituent of oil sands process-affected water (OSPW). This work investigated the degradation of cyclohexanoic acid (CHA), a model NA compound, and natural occurring NAs during the UV photolysis of Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton processes. The results indicated that in the UV-Fe(III)NTA process at pH 8, the CHA removal increased with increasing NTA dose (0.18, 0.36 and 0.72 mM), while it was independent of the Fe(III) dose (0.09, 0.18 and 0.36 mM). Moreover, the three Fe concentrations had no influence on the photolysis of the Fe(III)NTA complex. The main responsible species for the CHA degradation was hydroxyl radical (OH), and the role of dissolved O 2 in the OH generation was found to be negligible. Real OSPW was treated with the UV-Fe(III)NTA and UV-NTA-Fenton advanced oxidation processes (AOPs). The removals of classical NAs (O 2 -NAs), oxidized NAs with one additional oxygen atom (O 3 -NAs) and with two additional oxygen atoms (O 4 -NAs) were 44.5%, 21.3%, and 25.2% in the UV-Fe(III)NTA process, respectively, and 98.4%, 86.0%, and 81.0% in the UV-NTA-Fenton process, respectively. There was no influence of O 2 on the NA removal in these two processes. The results also confirmed the high reactivity of the O 2 -NA species with more carbons and increasing number of rings or double bond equivalents. This work opens a new window for the possible treatment of OSPW at natural pH using these AOPs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study on superstructure in ion co-doped BiFeO3 by using transmission electron microscopy

NASA Astrophysics Data System (ADS)

Pu, Shi-Zhou; Guo, Chao; Li, Mei-Ya; Chen, Zhen-Lian; Zou, Hua-Min

2015-04-01

La3+ and V5+ co-doped BiFeO3 ceramics are synthesized by rapid liquid sintering technique. The modulated structure in Bi0.85La0.15Fe0.97V0.03O3 is investigated by using transmission electron microscopy (TEM). Two kinds of superstructures are observed in the samples. One is the component modulated superstructure and twin-domain, which is generated by La3+ ordered substitution for Bi3+ and frequently appears. The chemical composition of the superstructure is explored by x-ray energy dispersive spectroscopy (EDS). The model of the ordered structure is proposed. Simulation based on the model is conducted. The second is the fluorite-type δ-Bi2O3 related superstructure. The relation between the ferroelectric property and the microstructure of the sample is also discussed. Project supported by the National Natural Science Foundation of China (Grant Nos. 51372174, 11074193, and 51132001) and the Fundamental Research Funds for the Central Universities.

Finite element modeling for predicting the contact pressure between a foam mattress and the human body in a supine position.

PubMed

Lee, Wookjin; Won, Byeong Hee; Cho, Seong Wook

2017-01-01

In this paper, we generated finite element (FE) models to predict the contact pressure between a foam mattress and the human body in a supine position. Twenty-year-old males were used for three-dimensional scanning to produce the FE human models, which was composed of skin and muscle tissue. A linear elastic isotropic material model was used for the skin, and the Mooney-Rivlin model was used for the muscle tissue because it can effectively represent the nonlinear behavior of muscle. The contact pressure between the human model and the mattress was predicted by numerical simulation. The human models were validated by comparing the body pressure distribution obtained from the same human subject when he was lying on two different mattress types. The experimental results showed that the slope of the lower part of the mattress caused a decrease in the contact pressure at the heels, and the effect of bone structure was most pronounced in the scapula. After inserting a simple structure to function as the scapula, the contact pressure predicted by the FE human models was consistent with the experimental body pressure distribution for all body parts. These results suggest that the models proposed in this paper will be useful to researchers and designers of products related to the prevention of pressure ulcers.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

PubMed Central

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-01-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

Field dependent magnetic anisotropy of Fe1-xZnx thin films

NASA Astrophysics Data System (ADS)

Resnick, Damon A.; McClure, A.; Kuster, C. M.; Rugheimer, P.; Idzerda, Y. U.

2013-05-01

Using longitudinal magneto-optical Kerr effect in combination with a variable strength rotating magnetic field, called the Rotational Magneto-Optic Kerr Effect (ROTMOKE) method, we show that the magnetic anisotropy for thin Fe82Zn18 single crystal films, grown on MgO(001) substrates, depends linearly on the strength of the applied magnetic field at low fields but is constant (saturates) at fields greater than 350 Oe. The torque moment curves generated using ROTMOKE are well fit with a model that accounts for the uniaxial and cubic anisotropy with the addition of a cubic anisotropy that depends linearly on the applied magnetic field. The field dependent term is evidence of a large effect on the effective magnetic anisotropy in Fe1-xZnx thin films by the magnetostriction.

Fahlore and Sphalerite from the Darasun Gold Deposit in the Eastern Transbaikal Region, Russia: I. Mineral Assemblages and Intergrowths, Chemical Composition, and Its Evolution

NASA Astrophysics Data System (ADS)

Lyubimtseva, N. G.; Bortnikov, N. S.; Borisovsky, S. E.; Prokofiev, V. Yu.; Vikent'eva, O. V.

2018-03-01

The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite-Zn-tetrahedrite-Fe-tennantite-Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.

Nanostructured Fe-Cr Alloys for Advanced Nuclear Energy Applications

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

Scattergood, Ronald O.

2016-04-26

We have completed research on the grain-size stabilization of model nanostructured Fe14Cr base alloys at high temperatures by the addition of non-equilibrium solutes. Fe14Cr base alloys are representative for nuclear reactor applications. The neutron flux in a nuclear reactor will generate He atoms that coalesce to form He bubbles. These can lead to premature failure of the reactor components, limiting their lifetime and increasing the cost and capacity for power generation. In order to mitigate such failures, Fe14Cr base alloys have been processed to contain very small nano-size oxide particles (less than 10 nm in size) that trap He atomsmore » and reduce bubble formation. Theoretical and experimental results indicate that the grain boundaries can also be very effective traps for He atoms and bubble formation. An optimum grain size will be less than 100 nm, ie., nanocrystalline alloys must be used. Powder metallurgy methods based on high-energy ball milling can produce Fe-Cr base nanocrystalline alloys that are suitable for nuclear energy applications. The problem with nanocrystalline alloys is that excess grain-boundary energy will cause grains to grow at higher temperatures and their propensity for He trapping will be lost. The nano-size oxide particles in current generation nuclear alloys provide some grain size stabilization by reducing grain-boundary mobility (Zener pinning – a kinetic effect). However the current mitigation strategy minimizing bubble formation is based primarily on He trapping by nano-size oxide particles. An alternate approach to nanoscale grain size stabilization has been proposed. This is based on the addition of small amounts of atoms that are large compared to the base alloy. At higher temperatures these will diffuse to the grain boundaries and will produce an equilibrium state for the grain size at higher temperatures (thermodynamic stabilization – an equilibrium effect). This would be preferred compared to a kinetic effect, which is not based on an equilibrium state. The PI and coworkers have developed thermodynamic-based models that can be used to select appropriate solute additions to Fe14Cr base alloys to achieve a contribution to grain-size stabilization and He bubble mitigation by the thermodynamic effect. All such models require approximations and the proposed research was aimed at alloy selection, processing and detailed atomic-level microstructure evaluations to establish the efficacy of the thermodynamic effect. The outcome of this research shows that appropriate alloy additions can produce a contribution from the thermodynamic stabilization effect. Furthermore, due to the oxygen typically present in nominally high purity elemental powders used for powder metallurgy processing, the optimum results obtained appeared as a synergistic combination of nano-size oxide particle pinning kinetic effect and the grain-boundary segregation thermodynamic effect.« less

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Zn-Fe-CNTs catalytic in situ generation of H2O2 for Fenton-like degradation of sulfamethoxazole.

PubMed

Liu, Yong; Fan, Qin; Wang, Jianlong

2018-01-15

A novel Fenton-like catalyst (Zn-Fe-CNTs) capable of converting O 2 to H 2 O 2 and further to OH was prepared through infiltration fusion method followed by chemical replacement in argon atmosphere. The catalyst was characterized by SEM, EDS, TEM, XRD and XPS. The reaction between Zn-Fe-CNTs and O 2 in aqueous solution could generate H 2 O 2 in situ, which was further transferred to OH. The Fenton-like degradation of sulfamethoxazole (SMX) using Zn-Fe-CNTs as catalyst was evaluated. The results indicated that Zn-Fe-CNTs had a coral porous structure with a BET area of 51.67m 2 /g, exhibiting excellent adsorption capacity for SMX, which enhanced its degradation. The particles of Zn 0 and Fe 0 /Fe 2 O 3 were observed on the surface of Zn-Fe-CNTs. The mixture of Zn 0 and CNTs could reduce O 2 into H 2 O 2 by micro-electrolysis and Fe 0 /Fe 2 O 3 could catalyze in-situ generation of H 2 O 2 to produce OH through Fenton-like process. When initial pH=1.5, T=25°C, O 2 flow rate=400mL/min, Zn-Fe-CNTs=0.6g/L, SMX=25mg/L and reaction time=10min, the removal efficiency of SMX and TOC was 100% and 51.3%, respectively. The intermediates were detected and the possible pathway of SMX degradation and the mechanism of Zn-Fe-CNTs/O 2 process were tentatively proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-current induced spin-orbit torque in FeMn/Pt multilayers

NASA Astrophysics Data System (ADS)

Xu, Yanjun; Yang, Yumeng; Yao, Kui; Xu, Baoxi; Wu, Yihong

2016-05-01

Extensive efforts have been devoted to the study of spin-orbit torque in ferromagnetic metal/heavy metal bilayers and exploitation of it for magnetization switching using an in-plane current. As the spin-orbit torque is inversely proportional to the thickness of the ferromagnetic layer, sizable effect has only been realized in bilayers with an ultrathin ferromagnetic layer. Here we demonstrate that, by stacking ultrathin Pt and FeMn alternately, both ferromagnetic properties and current induced spin-orbit torque can be achieved in FeMn/Pt multilayers without any constraint on its total thickness. The critical behavior of these multilayers follows closely three-dimensional Heisenberg model with a finite Curie temperature distribution. The spin torque effective field is about 4 times larger than that of NiFe/Pt bilayer with a same equivalent NiFe thickness. The self-current generated spin torque is able to switch the magnetization reversibly without the need for an external field or a thick heavy metal layer. The removal of both thickness constraint and necessity of using an adjacent heavy metal layer opens new possibilities for exploiting spin-orbit torque for practical applications.

Crystallographic studies of [NiFe]-hydrogenase mutants: towards consensus structures for the elusive unready oxidized states.

PubMed

Volbeda, Anne; Martin, Lydie; Barbier, Elodie; Gutiérrez-Sanz, Oscar; De Lacey, Antonio L; Liebgott, Pierre-Pol; Dementin, Sébastien; Rousset, Marc; Fontecilla-Camps, Juan C

2015-01-01

Catalytically inactive oxidized O2-sensitive [NiFe]-hydrogenases are characterized by a mixture of the paramagnetic Ni-A and Ni-B states. Upon O2 exposure, enzymes in a partially reduced state preferentially form the unready Ni-A state. Because partial O2 reduction should generate a peroxide intermediate, this species was previously assigned to the elongated Ni-Fe bridging electron density observed for preparations of [NiFe]-hydrogenases known to contain the Ni-A state. However, this proposition has been challenged based on the stability of this state to UV light exposure and the possibility of generating it anaerobically under either chemical or electrochemical oxidizing conditions. Consequently, we have considered alternative structures for the Ni-A species including oxidation of thiolate ligands to either sulfenate or sulfenic acid. Here, we report both new and revised [NiFe]-hydrogenases structures and conclude, taking into account corresponding characterizations by Fourier transform infrared spectroscopy (FTIR), that the Ni-A species contains oxidized cysteine and bridging hydroxide ligands instead of the peroxide ligand we proposed earlier. Our analysis was rendered difficult by the typical formation of mixtures of unready oxidized states that, furthermore, can be reduced by X-ray induced photoelectrons. The present study could be carried out thanks to the use of Desulfovibrio fructosovorans [NiFe]-hydrogenase mutants with special properties. In addition to the Ni-A state, crystallographic results are also reported for two diamagnetic unready states, allowing the proposal of a revised oxidized inactive Ni-SU model and a new structure characterized by a persulfide ion that is assigned to an Ni-'Sox' species.

Spin-polarized currents generated by magnetic Fe atomic chains.

PubMed

Lin, Zheng-Zhe; Chen, Xi

2014-06-13

Fe-based devices are widely used in spintronics because of high spin-polarization and magnetism. In this work, freestanding Fe atomic chains, the thinnest wires, were used to generate spin-polarized currents due to the spin-polarized energy bands. By ab initio calculations, the zigzag structure was found to be more stable than the wide-angle zigzag structure and had a higher ratio of spin-up and spin-down currents. By our theoretical prediction, Fe atomic chains have a sufficiently long thermal lifetime only at T ≦̸ 150 K, while C atomic chains are very stable even at T = 1000 K. This means that the spintronic devices based on Fe chains could work only at low temperatures. A system constructed by a short Fe chain sandwiched between two graphene electrodes could be used as a spin-polarized current generator, while a C chain could not be used in this way. The present work may be instructive and meaningful to further practical applications based on recent technical developments on the preparation of metal atomic chains (Proc. Natl. Acad. Sci. USA 107 9055 (2010)).

Arterial thrombosis is accelerated in mice deficient in histidine-rich glycoprotein.

PubMed

Vu, Trang T; Zhou, Ji; Leslie, Beverly A; Stafford, Alan R; Fredenburgh, James C; Ni, Ran; Qiao, Shengjun; Vaezzadeh, Nima; Jahnen-Dechent, Willi; Monia, Brett P; Gross, Peter L; Weitz, Jeffrey I

2015-04-23

Factor (F) XII, a key component of the contact system, triggers clotting via the intrinsic pathway, and is implicated in propagating thrombosis. Although nucleic acids are potent activators, it is unclear how the contact system is regulated to prevent uncontrolled clotting. Previously, we showed that histidine-rich glycoprotein (HRG) binds FXIIa and attenuates its capacity to trigger coagulation. To investigate the role of HRG as a regulator of the intrinsic pathway, we compared RNA- and DNA-induced thrombin generation in plasma from HRG-deficient and wild-type mice. Thrombin generation was enhanced in plasma from HRG-deficient mice, and accelerated clotting was restored to normal with HRG reconstitution. Although blood loss after tail tip amputation was similar in HRG-deficient and wild-type mice, carotid artery occlusion after FeCl3 injury was accelerated in HRG-deficient mice, and HRG administration abrogated this effect. To confirm that HRG modulates the contact system, we used DNase, RNase, and antisense oligonucleotides to characterize the FeCl3 model. Whereas DNase or FVII knockdown had no effect, carotid occlusion was abrogated with RNase or FXII knockdown, confirming that FeCl3-induced thrombosis is triggered by RNA in a FXII-dependent fashion. Therefore, in a nucleic acid-driven model, HRG inhibits thrombosis by modulating the intrinsic pathway of coagulation. © 2015 by The American Society of Hematology.

Siderophores in Cloud Waters and Potential Impact on Atmospheric Chemistry: Photoreactivity of Iron Complexes under Sun-Simulated Conditions.

PubMed

Passananti, Monica; Vinatier, Virginie; Delort, Anne-Marie; Mailhot, Gilles; Brigante, Marcello

2016-09-06

In the present work, the photoreactivity of a mixture of iron(III)–pyoverdin (Fe(III)–Pyo) complexes was investigated under simulated cloud conditions. Pyoverdins are expected to complex ferric ions naturally present in cloudwater, thus modifying their availability and photoreactivity. The spectroscopic properties and photoreactivity of Fe(III)-Pyo were investigated, with particular attention to their fate under solar irradiation, also studied through simulations. The photolysis of the Fe(III)–Pyo complex leads to the generation of Fe(II), with rates of formation (RFe(II)f) of 6.98 and 3.96 × 10–9 M s–1 at pH 4.0 and 6.0, respectively. Interestingly, acetate formation was observed during the iron-complex photolysis, suggesting that fragmentation can occur after the ligand-to-metal charge transfer (LMCT) via a complex reaction mechanism. Moreover, photogenerated Fe(II) represent an important source of hydroxyl radical via the Fenton reaction in cloudwater. This reactivity might be relevant for the estimation of the rates of formation and steady-state concentrations of the hydroxyl radical by cloud chemistry models and for organic matter speciation in the cloud aqueous phase. In fact, the conventional models, which describe the iron photoreactivity in terms of iron–aqua and oxalate complexes, are not in accordance with our results.

Green Rust: Its Electrochemical Generation, Characterization, and Implications

DTIC Science & Technology

2009-02-01

FeOOH), and lepidocrocite ( γ -FeOOH) in well-aerated systems, and hematite (α- Fe2O3 ) maghemite (δ- Fe2O3 ) or magnetite (Fe3O4) in oxygen-depleted...ferric hydroxides that belong to a family of minerals known as layered double hydroxides ( LDH ). Its general formula is [FeII(6-x) FeIIIx (OH)12]x+[Ax...of ferrous and ferric hydroxides that belong to a family of minerals known as layered double hydroxides ( LDH ). Its general formula is [FeII (6-x) FeIII

Model Simulation of Ionosphere Electron Density with Dynamic Transportation and Mechanism of Sporadic E Layers in Lower Part of Ionosphere

NASA Astrophysics Data System (ADS)

Lin, Y. C.; Chu, Y. H.

2015-12-01

There are many physical theories responsible for explanation the generation mechanism of sporadic E (Es) plasma irregularities. In middle latitude, it's generally believed that sporadic E layers occur in vertical ion convergent areas driven by horizontal neutral wind shear. The sporadic E layers appear characteristic of abundant metallic ion species (i.e., Fe+, Mg+, Na+), that lifetime are longer than molecular ions by a factor of several orders, have been demonstrated by rocket-borne mass spectrometric measurements. On the basic of the GPS Radio Occultation (RO), using the scintillations of the GPS signal-to-noise ratio and intense fluctuation of excess phase, the global and seasonal sporadic E layers occurrence rates could be retrieved. In our previous study we found there is averaged 10 kilometers shift in height between the COSMIC-retrieved sporadic E layer occurrence rate and the sporadic E occurrence rate modeled from considering the convergence/divergence of Fe+ vertical flux. There are many reasons that maybe result in the altitude differences, e.g., tidal wind with phase shift, electric field driven force, iron species distributions. In this research, the quantitative analyses for electric field drives Es layers translations in vertical direction are presented. The tidal wind driven sporadic E layers have been simulating by modeling several nonmetallic ions (O+(4S), O+(2D), O+(2p), N+, N2+, O2+, NO+) and metallic ions (Fe+, FeO2+, FeN2+, FeO+) with wind shear transportation. The simulation result shows the Fe+ particles accumulate at zonal wind shear convergent regions and form the thin sporadic E layers. With the electric field taking into account, the whole shape of sporadic E layers vertical shift 2~5 km that depending on what magnitude and direction of electric field is added.

Cyanide-bridged Fe(III)-Mn(III) bimetallic complexes with dimeric and chain structures constructed from a newly made mer-Fe tricyanide: structures and magnetic properties.

PubMed

Kim, Jae Il; Kwak, Hyun Young; Yoon, Jung Hee; Ryu, Dae Won; Yoo, In Young; Yang, Namgeun; Cho, Beong Ki; Park, Je-Geun; Lee, Hyosug; Hong, Chang Seop

2009-04-06

Four cyanide-linked Fe(III)-Mn(III) complexes were prepared by reacting Mn Schiff bases with a new molecular precursor (PPh(4))[Fe(qcq)(CN)(3)] [1; qcq = 8-(2-quinolinecarboxamido)quinoline anion]. They include a dimeric molecule, [Fe(qcq)(CN)(3)][Mn(3-MeOsalen)(H(2)O)] x 2 H(2)O [2 x 2 H(2)O; 3-MeOsalen = N,N'-ethylenebis(3-methoxysalicylideneiminato) dianion], and three 1D zigzag chains, [Fe(qcq)(CN)(3)][Mn(5-Clsalen)] x 3 H(2)O [3 x 2 MeOH; 5-Clsalen = N,N'-ethylenebis(5-chlorosalicylideneiminato) dianion], [Fe(qcq)(CN)(3)][Mn(5-Brsalen)] x 2 MeOH [4 x 2 MeOH; 5-Brsalen = N,N'-ethylenebis(5-bromosalicylideneiminato) dianion], and Fe(qcq)(CN)(3)][Mn(salen)].MeCN x H(2)O [5 x MeCN; salen = N,N'-ethylenebis(salicylideneiminato) dianion]. The complexes consist of extensive hydrogen bonding and pi-pi stacking interactions, generating multidimensional structures. Magnetic studies demonstrate that antiferromagnetic couplings are operative between Fe(III) and Mn(III) centers bridged by cyanide ligands. On the basis of an infinite chain model, magnetic coupling parameters of 2-5 range from -9.3 to -14.1 cm(-1). A long-range order is observed at 2.3 K for 3 and 2.2 K for 4, while compound 5 shows spin glass behavior possibly coupled with magnetic ordering.

Impact of metal ionic characteristics on adsorption potential of Ficus carica leaves using QSPR modeling.

PubMed

Batool, Fozia; Iqbal, Shahid; Akbar, Jamshed

2018-04-03

The present study describes Quantitative Structure Property Relationship (QSPR) modeling to relate metal ions characteristics with adsorption potential of Ficus carica leaves for 13 selected metal ions (Ca +2 , Cr +3 , Co +2 , Cu +2 , Cd +2 , K +1 , Mg +2 , Mn +2 , Na +1 , Ni +2 , Pb +2 , Zn +2 , and Fe +2 ) to generate QSPR model. A set of 21 characteristic descriptors were selected and relationship of these metal characteristics with adsorptive behavior of metal ions was investigated. Stepwise Multiple Linear Regression (SMLR) analysis and Artificial Neural Network (ANN) were applied for descriptors selection and model generation. Langmuir and Freundlich isotherms were also applied on adsorption data to generate proper correlation for experimental findings. Model generated indicated covalent index as the most significant descriptor, which is responsible for more than 90% predictive adsorption (α = 0.05). Internal validation of model was performed by measuring [Formula: see text] (0.98). The results indicate that present model is a useful tool for prediction of adsorptive behavior of different metal ions based on their ionic characteristics.

Engine dynamic analysis with general nonlinear finite element codes. II - Bearing element implementation, overall numerical characteristics and benchmarking

NASA Technical Reports Server (NTRS)

Padovan, J.; Adams, M.; Lam, P.; Fertis, D.; Zeid, I.

1982-01-01

Second-year efforts within a three-year study to develop and extend finite element (FE) methodology to efficiently handle the transient/steady state response of rotor-bearing-stator structure associated with gas turbine engines are outlined. The two main areas aim at (1) implanting the squeeze film damper element into a general purpose FE code for testing and evaluation; and (2) determining the numerical characteristics of the FE-generated rotor-bearing-stator simulation scheme. The governing FE field equations are set out and the solution methodology is presented. The choice of ADINA as the general-purpose FE code is explained, and the numerical operational characteristics of the direct integration approach of FE-generated rotor-bearing-stator simulations is determined, including benchmarking, comparison of explicit vs. implicit methodologies of direct integration, and demonstration problems.

Radical induced degradation of acetaminophen with Fe3O4 magnetic nanoparticles as heterogeneous activator of peroxymonosulfate.

PubMed

Tan, Chaoqun; Gao, Naiyun; Deng, Yang; Deng, Jing; Zhou, Shiqing; Li, Jun; Xin, Xiaoyan

2014-07-15

Magnetic nano-scaled particles Fe3O4 were studied for the activation of peroxymonosulfate (PMS) to generate active radicals for degradation of acetaminophen (APAP) in water. The Fe3O4 MNPs were found to effectively catalyze PMS for removal of APAP, and the reactions well followed a pseudo-first-order kinetics pattern (R(2)>0.95). Within 120min, approximately 75% of 10ppm APAP was accomplished by 0.2mM PMS in the presence of 0.8g/L Fe3O4 MNPs with little Fe(3+) leaching (<4μg/L). Higher Fe3O4 MNP dose, lower initial APAP concentration, neutral pH, and higher reaction temperature favored the APAP degradation. The production of sulfate radicals and hydroxyl radicals was validated through two ways: (1) indirectly from the scavenging tests with scavenging agents, tert-butyl alcohol (TBA) and ethanol (EtOH); (2) directly from the electron paramagnetic resonance (ESR) tests with 0.1M 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO). Plausible mechanisms on the radical generation from Fe3O4 MNP activation of PMS are proposed based on the results of radical identification tests and XPS analysis. It appeared that Fe(2+)Fe(3+) on the catalyst surface was responsible for the radical generation. The results demonstrated that Fe3O4 MNPs activated PMS is a promising technology for water pollution caused by contaminants such as pharmaceuticals. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoscale zerovalent iron (nZVI) at environmentally relevant concentrations induced multigenerational reproductive toxicity in Caenorhabditis elegans.

PubMed

Yang, Ying-Fei; Chen, Pei-Jen; Liao, Vivian Hsiu-Chuan

2016-05-01

Nanoscale zerovalent iron (nZVI) is widely used with large scale for environmental remediation for in situ or ex situ applications. The potential impact of nZVI on biota at environmentally relevant concentrations needs to be elucidated. In this study, the reproductive toxicities of three irons species: carboxymethyl cellulose (CMC)-stabilized nZVI, nanoscale iron oxide (nFe3O4), and ferrous ion (Fe(II)aq) in the soil-dwelling nematode Caenorhabditis elegans were examined. In addition, the generational transfer of reproductive toxicity of CMC-nZVI on C. elegans was investigated. The results showed that CMC-nZVI, nFe3O4, and Fe(II)aq did not cause significant mortality after 24 h exposure at the examined concentrations. Reproductive toxicity assays revealed that CMC-nZVI, nFe3O4, and Fe(II)aq significantly decreased offsprings in parental generation (F0) in accompany with the increased intracellular reactive oxygen species (ROS). Furthermore, the reproductive toxicity of CMC-nZVI at environmentally relevant concentrations was transferrable from the F0 to the F1 and F2 generations, but then recovered in the F3 and F4 generations. Further evidence showed that total irons were accumulated in the F0 and F1 generations of C. elegans after CMC-nZVI parental exposure. This study demonstrated that environmentally relevant concentrations of CMC-nZVI induced multigenerational reproductive toxicity which can be ascribed to its high production of ROS in F0 generation, toxicity of Fe(II)aq, and iron accumulation in C. elegans. Since nZVI is widely used for environmental remediation, considering the multigenerational toxicity, this study thus implicates a potential environmental risk of nZVI-induced nanotoxicity in the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Exploring the mechanism and kinetics of Fe-Cu-Ag trimetallic particles for p-nitrophenol reduction.

PubMed

Yuan, Yue; Yuan, Donghai; Zhang, Yunhong; Lai, Bo

2017-11-01

Preparation conditions of Fe-Cu-Ag trimetallic particles were optimized by single-factor and response surface methodology (RSM) batch experiments to obtain high-reactive Fe 0 -based materials for p-nitrophenol (PNP) removal. Under the optimal conditions (i.e., Fe 0 dosage of 34.86 g L -1 , theoretical Cu mass loading of 81.87 mg Cu/g Fe, theoretical Ag mass loading of 1.15 mg Ag/g Fe, and preparation temperature of 52.1 °C), the actual rate constant (k obs ) of PNP reduction in 5 min was 1.64 min -1 , which shows a good agreement between the model prediction (1.85 min -1 ) of RSM and the experimental data. Furthermore, the high reactivity of Fe 0 -based trimetals was mainly attributed to the plating order of transition metals (i.e., Ag and Cu). Furthermore, we propose a new theory that the pyramid trimetallic structure of Fe-Cu-Ag could improve the electron transport and create active sites with high electron density at the surface (Ag layer) that could enhance the generation of surface-bonded atomic hydrogen ([H] abs ) or the direct reduction of pollutant. Moreover, Fe-Cu-Ag trimetallic particles were characterized by SEM, EDS, and XPS, which also could confirm the proposed theory. In addition, the leached Cu 2+ (<10 μg L -1 ) and Ag + (below detection limits) in Fe-Cu-Ag system could be neglected completely, which suggests that Fe-Cu-Ag is reliable, safe, and environment friendly. Therefore, Fe-Cu-Ag trimetallic system would be promising for the removal of pollutants from industrial wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Artificial neural networks for AC losses prediction in superconducting round filaments

NASA Astrophysics Data System (ADS)

Leclerc, J.; Makong Hell, L.; Lorin, C.; Masson, P. J.

2016-06-01

An extensive and fast method to estimate superconducting AC losses within a superconducting round filament carrying an AC current and subjected to an elliptical magnetic field (both rotating and oscillating) is presented. Elliptical fields are present in rotating machine stators and being able to accurately predict AC losses in fully superconducting machines is paramount to generating realistic machine designs. The proposed method relies on an analytical scaling law (ASL) combined with two artificial neural network (ANN) estimators taking 9 input parameters representing the superconductor, external field and transport current characteristics. The ANNs are trained with data generated by finite element (FE) computations with a commercial software (FlexPDE) based on the widely accepted H-formulation. After completion, the model is validated through comparison with additional randomly chosen data points and compared for simple field configurations to other predictive models. The loss estimation discrepancy is about 3% on average compared to the FEA analysis. The main advantages of the model compared to FE simulations is the fast computation time (few milliseconds) which allows it to be used in iterated design processes of fully superconducting machines. In addition, the proposed model provides a higher level of fidelity than the scaling laws existing in literature usually only considering pure AC field.

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

NASA Astrophysics Data System (ADS)

Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

1986-01-01

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

On the estimation of stellar parameters with uncertainty prediction from Generative Artificial Neural Networks: application to Gaia RVS simulated spectra

NASA Astrophysics Data System (ADS)

Dafonte, C.; Fustes, D.; Manteiga, M.; Garabato, D.; Álvarez, M. A.; Ulla, A.; Allende Prieto, C.

2016-10-01

Aims: We present an innovative artificial neural network (ANN) architecture, called Generative ANN (GANN), that computes the forward model, that is it learns the function that relates the unknown outputs (stellar atmospheric parameters, in this case) to the given inputs (spectra). Such a model can be integrated in a Bayesian framework to estimate the posterior distribution of the outputs. Methods: The architecture of the GANN follows the same scheme as a normal ANN, but with the inputs and outputs inverted. We train the network with the set of atmospheric parameters (Teff, log g, [Fe/H] and [α/ Fe]), obtaining the stellar spectra for such inputs. The residuals between the spectra in the grid and the estimated spectra are minimized using a validation dataset to keep solutions as general as possible. Results: The performance of both conventional ANNs and GANNs to estimate the stellar parameters as a function of the star brightness is presented and compared for different Galactic populations. GANNs provide significantly improved parameterizations for early and intermediate spectral types with rich and intermediate metallicities. The behaviour of both algorithms is very similar for our sample of late-type stars, obtaining residuals in the derivation of [Fe/H] and [α/ Fe] below 0.1 dex for stars with Gaia magnitude Grvs < 12, which accounts for a number in the order of four million stars to be observed by the Radial Velocity Spectrograph of the Gaia satellite. Conclusions: Uncertainty estimation of computed astrophysical parameters is crucial for the validation of the parameterization itself and for the subsequent exploitation by the astronomical community. GANNs produce not only the parameters for a given spectrum, but a goodness-of-fit between the observed spectrum and the predicted one for a given set of parameters. Moreover, they allow us to obtain the full posterior distribution over the astrophysical parameters space once a noise model is assumed. This can be used for novelty detection and quality assessment.

Iron Bioavailability Studies of the First Generation of Iron-Biofortified Beans Released in Rwanda.

PubMed

Glahn, Raymond; Tako, Elad; Hart, Jonathan; Haas, Jere; Lung'aho, Mercy; Beebe, Steve

2017-07-21

This paper represents a series of in vitro iron (Fe) bioavailability experiments, Fe content analysis and polyphenolic profile of the first generation of Fe biofortified beans ( Phaseolus vulgaris ) selected for human trials in Rwanda and released to farmers of that region. The objective of the present study was to demonstrate how the Caco-2 cell bioassay for Fe bioavailability can be utilized to assess the nutritional quality of Fe in such varieties and how they may interact with diets and meal plans of experimental studies. Furthermore, experiments were also conducted to directly compare this in vitro approach with specific human absorption studies of these Fe biofortified beans. The results show that other foods consumed with beans, such as rice, can negatively affect Fe bioavailability whereas potato may enhance the Fe absorption when consumed with beans. The results also suggest that the extrinsic labelling approach to measuring human Fe absorption can be flawed and thus provide misleading information. Overall, the results provide evidence that the Caco-2 cell bioassay represents an effective approach to evaluate the nutritional quality of Fe-biofortified beans, both separate from and within a targeted diet or meal plan.

Iron Bioavailability Studies of the First Generation of Iron-Biofortified Beans Released in Rwanda

PubMed Central

Glahn, Raymond; Tako, Elad; Hart, Jonathan; Haas, Jere; Beebe, Steve

2017-01-01

This paper represents a series of in vitro iron (Fe) bioavailability experiments, Fe content analysis and polyphenolic profile of the first generation of Fe biofortified beans (Phaseolus vulgaris) selected for human trials in Rwanda and released to farmers of that region. The objective of the present study was to demonstrate how the Caco-2 cell bioassay for Fe bioavailability can be utilized to assess the nutritional quality of Fe in such varieties and how they may interact with diets and meal plans of experimental studies. Furthermore, experiments were also conducted to directly compare this in vitro approach with specific human absorption studies of these Fe biofortified beans. The results show that other foods consumed with beans, such as rice, can negatively affect Fe bioavailability whereas potato may enhance the Fe absorption when consumed with beans. The results also suggest that the extrinsic labelling approach to measuring human Fe absorption can be flawed and thus provide misleading information. Overall, the results provide evidence that the Caco-2 cell bioassay represents an effective approach to evaluate the nutritional quality of Fe-biofortified beans, both separate from and within a targeted diet or meal plan. PMID:28754026

Electrochemical Features of the Ferric Sulfate Leaching of CuFeS2/C Aggregates.

DTIC Science & Technology

1984-11-28

HCl at room temperature by linear sweep f’ -" !, voltametry Ai potentiostatic electrolysis. For example, they found #i j n one case that the anodic...converter and Model 175 potential sweep generator. Potentlo- * dynamic polarization experiments were designed to examine the nature :of the half-cell

An automated method to morph finite element whole-body human models with a wide range of stature and body shape for both men and women.

PubMed

Zhang, Kai; Cao, Libo; Fanta, Abeselom; Reed, Matthew P; Neal, Mark; Wang, Jenne-Tai; Lin, Chin-Hsu; Hu, Jingwen

2017-07-26

Field data analyses have shown that small female, obese, and/or older occupants are at increased risks of death and serious injury in motor-vehicle crashes compared with mid-size young men. The current adult finite element (FE) human models represent occupants in the same three body sizes (large male, mid-size male, and small female) as those for the contemporary adult crash dummies. Further, the time needed to develop an FE human model using the traditional method is measured in months or even years. In the current study, an improved regional mesh morphing method based on landmark-based radial basis function (RBF) interpolation was developed to rapidly morph a mid-size male FE human model into different geometry targets. A total of 100 human models with a wide range of human attributes were generated. A pendulum chest impact condition was applied to each model as an initial assessment of the resulting variability in response. The morphed models demonstrated mesh quality similar to the baseline model. The peak impact forces and chest deflections in the chest pendulum impacts varied substantially with different models, supportive of consideration of population variation in evaluating the occupant injury risks. The method developed in this study will enable future safety design optimizations targeting at various vulnerable populations that cannot be considered with the current models. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidative degradation of phenols in sono-Fenton-like systems upon high-frequency ultrasound irradiation

NASA Astrophysics Data System (ADS)

Aseev, D. G.; Sizykh, M. R.; Batoeva, A. A.

2017-12-01

The kinetics of oxidative degradation of phenol and chlorophenols upon acoustic cavitation in the megahertz range (1.7 MHz) is studied experimentally in model systems, and the involvement of in situ generated reactive oxygen species (ROSs) is demonstrated. The phenols subjected to high frequency ultrasound (HFUS) are ranked in terms of their rate of conversion: 2,4,6-trichlorophenol > 2,4-dichlorophenol 2-chlorophenol > 4-chlorophenol phenol. Oxidative degradation upon HFUS irradiation is most efficient at low concentrations of pollutants, due to the low steady-state concentrations of the in situ generated ROSs. A dramatic increase is observed in the efficiency of oxidation in several sonochemical oxidative systems (HFUS in combination with other chemical oxidative factors). The system with added Fe2+ (a sono-Fenton system) derives its efficiency from hydrogen peroxide generated in situ as a result of the recombination of OH radicals. The S2O8 2-/Fe2+/HFUS system has a synergetic effect on substrate oxidation that is attributed to a radical chain mechanism. In terms of the oxidation rates, degrees of conversion, and specific energy efficiencies of 4-chlorophenol oxidation based on the amount of oxidized substance per unit of expended energy the considered sonochemical oxidative systems form the series HFUS < S2O8 2-/HFUS < S2O8 2-/Fe2+/HFUS.

Predicting the constitutive behavior of semi-solids via a direct finite element simulation: application to AA5182

NASA Astrophysics Data System (ADS)

Phillion, A. B.; Cockcroft, S. L.; Lee, P. D.

2009-07-01

The methodology of direct finite element (FE) simulation was used to predict the semi-solid constitutive behavior of an industrially important aluminum-magnesium alloy, AA5182. Model microstructures were generated that detail key features of the as-cast semi-solid: equiaxed-globular grains of random size and shape, interconnected liquid films, and pores at the triple-junctions. Based on the results of over fifty different simulations, a model-based constitutive relationship which includes the effects of the key microstructure features—fraction solid, grain size and fraction porosity—was derived using regression analysis. This novel constitutive equation was then validated via comparison with both the FE simulations and experimental stress/strain data. Such an equation can now be used to incorporate the effects of microstructure on the bulk semi-solid flow stress within a macro- scale process model.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Mechanical stability analysis on spherical sandwich sheet at low temperature loading conditions

NASA Astrophysics Data System (ADS)

Wang, Shanshuai; Li, Shuhui; Li, Zhimin

2013-12-01

The spherical sandwich sheet (S-S-S) is generally used in the aerospace industry, for example, the airplane, the rocket's fairing, the spacecraft and the satellite for the purpose of heat-insulation, weight-saving and dimension-reducing. The stability of the S-S-S is of general concern because of its particularly thin but large size. For some S-S-S used in fuel tank storing liquid oxygen of the rocket, it must be facing low temperature down to about -183 °C. Low temperature condition affects the stability of the S-S-S and then causes buckling of the structure. In this paper, a finite element (FE) model is established for evaluating the stability of the S-S-S via the sequential coupling mode. The material mechanical properties related to temperature are concerned in the FE model. The buckling modes and critical buckling loading are predicted accurately, since the FE model includes heat transfer simulating, thermal stress computing, buckling and post buckling process. It is found that the thermal stress generated from the low temperature loading reduces the critical buckling loading and changes the buckling modes of the S-S-S.

A Finite Element Model of a Midsize Male for Simulating Pedestrian Accidents.

PubMed

Untaroiu, Costin D; Pak, Wansoo; Meng, Yunzhu; Schap, Jeremy; Koya, Bharath; Gayzik, Scott

2018-01-01

Pedestrians represent one of the most vulnerable road users and comprise nearly 22% the road crash-related fatalities in the world. Therefore, protection of pedestrians in car-to-pedestrian collisions (CPC) has recently generated increased attention with regulations involving three subsystem tests. The development of a finite element (FE) pedestrian model could provide a complementary component that characterizes the whole-body response of vehicle-pedestrian interactions and assesses the pedestrian injuries. The main goal of this study was to develop and to validate a simplified full body FE model corresponding to a 50th male pedestrian in standing posture (M50-PS). The FE model mesh and defined material properties are based on a 50th percentile male occupant model. The lower limb-pelvis and lumbar spine regions of the human model were validated against the postmortem human surrogate (PMHS) test data recorded in four-point lateral knee bending tests, pelvic\\abdomen\\shoulder\\thoracic impact tests, and lumbar spine bending tests. Then, a pedestrian-to-vehicle impact simulation was performed using the whole pedestrian model, and the results were compared to corresponding PMHS tests. Overall, the simulation results showed that lower leg response is mostly within the boundaries of PMHS corridors. In addition, the model shows the capability to predict the most common lower extremity injuries observed in pedestrian accidents. Generally, the validated pedestrian model may be used by safety researchers in the design of front ends of new vehicles in order to increase pedestrian protection.

Femtosecond Polarization Phase Selective (PPS) High Magnetic Field Studies of Electron-Spin-Hole (ESH) Dynamics: New Tools for Ultrafast Imaging Fe-centered ESH Transfer Mechanisms Steps

NASA Astrophysics Data System (ADS)

Rupnik, Kresimir; Cooper, Benjamin; Dunne, Taylor; Gerosa, Katherine; Mercer, Kaitlyn; McGill, Stephen

In previous work, new Nanoparticle-enzyme Based Hybrids (NEBH) synthesis methods were investigated for nanoparticles of different shapes and electron energies. These hybrids can provide electromagnetic-field-driven ESH separations and transfers to desired molecular locations. Of paramount biomedical interest are the activity centers (including Fe-clusters) in proteins that perform their intended function and help synthesize other molecules. In this work we discuss results of our recent in situ ESH dynamics measurements: we use <15fs (Vitara) PPS broad band pulses and ultrahigh, 25T, magnetic fields from Split-helix magnet at NHMFL. Work included multi-spectral domain PPS harmonic generations and PPS sum frequency generations. Model compounds, including cytochromes, were used for testing and calibrations and previously studied Fe-S enzymes were prepared for measurements. While PPS opto-magnetic methods are known for their insight into electronic structure, our femtosecond measurements can provide ultrafast dynamic imaging of ESH mechanisms decision making steps. UF-PPS Project, performed in part at NHMFL, supported by NSF CA No. DMR-1157490, and 0654118 and U.S. DOE.

Testing Metal-Poor Stellar Models and Isochrones with HST Parallaxes of Metal-Poor Stars

NASA Astrophysics Data System (ADS)

Chaboyer, B.; McArthur, B. E.; O'Malley, E.; Benedict, G. F.; Feiden, G. A.; Harrison, T. E.; McWilliam, A.; Nelan, E. P.; Patterson, R. J.; Sarajedini, A.

2017-02-01

Hubble Space Telescope (HST) fine guidance sensor observations were used to obtain parallaxes of eight metal-poor ([Fe/H] < -1.4) stars. The parallaxes of these stars determined by the new Hipparcos reduction average 17% accuracy, in contrast to our new HST parallaxes, which average 1% accuracy and have errors on the individual parallaxes ranging from 85 to 144 μas. These parallax data were combined with HST Advanced Camera for Surveys photometry in the F606W and F814W filters to obtain the absolute magnitudes of the stars with an accuracy of 0.02-0.03 mag. Six of these stars are on the main sequence (MS) (with -2.7 < [Fe/H] < -1.8) and are suitable for testing metal-poor stellar evolution models and determining the distances to metal-poor globular clusters (GCs). Using the abundances obtained by O’Malley et al., we find that standard stellar models using the VandenBerg & Clem color transformation do a reasonable job of matching five of the MS stars, with HD 54639 ([Fe/H] = -2.5) being anomalous in its location in the color-magnitude diagram. Stellar models and isochrones were generated using a Monte Carlo analysis to take into account uncertainties in the models. Isochrones that fit the parallax stars were used to determine the distances and ages of nine GCs (with -2.4 ≤ [Fe/H] ≤ -1.9). Averaging together the age of all nine clusters led to an absolute age of the oldest, most metal-poor GCs of 12.7 ± 1.0 Gyr, where the quoted uncertainty takes into account the known uncertainties in the stellar models and isochrones, along with the uncertainty in the distance and reddening of the clusters.

Contrasting intra- and extracellular distribution of catalytic ferrous iron in ovalbumin-induced peritonitis.

PubMed

Ito, Fumiya; Nishiyama, Takahiro; Shi, Lei; Mori, Masahiko; Hirayama, Tasuku; Nagasawa, Hideko; Yasui, Hiroyuki; Toyokuni, Shinya

2016-08-05

Iron is an essential nutrient for every type of life on earth. However, excess iron is cytotoxic and can lead to an increased cancer risk in humans. Catalytic ferrous iron [Fe(II)] is an initiator of the Fenton reaction, which causes oxidative stress by generating hydroxyl radicals. Recently, it became possible to localize catalytic Fe(II) in situ with a turn-on fluorescent probe, RhoNox-1. Here, we screened each organ/cell of rats to globally evaluate the distribution of catalytic Fe(II) and found that eosinophils showed the highest abundance. In various cells, lysosomes were the major organelle, sharing ∼40-80% of RhoNox-1 fluorescence. We then used an ovalbumin-induced allergic peritonitis model to study the dynamics of catalytic Fe(II). Peritoneal lavage revealed that the total iron contents per cell were significantly decreased, whereas an increase in the number of inflammatory cells (macrophages, neutrophils, eosinophils and lymphocytes) resulted in an increased total iron content of the peritoneal inflammatory cells. Notably, macrophages, eosinophils and neutrophils exhibited significantly increased catalytic Fe(II) with increased DMT1 expression and decreased ferritin expression, though catalytic Fe(II) was significantly decreased in the peritoneal lavage fluid. In conclusion, catalytic Fe(II) in situ more directly reflects cellular activity and the accompanying pathology than total iron does. Copyright © 2016 Elsevier Inc. All rights reserved.

A time-domain finite element boundary integral approach for elastic wave scattering

NASA Astrophysics Data System (ADS)

Shi, F.; Lowe, M. J. S.; Skelton, E. A.; Craster, R. V.

2018-04-01

The response of complex scatterers, such as rough or branched cracks, to incident elastic waves is required in many areas of industrial importance such as those in non-destructive evaluation and related fields; we develop an approach to generate accurate and rapid simulations. To achieve this we develop, in the time domain, an implementation to efficiently couple the finite element (FE) method within a small local region, and the boundary integral (BI) globally. The FE explicit scheme is run in a local box to compute the surface displacement of the scatterer, by giving forcing signals to excitation nodes, which can lie on the scatterer itself. The required input forces on the excitation nodes are obtained with a reformulated FE equation, according to the incident displacement field. The surface displacements computed by the local FE are then projected, through time-domain BI formulae, to calculate the scattering signals with different modes. This new method yields huge improvements in the efficiency of FE simulations for scattering from complex scatterers. We present results using different shapes and boundary conditions, all simulated using this approach in both 2D and 3D, and then compare with full FE models and theoretical solutions to demonstrate the efficiency and accuracy of this numerical approach.

Fragment emission from the mass-symmetric reactions 58Fe,58Ni +58Fe,58Ni at Ebeam=30 MeV/nucleon

NASA Astrophysics Data System (ADS)

Ramakrishnan, E.; Johnston, H.; Gimeno-Nogues, F.; Rowland, D. J.; Laforest, R.; Lui, Y.-W.; Ferro, S.; Vasal, S.; Yennello, S. J.

1998-04-01

The mass-symmetric reactions 58Fe,58Ni +58Fe,58Ni were studied at a beam energy of Ebeam=30 MeV/nucleon in order to investigate the isospin dependence of fragment emission. Ratios of inclusive yields of isotopic fragments from hydrogen through nitrogen were extracted as a function of laboratory angle. A moving source analysis of the data indicates that at laboratory angles around 40° the yield of intermediate mass fragments (IMF's) beyond Z=3 is predominantly from a midrapidity source. The angular dependence of the relative yields of isotopes beyond Z=3 indicates that the IMF's at more central angles originate from a source which is more neutron deficient than the source responsible for fragments emitted at forward angles. The charge distributions and kinetic energy spectra of the IMF's at various laboratory angles were well reproduced by calculations employing a quantum molecular-dynamics code followed by a statistical multifragmentation model for generating fragments. The calculations indicate that the measured IMF's originate mainly from a single source. The isotopic composition of the emitted fragments is, however, not reproduced by the same calculation. The measured isotopic and isobaric ratios indicate an emitting source that is more neutron rich in comparison to the source predicted by model calculations.

Enhanced dielectric properties of poly(vinylidene fluoride) composites filled with nano iron oxide-deposited barium titanate hybrid particles

NASA Astrophysics Data System (ADS)

Zhang, Changhai; Chi, Qingguo; Dong, Jiufeng; Cui, Yang; Wang, Xuan; Liu, Lizhu; Lei, Qingquan

2016-09-01

We report enhancement of the dielectric permittivity of poly(vinylidene fluoride) (PVDF) generated by depositing magnetic iron oxide (Fe3O4) nanoparticles on the surface of barium titanate (BT) to fabricate BT-Fe3O4/PVDF composites. This process introduced an external magnetic field and the influences of external magnetic field on dielectric properties of composites were investigated systematically. The composites subjected to magnetic field treatment for 30 min at 60 °C exhibited the largest dielectric permittivity (385 at 100 Hz) when the BT-Fe3O4 concentration is approximately 33 vol.%. The BT-Fe3O4 suppressed the formation of a conducting path in the composite and induced low dielectric loss (0.3) and low conductivity (4.12 × 10-9 S/cm) in the composite. Series-parallel model suggested that the enhanced dielectric permittivity of BT-Fe3O4/PVDF composites should arise from the ultrahigh permittivity of BT-Fe3O4 hybrid particles. However, the experimental results of the BT-Fe3O4/PVDF composites treated by magnetic field agree with percolation theory, which indicates that the enhanced dielectric properties of the BT-Fe3O4/PVDF composites originate from the interfacial polarization induced by the external magnetic field. This work provides a simple and effective way for preparing nanocomposites with enhanced dielectric properties for use in the electronics industry.

Enhanced dielectric properties of poly(vinylidene fluoride) composites filled with nano iron oxide-deposited barium titanate hybrid particles.

PubMed

Zhang, Changhai; Chi, Qingguo; Dong, Jiufeng; Cui, Yang; Wang, Xuan; Liu, Lizhu; Lei, Qingquan

2016-09-16

We report enhancement of the dielectric permittivity of poly(vinylidene fluoride) (PVDF) generated by depositing magnetic iron oxide (Fe3O4) nanoparticles on the surface of barium titanate (BT) to fabricate BT-Fe3O4/PVDF composites. This process introduced an external magnetic field and the influences of external magnetic field on dielectric properties of composites were investigated systematically. The composites subjected to magnetic field treatment for 30 min at 60 °C exhibited the largest dielectric permittivity (385 at 100 Hz) when the BT-Fe3O4 concentration is approximately 33 vol.%. The BT-Fe3O4 suppressed the formation of a conducting path in the composite and induced low dielectric loss (0.3) and low conductivity (4.12 × 10(-9) S/cm) in the composite. Series-parallel model suggested that the enhanced dielectric permittivity of BT-Fe3O4/PVDF composites should arise from the ultrahigh permittivity of BT-Fe3O4 hybrid particles. However, the experimental results of the BT-Fe3O4/PVDF composites treated by magnetic field agree with percolation theory, which indicates that the enhanced dielectric properties of the BT-Fe3O4/PVDF composites originate from the interfacial polarization induced by the external magnetic field. This work provides a simple and effective way for preparing nanocomposites with enhanced dielectric properties for use in the electronics industry.

Enhanced dielectric properties of poly(vinylidene fluoride) composites filled with nano iron oxide-deposited barium titanate hybrid particles

PubMed Central

Zhang, Changhai; Chi, Qingguo; Dong, Jiufeng; Cui, Yang; Wang, Xuan; Liu, Lizhu; Lei, Qingquan

2016-01-01

We report enhancement of the dielectric permittivity of poly(vinylidene fluoride) (PVDF) generated by depositing magnetic iron oxide (Fe3O4) nanoparticles on the surface of barium titanate (BT) to fabricate BT–Fe3O4/PVDF composites. This process introduced an external magnetic field and the influences of external magnetic field on dielectric properties of composites were investigated systematically. The composites subjected to magnetic field treatment for 30 min at 60 °C exhibited the largest dielectric permittivity (385 at 100 Hz) when the BT–Fe3O4 concentration is approximately 33 vol.%. The BT–Fe3O4 suppressed the formation of a conducting path in the composite and induced low dielectric loss (0.3) and low conductivity (4.12 × 10−9 S/cm) in the composite. Series-parallel model suggested that the enhanced dielectric permittivity of BT–Fe3O4/PVDF composites should arise from the ultrahigh permittivity of BT–Fe3O4 hybrid particles. However, the experimental results of the BT–Fe3O4/PVDF composites treated by magnetic field agree with percolation theory, which indicates that the enhanced dielectric properties of the BT–Fe3O4/PVDF composites originate from the interfacial polarization induced by the external magnetic field. This work provides a simple and effective way for preparing nanocomposites with enhanced dielectric properties for use in the electronics industry. PMID:27633958

Characterisation of high temperature refractory ceramics for nuclear applications

NASA Astrophysics Data System (ADS)

Bottomley, P. D. W.; Wiss, Th; Janssen, A.; Cremer, B.; Thiele, H.; Manara, D.; Scheindlin, M.; Murray-Farthing, M.; Lajarge, P.; Menna, M.; Bouexière, D.; Rondinella, V. V.

2012-03-01

The ternary oxide ceramic system UO2-ZrO2-FeO is a refractory system that is of great relevance to the nuclear industry as it represents one of the main systems resulting from the interaction of the Zircaloy cladding, the UO2 fuel and the structural elements of a nuclear reactor. It is particularly the high temperature properties that require investigation; that is, when substantial overheating of the nuclear core occurs and interactions can lead to its degradation, melting and result in a severe nuclear accident. There has been much work on the UO2-ZrO2 system and also on the ternary system with FeO but there is still a need to examine 2 further aspects; firstly the effect of sub-oxidized systems, the UO2-Zr and FeO-Zr systems, and secondly the effect of Fe/Zr or Fe/U ratios on the melting point of the U-Zr-Fe oxide system. Samples of UO2-Zr and UO2-ZrO2-FeO were fabricated at ITU and then characterized by optical microscopy (OM) and X-ray diffraction to determine the ceramic's structure and verify the composition. Thereafter the samples are to be melted by laser flash heating and their liquidus and solidus temperatures determined by pyrometry. This programme is currently ongoing. The frozen samples, after testing, were then sectioned, polished and the molten zone micro-analytically examined by OM & SEM-EDS in order to determine its structure and composition and to compare with the existing phase diagrams. Examples of results from these systems will be given. Finally, a reacted Zr-FeO thermite mixture was examined, which had been used to generate high temperatures during tests of reactor melt-concrete interactions. The aim was to assess the reaction and estimate the heat generation from this novel technique. These results allow verification or improvement of the phase diagram and are of primary importance as input to models used to predict materials interactions in a severe nuclear accident.

Foam model of planetary formation

NASA Astrophysics Data System (ADS)

Andreev, Y.; Potashko, O.

The Analysis of 2637 terrestrial minerals shows presence of characteristic element and isotope structure for each ore irrespective of its site. The model of processes geo-nuclear syntheses elements is offered due to avalanche merge of nucleus which simply explains these laws. Main assumption: nucleus, atoms, connections, ores and minerals were formed in volume of the modern Earth at an early stage of its evolution from uniform proto-substance. Substantive provisions of the model: 1)The most part of nucleus of atoms of all chemical elements of the Earth's crust were formed on the mechanism of avalanche chain merge practically in one stage (in geological scales) in a course of correlated(in scales of a planet) process with allocation of a plenty of heat. 2) Atoms of chemical elements were generated during cooling a planet with preservation of a relative spatial arrangement of nucleus. 3) Chemical compounds have arisen at cooling a surface of a planet and were accompanied by reorganizations (hashing) macro- and geo-scale. 4) Mineral formations are consequence of correlated behaviour of chemical compounds on microscopic scales during phase transition from gaseous or liquid to a firm condition. 5) Synthesis of chemical elements in deep layers of the Earth occurs till now. "Foaming'' instead of "Big Bang" The physical space is continual gas-fluid environment consist of super fluid foam. The continuity, keeping and uniqueness of proto-substance are postulated. Scenario: primary singularity-> droplets(proto-galaxies) droplets(proto-stars)-> droplets(proto-planets)-> droplets(proto- satellites)-> droplets. Proto-planet substance->proton+electron as 1st generation disintegration result of primary foam. Nuclei or nucleonic crystals are the 2nd generation in result of cascade merge of protons into conglomerates. The theory has applied to the analysis of samples of native copper deposit from Rafalovka's ore deposit in Ukraine. The abundance of elements by use of the roentgen fluorescent microanalysis has been made. Changes of a parity of elements are described by nuclear synthesis reactions: 16O+47Ti, 23Na+40Ca, 24Mg+39K, 31P+32S-> 63Cu; 16O+49Ti, 23Na+42Ca, 26Mg+39K, 31P+34S-> 65Cu Dramatical change of isotope parities of 56Fe and 57Fe in the sites of space carried on 3 millimetres. The content of 57Fe is greater then 56Fe in Cu granule.

Quantitative computed tomography-based predictions of vertebral strength in anterior bending.

PubMed

Buckley, Jenni M; Cheng, Liu; Loo, Kenneth; Slyfield, Craig; Xu, Zheng

2007-04-20

This study examined the ability of QCT-based structural assessment techniques to predict vertebral strength in anterior bending. The purpose of this study was to compare the abilities of QCT-based bone mineral density (BMD), mechanics of solids models (MOS), e.g., bending rigidity, and finite element analyses (FE) to predict the strength of isolated vertebral bodies under anterior bending boundary conditions. Although the relative performance of QCT-based structural measures is well established for uniform compression, the ability of these techniques to predict vertebral strength under nonuniform loading conditions has not yet been established. Thirty human thoracic vertebrae from 30 donors (T9-T10, 20 female, 10 male; 87 +/- 5 years of age) were QCT scanned and destructively tested in anterior bending using an industrial robot arm. The QCT scans were processed to generate specimen-specific FE models as well as trabecular bone mineral density (tBMD), integral bone mineral density (iBMD), and MOS measures, such as axial and bending rigidities. Vertebral strength in anterior bending was poorly to moderately predicted by QCT-based BMD and MOS measures (R2 = 0.14-0.22). QCT-based FE models were better strength predictors (R2 = 0.34-0.40); however, their predictive performance was not statistically different from MOS bending rigidity (P > 0.05). Our results suggest that the poor clinical performance of noninvasive structural measures may be due to their inability to predict vertebral strength under bending loads. While their performance was not statistically better than MOS bending rigidities, QCT-based FE models were moderate predictors of both compressive and bending loads at failure, suggesting that this technique has the potential for strength prediction under nonuniform loads. The current FE modeling strategy is insufficient, however, and significant modifications must be made to better mimic whole bone elastic and inelastic material behavior.

Spent caustic oxidation using electro-generated Fenton's reagent in a batch reactor.

PubMed

Rodriguez, Nicolas; Hansen, Henrik K; Nunez, Patricio; Guzman, Jaime

2008-07-01

This work shows the results of four Electro-Fenton laboratory tests to reduce the chemical oxygen demand (COD) in spent caustic solutions. The treatment consisted of (i) a pH reduction followed by (ii) an Electro-Fenton process, which was analyzed in this work. The Fenton's reagent was produced in a specially designed reactor, where the waste stream flowed through a labyrinth made by ferrous plates. These plates acted as sacrificial anodes-releasing Fe(2 +) cations to the solution, where H(2)O(2) was also added. The Electro-Fenton process was analyzed varying the ferrous ion concentration ([Fe(+ 2)]), the spent caustic's initial temperature and the initial pH. Close to 95% removal of COD (from 8800 mg L(- 1)) was achieved at a pH of 4, a temperature of 40 degrees C and 100 mg L(- 1) of Fe(+ 2) (applying 1 A). Two models were considered to simulate the behavior of the reactor considering (i) axial dispersion and (ii) kinetic rate, respectively. The model that was based on kinetics, proved to be the slightly closest fit to the experimental values.

Relationship between the structure of Fe-MCM-48 and its activity in catalytic ozonation for diclofenac mineralization.

PubMed

Li, Xukai; Chen, Weirui; Tang, Yiming; Li, Laisheng

2018-05-12

Fe-MCM-48 catalyst with a three-dimensional cubic pore structure was directly synthesized via a hydrothermal method, and the mineralization efficiency of diclofenac (DCF) in the catalytic ozonation process (Fe-MCM-48/O 3 ) was assessed. X-ray diffraction (XRD), N 2 adsorption desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) characterizations revealed that Fe existed in the framework of MCM-48, and Fe-MCM-48 possessed a large surface area and a highly ordered cubic mesoporous structure, which could accelerate reactants and products diffusion. Regarding mineralization efficiency, the addition of Fe-MCM-48 significantly improved total organic carbon (TOC) removal, and approximately 49.9% TOC were removed through the Fe-MCM-48/O 3 process at 60 min, which was 2.0 times higher than that in single ozonation. Due to this catalyst's superior structure, Fe-MCM-48 showed the better catalytic activity compared with Fe-MCM-41 and Fe loaded MCM-48 (Fe/MCM-48, Fe existed on the surface of MCM-48). DCF removal in the Fe-MCM-48/O 3 process was primarily based on ozone direct oxidation. The improvement of mineralization efficiency was attributed to the function of generated hydroxyl radicals (•OH), which indicated that the presence of Fe-MCM-48 accelerated ozone decomposition. Moreover, the negatively charged surface of Fe-MCM-48 and the proper pH value of the DCF solution played an essential role in OH generation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhanced phosphate removal from wastewater by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) on CaCO3.

PubMed

Li, Yujie; He, Xiaoman; Hu, Huimin; Zhang, Tingting; Qu, Jun; Zhang, Qiwu

2018-05-21

Excessive existences of nutrients such as phosphate in the aqueous environment remain as a heavy concern although many researches have been reported for dealing with their removal. Based on the understanding toward the interactions of Fe compounds with phosphate and carbonate from many available researches, we designed a very simple and efficient approach for phosphate removal by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) as FeSO 4 on CaCO 3 . Addition and agitation of Fe(II) and CaCO 3 simultaneously to phosphate solution allowed an amorphous Fe(III)-P or Ca-Fe(III)-P precipitation, with a phosphate removal rate close to 100%, to reduce the residual phosphorus concentration less than 0.03 mg/L from 100 mg/L, reaching the discharge limit, even with the addition amounts of CaCO 3 as low as a stoichiometric ratio of CaCO 3 /PO 4 3- at 0.9 and ratio of Fe(II)/PO 4 3- at 1.5, and the percent of P 2 O 5 in the precipitate was as high as 19.4% enough as phosphate source for fertilizer production. Different from the alkaline process with enough OH - group, the slow hydrolysis of CaCO 3 resulting in low concentration of OH - group for the formation of Fe(OH) 2 , which was oxidized soon by air into trivalent Fe, achieved a continuous generation of fresh ferric composition for phosphate precipitation and could avoid its rapid formation and subsequent transformation into stable FeOOH of large particle size to lose the activity. These results based on the synergistic effect of using CaCO 3 and Fe(II) together may have applications in the treatment of eutrophic wastewater through a process with many advantages of easy operation and low-cost besides the high removal efficiency with phosphate percentage inside the precipitate high enough to serve for fertilizer production. Copyright © 2018 Elsevier Ltd. All rights reserved.

Localized parallel parametric generation of spin waves in a Ni{sub 81}Fe{sub 19} waveguide by spatial variation of the pumping field

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

Brächer, T.; Graduate School Materials Science in Mainz, Gottlieb-Daimler-Strasse 47, D-67663 Kaiserslautern; Pirro, P.

2014-03-03

We present the experimental observation of localized parallel parametric generation of spin waves in a transversally in-plane magnetized Ni{sub 81}Fe{sub 19} magnonic waveguide. The localization is realized by combining the threshold character of parametric generation with a spatially confined enhancement of the amplifying microwave field. The latter is achieved by modulating the width of the microstrip transmission line which is used to provide the pumping field. By employing microfocussed Brillouin light scattering spectroscopy, we analyze the spatial distribution of the generated spin waves and compare it with numerical calculations of the field distribution along the Ni{sub 81}Fe{sub 19} waveguide. Thismore » provides a local spin-wave excitation in transversally in-plane magnetized waveguides for a wide wave-vector range which is not restricted by the size of the generation area.« less

Self-current induced spin-orbit torque in FeMn/Pt multilayers

PubMed Central

Xu, Yanjun; Yang, Yumeng; Yao, Kui; Xu, Baoxi; Wu, Yihong

2016-01-01

Extensive efforts have been devoted to the study of spin-orbit torque in ferromagnetic metal/heavy metal bilayers and exploitation of it for magnetization switching using an in-plane current. As the spin-orbit torque is inversely proportional to the thickness of the ferromagnetic layer, sizable effect has only been realized in bilayers with an ultrathin ferromagnetic layer. Here we demonstrate that, by stacking ultrathin Pt and FeMn alternately, both ferromagnetic properties and current induced spin-orbit torque can be achieved in FeMn/Pt multilayers without any constraint on its total thickness. The critical behavior of these multilayers follows closely three-dimensional Heisenberg model with a finite Curie temperature distribution. The spin torque effective field is about 4 times larger than that of NiFe/Pt bilayer with a same equivalent NiFe thickness. The self-current generated spin torque is able to switch the magnetization reversibly without the need for an external field or a thick heavy metal layer. The removal of both thickness constraint and necessity of using an adjacent heavy metal layer opens new possibilities for exploiting spin-orbit torque for practical applications. PMID:27185656

Pelagic photoferrotrophy and iron cycling in a modern ferruginous basin.

PubMed

Llirós, Marc; García-Armisen, Tamara; Darchambeau, François; Morana, Cédric; Triadó-Margarit, Xavier; Inceoğlu, Özgül; Borrego, Carles M; Bouillon, Steven; Servais, Pierre; Borges, Alberto V; Descy, Jean-Pierre; Canfield, Don E; Crowe, Sean A

2015-09-08

Iron-rich (ferruginous) ocean chemistry prevailed throughout most of Earth's early history. Before the evolution and proliferation of oxygenic photosynthesis, biological production in the ferruginous oceans was likely driven by photoferrotrophic bacteria that oxidize ferrous iron {Fe(II)} to harness energy from sunlight, and fix inorganic carbon into biomass. Photoferrotrophs may thus have fuelled Earth's early biosphere providing energy to drive microbial growth and evolution over billions of years. Yet, photoferrotrophic activity has remained largely elusive on the modern Earth, leaving models for early biological production untested and imperative ecological context for the evolution of life missing. Here, we show that an active community of pelagic photoferrotrophs comprises up to 30% of the total microbial community in illuminated ferruginous waters of Kabuno Bay (KB), East Africa (DR Congo). These photoferrotrophs produce oxidized iron {Fe(III)} and biomass, and support a diverse pelagic microbial community including heterotrophic Fe(III)-reducers, sulfate reducers, fermenters and methanogens. At modest light levels, rates of photoferrotrophy in KB exceed those predicted for early Earth primary production, and are sufficient to generate Earth's largest sedimentary iron ore deposits. Fe cycling, however, is efficient, and complex microbial community interactions likely regulate Fe(III) and organic matter export from the photic zone.

Sensitivity Analysis and Parameter Estimation for a Reactive Transport Model of Uranium Bioremediation

NASA Astrophysics Data System (ADS)

Meyer, P. D.; Yabusaki, S.; Curtis, G. P.; Ye, M.; Fang, Y.

2011-12-01

A three-dimensional, variably-saturated flow and multicomponent biogeochemical reactive transport model of uranium bioremediation was used to generate synthetic data . The 3-D model was based on a field experiment at the U.S. Dept. of Energy Rifle Integrated Field Research Challenge site that used acetate biostimulation of indigenous metal reducing bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. A key assumption in past modeling studies at this site was that a comprehensive reaction network could be developed largely through one-dimensional modeling. Sensitivity analyses and parameter estimation were completed for a 1-D reactive transport model abstracted from the 3-D model to test this assumption, to identify parameters with the greatest potential to contribute to model predictive uncertainty, and to evaluate model structure and data limitations. Results showed that sensitivities of key biogeochemical concentrations varied in space and time, that model nonlinearities and/or parameter interactions have a significant impact on calculated sensitivities, and that the complexity of the model's representation of processes affecting Fe(II) in the system may make it difficult to correctly attribute observed Fe(II) behavior to modeled processes. Non-uniformity of the 3-D simulated groundwater flux and averaging of the 3-D synthetic data for use as calibration targets in the 1-D modeling resulted in systematic errors in the 1-D model parameter estimates and outputs. This occurred despite using the same reaction network for 1-D modeling as used in the data-generating 3-D model. Predictive uncertainty of the 1-D model appeared to be significantly underestimated by linear parameter uncertainty estimates.

Prediction on electronic structure of CH3NH3PbI3/Fe3O4 interfaces

NASA Astrophysics Data System (ADS)

Hou, Xueyao; Wang, Xiaocha; Mi, Wenbo; Du, Zunfeng

2018-01-01

The interfacial electronic structures of CH3NH3PbI3(MAPbI3)/Fe3O4 heterostructures are predicted by density functional theory. Four models (MAI/FeBO, PbI2/FeBO, MAI/FeA and PbI2/FeA) are included. Especially, a half-metal to semiconductor transition of Fe3O4 appears in PbI2/FeA model. A series of electric field is added to PbI2/FeA model, and a direct-indirect bandgap transition of Fe3O4 appears at a 500-kV/cm field. The electric field can control the bandgap of Fe3O4 in PbI2/FeA model by modulating the hybridization. The prediction of spin-related bandgap characteristic in MAPbI3/Fe3O4 is meaningful for further study.

Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids.

PubMed

Carraher, Jack M; Pestovsky, Oleg; Bakac, Andreja

2012-05-21

Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe(3+) in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe(2+). The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe(2+). The photochemistry in the presence of halide ions (X(-) = Cl(-), Br(-)) generates ethyl halides via halogen atom abstraction from FeX(n)(3-n) by ethyl radicals. Near-quantitative yields of C(2)H(5)X are obtained at ≥0.05 M X(-). Competition experiments with Co(NH(3))(5)Br(2+) provided kinetic data for the reaction of ethyl radicals with FeCl(2+) (k = (4.0 ± 0.5) × 10(6) M(-1) s(-1)) and with FeBr(2+) (k = (3.0 ± 0.5) × 10(7) M(-1) s(-1)). Photochemical decarboxylation of propionic acid in the presence of Cu(2+) generates ethylene and Cu(+). Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu(+) to Cu(2+), and removes gaseous olefins to prevent accumulation of Cu(+)(olefin) complexes and depletion of Cu(2+). The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

Heme versus non-heme iron-nitroxyl {FeN(H)O}⁸ complexes: electronic structure and biologically relevant reactivity.

PubMed

Speelman, Amy L; Lehnert, Nicolai

2014-04-15

Researchers have completed extensive studies on heme and non-heme iron-nitrosyl complexes, which are labeled {FeNO}(7) in the Enemark-Feltham notation, but they have had very limited success in producing corresponding, one-electron reduced, {FeNO}(8) complexes where a nitroxyl anion (NO(-)) is formally bound to an iron(II) center. These complexes, and their protonated iron(II)-NHO analogues, are proposed key intermediates in nitrite (NO2(-)) and nitric oxide (NO) reducing enzymes in bacteria and fungi. In addition, HNO is known to have a variety of physiological effects, most notably in the cardiovascular system. HNO may also serve as a signaling molecule in mammals. For these functions, iron-containing proteins may mediate the production of HNO and serve as receptors for HNO in vivo. In this Account, we highlight recent key advances in the preparation, spectroscopic characterization, and reactivity of ferrous heme and non-heme nitroxyl (NO(-)/HNO) complexes that have greatly enhanced our understanding of the potential biological roles of these species. Low-spin (ls) heme {FeNO}(7) complexes (S = 1/2) can be reversibly reduced to the corresponding {FeNO}(8) species, which are stable, diamagnetic compounds. Because the reduction is ligand (NO) centered in these cases, it occurs at extremely negative redox potentials that are at the edge of the biologically feasible range. Interestingly, the electronic structures of ls-{FeNO}(7) and ls-{FeNO}(8) species are strongly correlated with very similar frontier molecular orbitals (FMOs) and thermodynamically strong Fe-NO bonds. In contrast, high-spin (hs) non-heme {FeNO}(7) complexes (S = 3/2) can be reduced at relatively mild redox potentials. Here, the reduction is metal-centered and leads to a paramagnetic (S = 1) {FeNO}(8) complex. The increased electron density at the iron center in these species significantly decreases the covalency of the Fe-NO bond, making the reduced complexes highly reactive. In the absence of steric bulk, monomeric high-spin {FeNO}(8) complexes decompose rapidly. Notably, in a recently prepared, dimeric [{FeNO}(7)]2 species, we observed that reduction leads to rapid N-N bond formation and N2O generation, which directly models the reactivity of flavodiiron NO reductases (FNORs). We have also made key progress in the preparation and stabilization of corresponding HNO complexes, {FeNHO}(8), using both heme and non-heme ligand sets. In both cases, we have taken advantage of sterically bulky coligands to stabilize these species. ls-{FeNO}(8) complexes are basic and easily form corresponding ls-{FeNHO}(8) species, which, however, decompose rapidly via disproportionation and H2 release. Importantly, we recently showed that we can suppress this reaction via steric protection of the bound HNO ligand. As a result, we have demonstrated that ls-{FeNHO}(8) model complexes are stable and amenable to spectroscopic characterization. Neither ls-{FeNO}(8) nor ls-{FeNHO}(8) model complexes are active for N-N coupling, and hence, seem unsuitable as reactive intermediates in nitric oxide reductases (NORs). Hs-{FeNO}(8) complexes are more basic than their hs-{FeNO}(7) precursors, but their electronic structure and reactivity is not as well characterized.

Emergence of gamma motor activity in an artificial neural network model of the corticospinal system.

PubMed

Grandjean, Bernard; Maier, Marc A

2017-02-01

Muscle spindle discharge during active movement is a function of mechanical and neural parameters. Muscle length changes (and their derivatives) represent its primary mechanical, fusimotor drive its neural component. However, neither the action nor the function of fusimotor and in particular of γ-drive, have been clearly established, since γ-motor activity during voluntary, non-locomotor movements remains largely unknown. Here, using a computational approach, we explored whether γ-drive emerges in an artificial neural network model of the corticospinal system linked to a biomechanical antagonist wrist simulator. The wrist simulator included length-sensitive and γ-drive-dependent type Ia and type II muscle spindle activity. Network activity and connectivity were derived by a gradient descent algorithm to generate reciprocal, known target α-motor unit activity during wrist flexion-extension (F/E) movements. Two tasks were simulated: an alternating F/E task and a slow F/E tracking task. Emergence of γ-motor activity in the alternating F/E network was a function of α-motor unit drive: if muscle afferent (together with supraspinal) input was required for driving α-motor units, then γ-drive emerged in the form of α-γ coactivation, as predicted by empirical studies. In the slow F/E tracking network, γ-drive emerged in the form of α-γ dissociation and provided critical, bidirectional muscle afferent activity to the cortical network, containing known bidirectional target units. The model thus demonstrates the complementary aspects of spindle output and hence γ-drive: i) muscle spindle activity as a driving force of α-motor unit activity, and ii) afferent activity providing continuous sensory information, both of which crucially depend on γ-drive.

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand† †Electronic supplementary information (ESI) available: Complete experimental procedures and magnetic measurements and models. CCDC 1417565–1417567. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03006d Click here for additional data file. Click here for additional data file.

PubMed Central

Wong, Janice L.; Higgins, Robert F.; Bhowmick, Indrani; Cao, David Xi; Szigethy, Géza; Ziller, Joseph W.

2016-01-01

A new bimetallic platform comprising a six-coordinate Fe(ONO)2 unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONOcat)H3 = bis(3,5-di-tert-butyl-2-phenol)amine). Reaction of Fe(ONO)2 with either (ONOcat)Fe(py)3 or with (ONOq)FeCl2 under reducing conditions led to the formation of the bimetallic complex Fe2(ONO)3, which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO)2 with the new synthon (ONOsq˙)Zn(py)2 led to the formation of the heterobimetallic complex FeZn(ONO)3, with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO)3 are consistent with a ground state S = 3/2 spin system, generated from a high-spin iron(ii) center that is antiferromagnetically coupled to a single (ONOsq˙)2– radical ligand. In the case of Fe2(ONO)3, the magnetic data revealed a ground state S = 7/2 spin system arising from the interactions of one high-spin iron(ii) center, one high-spin iron(iii) center, and two (ONOsq˙)2– radical ligands. PMID:28808535

Electro-optical detection of THz radiation in Fe implanted LiNbO3

NASA Astrophysics Data System (ADS)

Wang, Yuhua; Ni, Hongwei; Zhan, Weiting; Yuan, Jie; Wang, Ruwu

2013-01-01

In this letter, the authors present first observation of terahertz generation from Fe implantation of LiNbO3 crystal substrate. LiNbO3 single crystal is grown by Czochralski method. Metal nanoparticles synthesized by Fe ion implantation were implanted into LiNbO3 single crystal using metal vapor vacuum arc (MEVVA) ion source. 1 kHz, 35 fs laser pulsed centered at 800 nm were focused onto the samples. Terahertz was generated via optical rectification. The findings suggest that under the investigated implantation parameter, a spectral component in excess of 0.44 THz emission were found from Fe ion implantation of LiNbO3.

Tungsten fiber reinforced FeCralY: A first generation composite turbine blade material

NASA Technical Reports Server (NTRS)

Petrasek, D. W.; Winsa, E. A.; Westfall, L. J.; Signorelli, R. A.

1979-01-01

Tungsten-fiber/FeCrAlY (W/FeCrAlY) was identified as a promising aircraft engine, first generation, turbine blade composite material. Based on available data, W/FeCrAlY should have the stress-rupture, creep, tensile, fatigue, and impact strengths required for turbine blades operating from 1250 to 1370 K. It should also have adequate oxidation, hot corrosion, and thermal cycling damage resistance as well as high thermal conductivity. Concepts for potentially low cost blade fabrication were developed. These concepts were used to design a first stage JT9D convection cooled turbine blade having a calculated 50 K use-temperature advantage over the directionally solidified superalloy blade.

A universal algorithm for an improved finite element mesh generation Mesh quality assessment in comparison to former automated mesh-generators and an analytic model.

PubMed

Kaminsky, Jan; Rodt, Thomas; Gharabaghi, Alireza; Forster, Jan; Brand, Gerd; Samii, Madjid

2005-06-01

The FE-modeling of complex anatomical structures is not solved satisfyingly so far. Voxel-based as opposed to contour-based algorithms allow an automated mesh generation based on the image data. Nonetheless their geometric precision is limited. We developed an automated mesh-generator that combines the advantages of voxel-based generation with improved representation of the geometry by displacement of nodes on the object-surface. Models of an artificial 3D-pipe-section and a skullbase were generated with different mesh-densities using the newly developed geometric, unsmoothed and smoothed voxel generators. Compared to the analytic calculation of the 3D-pipe-section model the normalized RMS error of the surface stress was 0.173-0.647 for the unsmoothed voxel models, 0.111-0.616 for the smoothed voxel models with small volume error and 0.126-0.273 for the geometric models. The highest element-energy error as a criterion for the mesh quality was 2.61x10(-2) N mm, 2.46x10(-2) N mm and 1.81x10(-2) N mm for unsmoothed, smoothed and geometric voxel models, respectively. The geometric model of the 3D-skullbase resulted in the lowest element-energy error and volume error. This algorithm also allowed the best representation of anatomical details. The presented geometric mesh-generator is universally applicable and allows an automated and accurate modeling by combining the advantages of the voxel-technique and of improved surface-modeling.

Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres.

PubMed

Harrop, Todd C; Song, Datong; Lippard, Stephen J

2007-11-01

The interaction of nitric oxide (NO) with iron-sulfur cluster proteins results in the formation of dinitrosyl iron complexes (DNICs) coordinated by cysteine residues from the peptide backbone or with low molecular weight sulfur-containing molecules like glutathione. Such DNICs are among the modes available in biology to store, transport, and deliver NO to its relevant targets. In order to elucidate the fundamental chemistry underlying the formation of DNICs and to characterize possible intermediates in the process, we have investigated the interaction of NO (g) and NO(+) with iron-sulfur complexes having the formula [Fe(SR)(4)](2-), where R=(t)Bu, Ph, or benzyl, chosen to mimic sulfur-rich iron sites in biology. The reaction of NO (g) with [Fe(S(t)Bu)(4)](2-) or [Fe(SBz)(4)](2-) cleanly affords the mononitrosyl complexes (MNICs), [Fe(S(t)Bu)(3)(NO)](-) (1) and [Fe(SBz)(3)(NO)](-) (3), respectively, by ligand displacement. Mononitrosyl species of this kind were previously unknown. These complexes further react with NO (g) to generate the corresponding DNICs, [Fe(SPh)(2)(NO)(2)](-) (4) and [Fe(SBz)(2)(NO)(2)](-) (5), with concomitant reductive elimination of the coordinated thiolate donors. Reaction of [Fe(SR)(4)](2-) complexes with NO(+) proceeds by a different pathway to yield the corresponding dinitrosyl S-bridged Roussin red ester complexes, [Fe(2)(mu-S(t)Bu)(2)(NO)(4)] (2), [Fe(2)(mu-SPh)(2)(NO)(4)] (7) and [Fe(2)(mu-SBz)(2)(NO)(4)] (8). The NO/NO(+) reactivity of an Fe(II) complex with a mixed nitrogen/sulfur coordination sphere was also investigated. The DNIC and red ester species, [Fe(S-o-NH(2)C(6)H(4))(2)(NO)(2)](-) (6) and [Fe(2)(mu-S-o-NH(2)C(6)H(4))(2)(NO)(4)] (9), were generated. The structures of 8 and 9 were verified by X-ray crystallography. The MNIC complex 1 can efficiently deliver NO to iron-porphyrin complexes like [Fe(TPP)Cl], a reaction that is aided by light. Removal of the coordinated NO ligand of 1 by photolysis and addition of elemental sulfur generates higher nuclearity Fe/S clusters.

Field dependent magnetic anisotropy of Ga0.2Fe0.8 thin films

NASA Astrophysics Data System (ADS)

Resnick, Damon A.; McClure, A.; Kuster, C. M.; Rugheimer, P.; Idzerda, Y. U.

2011-04-01

Using longitudinal MOKE in combination with a variable strength rotating magnetic field, called the rotational MOKE (ROTMOKE) method, we show that the magnetic anisotropy for a Ga0.2Fe0.8 single crystal film with a thickness of 17 nm, grown on GaAs (001) with a thick ZnSe buffer layer, depends linearly on the strength of the applied magnetic field. The torque moment curves generated using ROTMOKE are well fit with a model that accounts for the uniaxial, cubic, or fourfold anisotropy, as well as additional terms with a linear dependence on the applied magnetic field. The uniaxial and cubic anisotropy fields, taken from both the hard and the easy axis scans, are seen to remain field independent. The field dependent terms are evidence of a large affect of the magnetostriction and its contribution to the effective magnetic anisotropy in GaxFe1-x thin films.

Genetic diversity in the feline leukemia virus gag gene.

PubMed

Kawamura, Maki; Watanabe, Shinya; Odahara, Yuka; Nakagawa, So; Endo, Yasuyuki; Tsujimoto, Hajime; Nishigaki, Kazuo

2015-06-02

Feline leukemia virus (FeLV) belongs to the Gammaretrovirus genus and is horizontally transmitted among cats. FeLV is known to undergo recombination with endogenous retroviruses already present in the host during FeLV-subgroup A infection. Such recombinant FeLVs, designated FeLV-subgroup B or FeLV-subgroup D, can be generated by transduced endogenous retroviral env sequences encoding the viral envelope. These recombinant viruses have biologically distinct properties and may mediate different disease outcomes. The generation of such recombinant viruses resulted in structural diversity of the FeLV particle and genetic diversity of the virus itself. FeLV env diversity through mutation and recombination has been studied, while gag diversity and its possible effects are less well understood. In this study, we investigated recombination events in the gag genes of FeLVs isolated from naturally infected cats and reference isolates. Recombination and phylogenetic analyses indicated that the gag genes often contain endogenous FeLV sequences and were occasionally replaced by entire endogenous FeLV gag genes. Phylogenetic reconstructions of FeLV gag sequences allowed for classification into three distinct clusters, similar to those previously established for the env gene. Analysis of the recombination junctions in FeLV gag indicated that these variants have similar recombination patterns within the same genotypes, indicating that the recombinant viruses were horizontally transmitted among cats. It remains to be investigated whether the recombinant sequences affect the molecular mechanism of FeLV transmission. These findings extend our understanding of gammaretrovirus evolutionary patterns in the field. Copyright © 2015 Elsevier B.V. All rights reserved.

Metabolism, survival, and gene expression of Pseudomonas putida to hematite nanoparticles mediated by surface-bound humic acid

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

Ouyang, Kai; Walker, Sharon L.; Yu, Xiao-Ying

Natural organic matter (NOM) is likely to coat naturally occurring nanoparticles (NNPs) in the soil environment and poses distinct effects on the interaction between NPs and soil microorganisms, however such topic has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) on the toxicity of hematite NPs (i.e., nano-Fe2O3) to Pseudomonas putida (P. putida). Results showed that nano-Fe2O3 could inhibit the bacterial growth with an IC50 of 23.58 mg L-1, while nanoparticle surface-bound HA could significantly alleviate the P. putida toxicity of nano-Fe2O3. IC50 of nano-Fe2O3 increased to 4774.23 mgmore » L-1 as a result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that nanoparticle surface-bound HA prevented the adhesion of nano-Fe2O3 to the cells as well as limited cell internalization of nanoparticles due to the increased electrostatic repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity. Interfacial interactions between hematite NPs and cell membrane were also evaluated on the basis of the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, and the magnitude of interaction energy barrier correlated well with the 48 h LC50 data of hematite NPs to P. putida. This result implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in microorganisms.« less

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

PubMed Central

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-01

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

PubMed

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-06

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

Phase-field model simulation of ferroelectric/antiferroelectric materials microstructure evolution under multiphysics loading

NASA Astrophysics Data System (ADS)

Zhang, Jingyi

Ferroelectric (FE) and closely related antiferroelectric (AFE) materials have unique electromechanical properties that promote various applications in the area of capacitors, sensors, generators (FE) and high density energy storage (AFE). These smart materials with extensive applications have drawn wide interest in the industrial and scientific world because of their reliability and tunable property. However, reliability issues changes its paradigms and requires guidance from detailed mechanism theory as the materials applications are pushed for better performance. A host of modeling work were dedicated to study the macro-structural behavior and microstructural evolution in FE and AFE material under various conditions. This thesis is focused on direct observation of domain evolution under multiphysics loading for both FE and AFE material. Landau-Devonshire time-dependent phase field models were built for both materials, and were simulated in finite element software Comsol. In FE model, dagger-shape 90 degree switched domain was observed at preexisting crack tip under pure mechanical loading. Polycrystal structure was tested under same condition, and blocking effect of the growth of dagger-shape switched domain from grain orientation difference and/or grain boundary was directly observed. AFE ceramic model was developed using two sublattice theory, this model was used to investigate the mechanism of energy efficiency increase with self-confined loading in experimental tests. Consistent results was found in simulation and careful investigation of calculation results gave confirmation that origin of energy density increase is from three aspects: self-confinement induced inner compression field as the cause of increase of critical field, fringe leak as the source of elevated saturation polarization and uneven defects distribution as the reason for critical field shifting and phase transition speed. Another important affecting aspect in polycrystalline materials is the texture of material, textured materials have better alignment and the alignment reorganization is associated with inelastic strain. We developed a vector field of alignment to describe texture degree and introduced the alignment vector into our FE and AFE model. The model with alignment field gave quantatively results for the well-recognized irreversible strain in AFE virgin ceramics during the first poling process. The texture field also shows a shielding zone under mechanical loading around existing crack tip. In conclusion, this thesis developed working models of FE and AFE material and systematically studied their behavior under multiphysics loading in a finite element analysis approach. Materials structure of polycrystal materials including grain orientation, grain boundary, defects and materials texture were tested for their effect on hysteresis and switched domain growth. Detailed microstructure development in domain switching and alignment was directly observed in this simulation.

Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

USGS Publications Warehouse

Cravotta,, Charles A.

1991-01-01

Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.

O 2 Activation by Non-Heme Iron Enzymes

DOE PAGES

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.

2016-10-28

The non-heme Fe enzymes are ubiquitous in nature and perform a wide range of functions involving O 2 activation. These had been difficult to study relative to heme enzymes; however, spectroscopic methods have now been developed that provide significant insight into the correlation of structure with function. This Current Topics article summarizes both the molecular mechanism these enzymes use to control O 2 activation in the presence of cosubstrates and the oxygen intermediates these reactions generate. Three types of O 2 activation are observed. First, non-heme reactivity is shown to be different from heme chemistry where a low-spin Fe III-OOHmore » non-heme intermediate directly reacts with substrate. Also, two subclasses of non-heme Fe enzymes generate high-spin Fe IV=O intermediates that provide both σ and π frontier molecular orbitals that can control selectivity. Lastly, for several subclasses of non-heme Fe enzymes, substrate binding to the Fe II site leads to the one electron reductive activation of O 2 to an Fe III-superoxide capable of H-atom abstraction and electrophilic attack.« less

O 2 Activation by Non-Heme Iron Enzymes

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

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.

The non-heme Fe enzymes are ubiquitous in nature and perform a wide range of functions involving O 2 activation. These had been difficult to study relative to heme enzymes; however, spectroscopic methods have now been developed that provide significant insight into the correlation of structure with function. This Current Topics article summarizes both the molecular mechanism these enzymes use to control O 2 activation in the presence of cosubstrates and the oxygen intermediates these reactions generate. Three types of O 2 activation are observed. First, non-heme reactivity is shown to be different from heme chemistry where a low-spin Fe III-OOHmore » non-heme intermediate directly reacts with substrate. Also, two subclasses of non-heme Fe enzymes generate high-spin Fe IV=O intermediates that provide both σ and π frontier molecular orbitals that can control selectivity. Lastly, for several subclasses of non-heme Fe enzymes, substrate binding to the Fe II site leads to the one electron reductive activation of O 2 to an Fe III-superoxide capable of H-atom abstraction and electrophilic attack.« less

Viability of thin wall tube forming of ATF FeCrAl

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

Maloy, Stuart Andrew; Aydogan, Eda; Anderoglu, Osman

Fabrication of thin walled tubing of FeCrAl alloys is critical to its success as a candidate enhanced accident-tolerant fuel cladding material. Alloys that are being investigated are Generation I and Generation II FeCrAl alloys produced at ORNL and an ODS FeCrAl alloy, MA-956 produced by Special Metals. Gen I and Gen II FeCrAl alloys were provided by ORNL and MA-956 was provided by LANL (initially produced by Special Metals). Three tube development efforts were undertaken. ORNL led the FeCrAl Gen I and Gen II alloy development and tube processing studies through drawing tubes at Rhenium Corporation. LANL received alloys frommore » ORNL and led tube processing studies through drawing tubes at Century Tubing. PNNL led the development of tube processing studies on MA-956 through pilger processing working with Sandvik Corporation. A summary of the recent progress on tube development is provided in the following report and a separate ORNL report: ORNL/TM-2015/478, “Development and Quality Assessments of Commercial Heat Production of ATF FeCrAl Tubes”.« less

Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2018-05-01

The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

Engineered Biocompatible Nanoparticles for in Vivo Imaging Applications

PubMed Central

2010-01-01

Iron−platinum alloy nanoparticles (FePt NPs) are extremely promising candidates for the next generation of contrast agents for magnetic resonance (MR) diagnostic imaging and MR-guided interventions, including hyperthermic ablation of solid cancers. FePt has high Curie temperature, saturation magnetic moment, magneto-crystalline anisotropy, and chemical stability. We describe the synthesis and characterization of a family of biocompatible FePt NPs suitable for biomedical applications, showing and discussing that FePt NPs can exhibit low cytotoxicity. The importance of engineering the interface of strongly magnetic NPs using a coating allowing free aqueous permeation is demonstrated to be an essential parameter in the design of new generations of diagnostic and therapeutic MRI contrast agents. We report effective cell internalization of FePt NPs and demonstrate that they can be used for cellular imaging and in vivo MRI applications. This opens the way for several future applications of FePt NPs, including regenerative medicine and stem cell therapy in addition to enhanced MR diagnostic imaging. PMID:20919679

Oxidizing Roasting Performances of Coke Fines Bearing Brazilian Specularite Pellets

NASA Astrophysics Data System (ADS)

Chun, Tiejun; Zhu, Deqing

2016-06-01

Oxidized pellets, consisting of Brazilian specularite fines and coke fines, were prepared by disc pelletizer using bentonite as binder. The roasting process of pellets includes preheating stage and firing stage. The compressive strength of preheated pellets and fired pellets reached the peak value at 1.5% coke fines dosage. During the initial stage of preheating, some original Fe2O3 was reduced to Fe3O4 because of partial reduction atmosphere in pellet. During the later stage of preheating and firing stage, coke fines were burnt out, and the secondary Fe2O3 (new generation Fe2O3) was generated due to the re-oxidization of Fe3O4, which improved the recrystallization of Fe2O3. Compared with the fired pellets without adding coke fines, fired pellets with 1.5% coke fines exhibited the comparable RSI (reduction swelling index) and RDI+3.15 mm (reduction degradation index), and slightly lower RI (reducibility index).

Fabrication and photocatalytic property of magnetic NiFe2O4/Cu2O composites

NASA Astrophysics Data System (ADS)

He, Zuming; Xia, Yongmei; Tang, Bin; Su, Jiangbin

2017-09-01

Magnetically separable NiFe2O4/Cu2O composites were successfully synthesized by a two-step method. The samples were characterized by XRD, XPS, SEM and VSM as well as their PL spectra and UV-vis adsorption spectra. The results showed that the NiFe2O4/Cu2O composites were composed of cubic-structured Cu2O and spinel-structured NiFe2O4, were able to absorb a large amount of visible light, exhibited excellent photocatalytic activity under simulated solar light irradiation and could be easily separated by an external magnetic field. The NiFe2O4/Cu2O composites exhibited higher photocatalytic performance than that of a single semiconductor. It was found that the prominently enhanced photocatalytic performance of NiFe2O4/Cu2O composites was ascribed to the effective separation of photo-generated electron-hole pairs and the effective generation of the hydroxyl radical •OH.

A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts† †Electronic supplementary information (ESI) available: Experimental, spectroscopic, additional electrochemical and computational details, X-ray crystallographic data (CIF) from the structure of the complexes [Ni–Fe]0, [Ni2–Fe2]2+, [Ni2–Fe]+, and computational coordinates are available. CCDC crystallographic data for the complexes [Ni–Fe]0, [Ni2–Fe2]2+ and [Ni2–Fe]+ were deposited in the Cambridge Crystallographic Data Centre. CCDC [Ni–Fe]0 (CCDC 1045461), [Ni2–Fe2]2+ (CCDC 1045460) and [Ni2–Fe]+ (CCDC 1565539). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03378h

PubMed Central

Ghosh, Pokhraj; Ding, Shengda; Chupik, Rachel B.; Quiroz, Manuel; Hsieh, Chung-Hung; Bhuvanesh, Nattami; Hall, Michael B.

2017-01-01

Experimental and computational studies address key questions in a structure–function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN2S2 or [(NO)Fe]N2S2 as donors to (η5-C5H5)Fe(CO)+ or [Fe(NO)2]+/0 generate a series of four bimetallics, gradually “softened” by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox levels, demonstrating required features of electrocatalysis. Computational modeling of experimental structures and likely transient intermediates that connect the electrochemical events find roles for electron delocalization by NO, as well as Fe–S bond dissociation that produce a terminal thiolate as pendant base well positioned to facilitate proton uptake and transfer. Dihydrogen formation is via proton/hydride coupling by internal S–H+···–H–Fe units of the “harder” bimetallic arrangements with more localized electron density, while softer units convert H–···H–via reductive elimination from two Fe–H deriving from the highly delocalized, doubly reduced [Fe2(NO)3]– derivative. Computational studies also account for the inactivity of a Ni2Fe complex resulting from entanglement of added H+ in a pinched –Sδ–···H+···δ–S– arrangement. PMID:29619175

Redox Heterogenity in MORB

NASA Astrophysics Data System (ADS)

Cottrell, E.; Kelley, K. A.

2012-12-01

Mantle oxygen fugacity (fO2) has a first-order effect on the petrogenesis of mantle-derived melts and the speciation of mantle fluids. Current debate centers on the spatial uniformity of upper mantle fO2 and its constancy through geologic time. We use iron K-edge X-ray absorption near-edge structure (μXANES) spectroscopy to provide Fe3+ /ΣFe ratios of submarine mantle-derived basalts from mid-ocean ridges (MORB) as a proxy for fO2. A global survey of primitive (>8.75 wt% MgO) MORB glasses at spreading centers, unaffected by plumes, reveals a decrease in Fe3+ /ΣFe ratio of 12% relative with indices of mantle enrichment such as 87/86Sr, 208/204Pb, Ba/La, and Rb/Sr ratios. The strong negative correlation between upper mantle fO2 and enrichment recorded by MORB glasses contrasts with the positive relationship hinted at by abyssal peridotite oxybarometry (e.g. Ballhaus, CMP, 1993) and the general prediction of a positive correlation born of the expectation that Fe3+ can be treated as more incompatible than Fe2+ during mantle melting. These data unequivocally link upper mantle oxidation state to mantle source enrichment. EMORB generation is commonly attributed to subduction-related processes. That EMORB is more reduced than NMORB implies that deeply subducted and recycled lithologies, such as anoxic sediment, may be more reduced than ambient mantle. Negative correlations between traditional tracers of recycled sediment (e.g. +Nb anomaly, high 87/86Sr, high LILE/LREE) and redox support this hypothesis. Preservation of redox signatures on plate-recycling timescales of hundreds of millions to billions of years would require the mantle to be very poorly buffered. Alternatively, MORB Fe3+ /ΣFe ratios may be generated in situ beneath ridges as a function of variable carbon content. The shallow MORB source is too oxidized to stabilize graphite (Cottrell and Kelley, EPSL, 2011) and carbon exists as oxides. Decreasing fO2 with increasing depth eventually stabilizes reduced carbon species (diamond, carbides, alloys), however, and aCO2 may buffer mantle assemblages. Upon ascent, reduced carbon in upwelling mantle must oxidize, reducing Fe in the process such that more carbon-rich mantle would arrive at the surface with a lower Fe3+ /ΣFe ratio. We cannot directly correlate Fe3+ /ΣFe ratios with CO2 concentrations because submarine basalts have variably degassed CO2; however, the unequivocally carbon-rich sample 2πD43 (popping rock) does record a low Fe3+ /ΣFe ratio. CO2 variations on the order of 80 ppm in the mantle source would explain the range of MORB/EMORB Fe3+ /ΣFe ratios we observe, indicating a possible range of carbon concentrations in subduction-related lithologies. The relationships between MORB Fe3+ /ΣFe ratios, trace elements, and isotopes are consistent with modeled mixtures of depleted melts and low-degree carbonatitic melts of ancient subducted igneous crust plus 5-15% sediment (Stracke et al., G3, 2001) using the near-solidus carbonatitic partition coefficients of Dasgupta et al., Chem Geol, (2009). It may be that low degree carbonatitic melts even act through geologic time to scavenge and fractionate trace elements, creating enriched high-carbon reservoirs. Low Fe3+ /ΣFe ratios, and even EMORB itself, may therefore herald greater carbon concentrations, and the influence of low-degree carbonatitic melts, in Earth's mantle.

Influence of the environment on the [4Fe-4S]2+ to [2Fe-2S]2+ cluster switch in the transcriptional regulator FNR.

PubMed

Crack, Jason C; Gaskell, Alisa A; Green, Jeffrey; Cheesman, Myles R; Le Brun, Nick E; Thomson, Andrew J

2008-02-06

In Escherichia coli, the switch between aerobic and anaerobic metabolism is primarily controlled by the fumarate and nitrate reduction transcriptional regulator FNR. In the absence of O2, FNR binds a [4Fe-4S]2+ cluster, generating a transcriptionally active dimeric form. Exposure to O2 results in the conversion of the cluster to a [2Fe-2S]2+ form, leading to dissociation of the protein into transcriptionally inactive monomers. The [4Fe-4S]2+ to [2Fe-2S]2+ cluster conversion proceeds in two steps. Step 1 involves the one-electron oxidation of the cluster, resulting in the release of Fe2+, generating a [3Fe-4S]1+ cluster intermediate, and a superoxide ion. In step 2, the cluster intermediate spontaneously rearranges to form the [2Fe-2S]2+ cluster, with the release of a Fe3+ ion and two sulfide ions. Here, we demonstrate that, in both native and reconstituted [4Fe-4S] FNR, the reaction environment and, in particular, the presence of Fe2+ and/or Fe3+ chelators can influence significantly the cluster conversion reaction. We demonstrate that while the rate of step 1 is largely insensitive to chelators, that of step 2 is significantly enhanced by both Fe2+ and Fe3+ chelators. We show that, for reactions in Fe3+-coordinating phosphate buffer, step 2 is enhanced to the extent that step 1 becomes the rate determining step and the [3Fe-4S]1+ intermediate is no longer detectable. Furthermore, Fe3+ released during this step is susceptible to reduction in the presence of Fe2+ chelators. This work, which may have significance for the in vivo FNR cluster conversion reaction in the cell cytoplasm, provides an explanation for apparently contradictory results reported from different laboratories.

A lateral-type spin-photodiode based on Fe/x-AlOx/p-InGaAs junctions with a refracting-facet side window

NASA Astrophysics Data System (ADS)

Roca, Ronel Christian; Nishizawa, Nozomi; Nishibayashi, Kazuhiro; Munekata, Hiro

2018-06-01

A lateral-type spin-photodiode having a refracting facet on a side edge of the device is proposed and demonstrated at room temperature. The light shed horizontally on the side of the device is refracted and introduced directly into a thin InGaAs active layer under the spin-detecting Fe contact in which spin-polarized carriers are generated and injected into the Fe contact through a crystalline AlOx tunnel barrier. Experiments have been carried out with a circular polarization spectrometry set up, through which the helicity-dependent photocurrent component, ΔI, is obtained with the conversion efficiency F ≈ 0.4%, where F is the ratio between ΔI and total photocurrent Iph. This value is the highest reported so far for pure lateral-type spin-photodiodes. It is discussed through the analysis with a model consisting of drift-diffusion and quantum tunneling equations that a factor that limits the F value is unoccupied spin-polarized density-of-states of Fe in energy region into which the spin-polarized electrons in a semiconductor are injected.

Impacts of antioxidants on hydroxyl radical production from individual and mixed transition metals in a surrogate lung fluid

NASA Astrophysics Data System (ADS)

Charrier, Jessica G.; Anastasio, Cort

2011-12-01

Inhalation of ambient particulate matter causes morbidity and mortality in humans. One hypothesized mechanism of toxicity is the particle-induced formation of reactive oxygen species (ROS) - including the highly damaging hydroxyl radical ( rad OH) - followed by inflammation and a variety of diseases. While past studies have found correlations between ROS formation and a variety of metals, there are no quantitative measurements of rad OH formation from transition metals at concentrations relevant to 24-hour ambient particulate exposure. This research reports specific and quantitative measurements of rad OH formation from 10 individual transition metals (and several mixtures) in a cell-free surrogate lung fluid (SLF) with four antioxidants: ascorbate, citrate, glutathione, and uric acid. We find that Fe and Cu can produce rad OH under all antioxidant conditions as long as ascorbate is present and that mixtures of the two metals synergistically increase rad OH production. Manganese and vanadium can also produce rad OH under some conditions, but given that their ambient levels are typically very low, these metals are not likely to chemically produce significant levels of rad OH in the lung fluid. Cobalt, chromium, nickel, zinc, lead, and cadmium do not produce rad OH under any of our experimental conditions. The antioxidant composition of our SLF significantly affects rad OH production from Fe and Cu: ascorbate is required for rad OH formation, citrate increases rad OH production from Fe, and both citrate and glutathione suppress rad OH production from Cu. MINTEQ ligand speciation modeling indicates that citrate and glutathione affect rad OH production by changing metal speciation, altering the reactivity of the metals. In the most realistic SLF (i.e., with all four antioxidants), Fe generates approximately six times more rad OH than does the equivalent amount of Cu. Since levels of soluble Fe in PM are typically higher than those of Cu, our results suggest that Fe dominates the chemical generation of rad OH from deposited particles in the lungs.

A Synthetic Single-Site Fe Nitrogenase: High Turnover, Freeze-Quench (57)Fe Mössbauer Data, and a Hydride Resting State.

PubMed

Del Castillo, Trevor J; Thompson, Niklas B; Peters, Jonas C

2016-04-27

The mechanisms of the few known molecular nitrogen-fixing systems, including nitrogenase enzymes, are of much interest but are not fully understood. We recently reported that Fe-N2 complexes of tetradentate P3(E) ligands (E = B, C) generate catalytic yields of NH3 under an atmosphere of N2 with acid and reductant at low temperatures. Here we show that these Fe catalysts are unexpectedly robust and retain activity after multiple reloadings. Nearly an order of magnitude improvement in yield of NH3 for each Fe catalyst has been realized (up to 64 equiv of NH3 produced per Fe for P3(B) and up to 47 equiv for P3(C)) by increasing acid/reductant loading with highly purified acid. Cyclic voltammetry shows the apparent onset of catalysis at the P3(B)Fe-N2/P3(B)Fe-N2(-) couple and controlled-potential electrolysis of P3(B)Fe(+) at -45 °C demonstrates that electrolytic N2 reduction to NH3 is feasible. Kinetic studies reveal first-order rate dependence on Fe catalyst concentration (P3(B)), consistent with a single-site catalyst model. An isostructural system (P3(Si)) is shown to be appreciably more selective for hydrogen evolution. In situ freeze-quench Mössbauer spectroscopy during turnover reveals an iron-borohydrido-hydride complex as a likely resting state of the P3(B)Fe catalyst system. We postulate that hydrogen-evolving reaction activity may prevent iron hydride formation from poisoning the P3(B)Fe system. This idea may be important to consider in the design of synthetic nitrogenases and may also have broader significance given that intermediate metal hydrides and hydrogen evolution may play a key role in biological nitrogen fixation.

Superconductor-insulator quantum phase transition in disordered FeSe thin films.

PubMed

Schneider, R; Zaitsev, A G; Fuchs, D; V Löhneysen, H

2012-06-22

The evolution of two-dimensional electronic transport with increasing disorder in epitaxial FeSe thin films is studied. Disorder is generated by reducing the film thickness. The extreme sensitivity of the films to disorder results in a superconductor-insulator transition. The finite-size scaling analysis in the critical regime based on the Bose-glass model strongly supports the idea of a continuous quantum phase transition. The obtained value for the critical-exponent product of approximately 7/3 suggests that the transition is governed by quantum percolation. Finite-size scaling with the same critical-exponent product is also substantiated when the superconductor-insulator transition is tuned with an applied magnetic field.

Resonant Hall effect under generation of a self-sustaining mode of spin current in nonmagnetic bipolar conductors with identical characters between holes and electrons

NASA Astrophysics Data System (ADS)

Sakai, Masamichi; Takao, Hiraku; Matsunaga, Tomoyoshi; Nishimagi, Makoto; Iizasa, Keitaro; Sakuraba, Takahito; Higuchi, Koji; Kitajima, Akira; Hasegawa, Shigehiko; Nakamura, Osamu; Kurokawa, Yuichiro; Awano, Hiroyuki

2018-03-01

We have proposed an enhancement mechanism of the Hall effect, the signal of which is amplified due to the generation of a sustaining mode of spin current. Our analytic derivations of the Hall resistivity revealed the conditions indispensable for the observation of the effect: (i) the presence of the transverse component of an effective electric field due to spin splitting in chemical potential in addition to the longitudinal component; (ii) the simultaneous presence of holes and electrons each having approximately the same characteristics; (iii) spin-polarized current injection from magnetized electrodes; (iv) the boundary condition for the transverse current (J c, y = 0). The model proposed in this study was experimentally verified by using van der Pauw-type Hall devices consisting of the nonmagnetic bipolar conductor YH x (x ≃ 2) and TbFeCo electrodes. Replacing Au electrodes with TbFeCo electrodes alters the Hall resistivity from the ordinary Hall effect to the anomalous Hall-like effect with an enhancement factor of approximately 50 at 4 T. We interpreted the enhancement phenomenon in terms of the present model.

Virtual reality simulators: valuable surgical skills trainers or video games?

PubMed

Willis, Ross E; Gomez, Pedro Pablo; Ivatury, Srinivas J; Mitra, Hari S; Van Sickle, Kent R

2014-01-01

Virtual reality (VR) and physical model (PM) simulators differ in terms of whether the trainee is manipulating actual 3-dimensional objects (PM) or computer-generated 3-dimensional objects (VR). Much like video games (VG), VR simulators utilize computer-generated graphics. These differences may have profound effects on the utility of VR and PM training platforms. In this study, we aimed to determine whether a relationship exists between VR, PM, and VG platforms. VR and PM simulators for laparoscopic camera navigation ([LCN], experiment 1) and flexible endoscopy ([FE] experiment 2) were used in this study. In experiment 1, 20 laparoscopic novices played VG and performed 0° and 30° LCN exercises on VR and PM simulators. In experiment 2, 20 FE novices played VG and performed colonoscopy exercises on VR and PM simulators. In both experiments, VG performance was correlated with VR performance but not with PM performance. Performance on VR simulators did not correlate with performance on respective PM models. VR environments may be more like VG than previously thought. © 2013 Published by Association of Program Directors in Surgery on behalf of Association of Program Directors in Surgery.

Characterization of a tricationic trigonal bipyramidal iron(IV) cyanide complex, with a very high reduction potential, and its iron(II) and iron(III) congeners.

PubMed

England, Jason; Farquhar, Erik R; Guo, Yisong; Cranswick, Matthew A; Ray, Kallol; Münck, Eckard; Que, Lawrence

2011-04-04

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of nonheme oxygen activating enzymes. The trigonal bipyramidal complex [Fe(IV)(O)(TMG(3)tren)](2+) (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG(3)tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [Fe(IV)(CN)(TMG(3)tren)](3+) (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [Fe(II)(CN)(TMG(3)tren)](+) (2), via the S = 5/2 complex [Fe(III)(CN)(TMG(3)tren)](2+) (3), the progress of which was conveniently monitored by using UV-vis spectroscopy to follow the growth of bathochromically shifting ligand-to-metal charge transfer (LMCT) bands. A combination of X-ray absorption spectroscopy (XAS), Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, extended X-ray absorption fine structure (EXAFS) analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an Fe(IV/III) reduction potential of ∼1.4 V vs Fc(+/o), the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t(1/2) in CD(3)CN solution containing 0.1 M KPF(6) at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to (13)C NMR at -40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG(3)tren ligand to support highly charged high-valent complexes.

Characterization of a Tricationic Trigonal Bipyramidal Iron(IV) Cyanide Complex, with a Very High Reduction Potential, and Its Iron(II) and Iron(III) Congeners

PubMed Central

England, Jason; Farquhar, Erik R.; Guo, Yisong; Cranswick, Matthew A.; Ray, Kallol

2011-01-01

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of non-heme oxygen activating enzymes. The trigonal bipyramidal complex [FeIV(O)(TMG3tren)]2+ (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG3tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [FeIV(CN)(TMG3tren)]3+ (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [FeII(CN)(TMG3tren)]+ (2), via the S = 5/2 complex [FeIII(CN)(TMG3tren)]2+ (3), the progress of which was conveniently monitored by using UV-Vis spectroscopy to follow the growth of bathochromically shifting LMCT bands. A combination of XAS, Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, EXAFS analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an FeIV/III reduction potential of ~1.4 V vs Fc+/o, the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t1/2 in CD3CN solution containing 0.1 M KPF6 at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to 13C NMR at −40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG3tren ligand to support highly charged high-valent complexes. PMID:21381646

The interactive biotic and abiotic processes of DDT transformation under dissimilatory iron-reducing conditions.

PubMed

Jin, Xin; Wang, Fang; Gu, Chenggang; Yang, Xinglun; Kengara, Fredrick O; Bian, Yongrong; Song, Yang; Jiang, Xin

2015-11-01

The objective of the study was to elucidate the biotic and abiotic processes under dissimilatory iron reducing conditions involved in reductive dechlorination and iron reduction. DDT transformation was investigated in cultures of Shewanella putrefaciens 200 with/without α-FeOOH. A modified first-order kinetics model was developed and described DDT transformation well. Both the α-FeOOH reduction rate and the dechlorination rate of DDT were positively correlated to the biomass. Addition of α-FeOOH enhanced reductive dechlorination of DDT by favoring the cell survival and generating Fe(II) which was absorbed on the surface of bacteria and iron oxide. 92% of the absorbed Fe(II) was Na-acetate (1M) extractable. However, α-FeOOH also played a negative role of competing for electrons as reflected by the dechlorination rate of DDT was inhibited when increasing the α-FeOOH from 1 g L(-1) to 5 g L(-1). DDT was measured to be toxic to S. putrefaciens 200. The metabolites DDD, DDE and DDMU were recalcitrant to S. putrefaciens 200. The results suggested that iron oxide was not the key factor to promote the dissipation of DDX (DDT and the metabolites), whereas the one-electron reduction potential (E1) of certain organochlorines is the main factor and that the E1 higher than the threshold of the reductive driving forces of DIRB probably ensures the occur of reductive dechlorination. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fine-structure excitation of Fe II and Fe III due to collisions with electrons

NASA Astrophysics Data System (ADS)

Wan, Yier; Qi, Yueying; Favreau, Connor; Loch, Stuart; Stancil, P.; Ballance, Connor; McLaughlin, Brendan

2018-06-01

Atomic data of iron peak elements are of great importance in astronomical observations. Among all the ionization stages of iron, Fe II and Fe III are of particular importance because of the high cosmic abundance, relatively low ionization potential and complex open d-shell atomic structure. Fe II and Fe III emission are observed from nearly all classes of astronomical objects over a wide spectral range from the infrared to the ultraviolet. To meaningfully interpret these spectra, astronomers have to employ highly complex modeling codes with reliable collision data to simulate the astrophysical observations. The major aim of this work is to provide reliable atomic data for diagnostics. We present new collision strengths and effective collisions for electron impact excitation of Fe II and Fe III for the forbidden transitions among the fine-structure levels of the ground terms. A very fine energy mesh is used for the collision strengths and the effective collision strengths are calculated over a wide range of electron temperatures of astrophysical importance (10-2000 K). The configuration interaction state wave functions are generated with a scaled Thomas-Fermi-Dirac-Amaldi (TFDA) potential, while the R-matrix plus intermediate coupling frame transformation (ICFT), Breit-Pauli R-matrix and Dirac R-matrix packages are used to obtain collision strengths. Influences of the different methods and configuration expansions on the collisional data are discussed. Comparison is made with earlier theoretical work and differences are found to occur at the low temperatures considered here.This work was funded by NASA grant NNX15AE47G.

Wiring photosystem I for direct solar hydrogen production.

PubMed

Lubner, Carolyn E; Grimme, Rebecca; Bryant, Donald A; Golbeck, John H

2010-01-26

The generation of H(2) by the use of solar energy is a promising way to supply humankind's energy needs while simultaneously mitigating environmental concerns that arise due to climate change. The challenge is to find a way to connect a photochemical module that harnesses the sun's energy to a catalytic module that generates H(2) with high quantum yields and rates. In this review, we describe a technology that employs a "molecular wire" to connect a terminal [4Fe-4S] cluster of Photosystem I directly to a catalyst, which can be either a Pt nanoparticle or the distal [4Fe-4S] cluster of an [FeFe]- or [NiFe]-hydrogenase enzyme. The keys to connecting these two moieties are surface-located cysteine residues, which serve as ligands to Fe-S clusters and which can be changed through site-specific mutagenesis to glycine residues, and the use of a molecular wire terminated in sulfhydryl groups to connect the two modules. The sulfhydryl groups at the end of the molecular wire form a direct chemical linkage to a suitable catalyst or can chemically rescue a [4Fe-4S] cluster, thereby generating a strong coordination bond. Specifically, the molecular wire can connect the F(B) iron-sulfur cluster of Photosystem I either to a Pt nanoparticle or, by using the same type of genetic modification, to the differentiated iron atom of the distal [4Fe-4S].(Cys)(3)(Gly) cluster of hydrogenase. When electrons are supplied by a sacrificial donor, this technology forms the cathode of a photochemical half-cell that evolves H(2) when illuminated. If such a device were connected to the anode of a photochemical half-cell that oxidizes water, an in vitro solar energy converter could be realized that generates only O(2) and H(2) in the light. A similar methodology can be used to connect Photosystem I to other redox proteins that have surface-located [4Fe-4S] clusters. The controlled light-driven production of strong reductants by such systems can be used to produce other biofuels or to provide mechanistic insights into enzymes catalyzing multielectron, proton-coupled reactions.

Meshing of a Spiral Bevel Gearset with 3D Finite Element Analysis

NASA Technical Reports Server (NTRS)

Bibel, George D.; Handschuh, Robert

1996-01-01

Recent advances in spiral bevel gear geometry and finite element technology make it practical to conduct a structural analysis and analytically roll the gearset through mesh. With the advent of user specific programming linked to 3D solid modelers and mesh generators, model generation has become greatly automated. Contact algorithms available in general purpose finite element codes eliminate the need for the use and alignment of gap elements. Once the gearset is placed in mesh, user subroutines attached to the FE code easily roll the gearset through mesh. The method is described in detail. Preliminary results for a gearset segment showing the progression of the contact lineload is given as the gears roll through mesh.

Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination

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

Thacker, Nathan C.; Ji, Pengfei; Lin, Zekai

2017-01-01

We report here the synthesis of a robust and highly porous Fe-phenanthroline-based metal–organic framework (MOF) and its application in catalyzing challenging inter- and intramolecular C–H amination reactions. For the intermolecular amination reactions, a FeBr 2-metalated MOF selectively functionalized secondary benzylic and allylic C–H bonds. The intramolecular amination reactions utilizing organic azides as the nitrene source required the reduction of the FeBr 2-metalated MOF with NaBHEt 3to generate the active catalyst. For both reactions, Fe or Zr leaching was less than 0.1%, and MOFs could be recycled and reused with no loss in catalytic activity. Furthermore, MOF catalysts were significantly moremore » active than the corresponding homogeneous analogs. This work demonstrates the great potential of MOFs in generating highly active, recyclable, and reusable earth abundant metal catalysts for challenging organic transformations.« less

Development of new vibration energy flow analysis software and its applications to vehicle systems

NASA Astrophysics Data System (ADS)

Kim, D.-J.; Hong, S.-Y.; Park, Y.-H.

2005-09-01

The Energy flow analysis (EFA) offers very promising results in predicting the noise and vibration responses of system structures in medium-to-high frequency ranges. We have developed the Energy flow finite element method (EFFEM) based software, EFADSC++ R4, for the vibration analysis. The software can analyze the system structures composed of beam, plate, spring-damper, rigid body elements and many other components developed, and has many useful functions in analysis. For convenient use of the software, the main functions of the whole software are modularized into translator, model-converter, and solver. The translator module makes it possible to use finite element (FE) model for the vibration analysis. The model-converter module changes FE model into energy flow finite element (EFFE) model, and generates joint elements to cover the vibrational attenuation in the complex structures composed of various elements and can solve the joint element equations by using the wave tra! nsmission approach very quickly. The solver module supports the various direct and iterative solvers for multi-DOF structures. The predictions of vibration for real vehicles by using the developed software were performed successfully.

Minor element distribution in iron disulfides in coal: a geochemical review

USGS Publications Warehouse

Kolker, Allan

2012-01-01

Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.

Effect of low-molecular-weight organic acids on photo-degradation of phenanthrene catalyzed by Fe(III)-smectite under visible light.

PubMed

Jia, Hanzhong; Chen, Hongxia; Nulaji, Gulimire; Li, Xiyou; Wang, Chuanyi

2015-11-01

The photolysis of polycyclic aromatic hydrocarbons (PAHs) is potentially an important process for its transformation and fate on contaminated soil surfaces. In this study, phenanthrene is employed as a model to explore PAH photodegradation with the assistance of Fe(III)-smectite under visible-light while focusing on roles played by five low-molecular-weight organic acids (LMWOAs), i.e., malic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid. Our results show that oxalic acid is most effective in promoting the photodegradation of phenanthrene, while only a slight increase in the rate of phenanthrene photodegradation is observed in the presence of malic acid. Electron paramagnetic resonance experiments confirm the formation of CO2(-) radicals in the presence of malic and oxalic acid, which provides strong evidence for generating OH and subsequent photoreaction pathways. The presence of EDTA or nitrilotriacetic acid significantly inhibits both Fe(II) formation and phenanthrene photodegradation because these organic anions tend to chelate with Fe(III), leading to decreases in the electron-accepting potential of Fe(III)-smectite and a weakened interaction between phenanthrene and Fe(III)-smectite. These observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and demonstrate the potential for using some LMWOAs as additives for the remediation of contaminated soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Investigation of pulmonary acoustic simulation: comparing airway model generation techniques

NASA Astrophysics Data System (ADS)

Henry, Brian; Dai, Zoujun; Peng, Ying; Mansy, Hansen A.; Sandler, Richard H.; Royston, Thomas

2014-03-01

Alterations in the structure and function of the pulmonary system that occur in disease or injury often give rise to measurable spectral, spatial and/or temporal changes in lung sound production and transmission. These changes, if properly quantified, might provide additional information about the etiology, severity and location of trauma, injury, or pathology. With this in mind, the authors are developing a comprehensive computer simulation model of pulmonary acoustics, known as The Audible Human Project™. Its purpose is to improve our understanding of pulmonary acoustics and to aid in interpreting measurements of sound and vibration in the lungs generated by airway insonification, natural breath sounds, and external stimuli on the chest surface, such as that used in elastography. As a part of this development process, finite element (FE) models were constructed of an excised pig lung that also underwent experimental studies. Within these models, the complex airway structure was created via two methods: x-ray CT image segmentation and through an algorithmic means called Constrained Constructive Optimization (CCO). CCO was implemented to expedite the segmentation process, as airway segments can be grown digitally. These two approaches were used in FE simulations of the surface motion on the lung as a result of sound input into the trachea. Simulation results were compared to experimental measurements. By testing how close these models are to experimental measurements, we are evaluating whether CCO can be used as a means to efficiently construct physiologically relevant airway trees.

Socioeconomic and Sociodemographic Factors Associated with Asthma Related Outcomes in Early Childhood: The Generation R Study

PubMed Central

Hafkamp-de Groen, Esther; Sonnenschein-van der Voort, Agnes M. M.; Mackenbach, Johan P.; Duijts, Liesbeth; Jaddoe, Vincent W. V.; Moll, Henriëtte A.; Hofman, Albert; de Jongste, Johan C.; Raat, Hein

2013-01-01

Rationale Few studies have analyzed the association of socioeconomic and sociodemographic factors with asthma related outcomes in early childhood, including Fraction of exhaled Nitric Oxide (FeNO) and airway resistance (Rint). We examined the association of socioeconomic and sociodemographic factors with wheezing, asthma, FeNO and Rint at age 6 years. Additionally, the role of potential mediating factors was studied. Methods The study included 6717 children participating in The Generation R Study, a prospective population-based cohort study. Data on socioeconomic and sociodemographic factors, wheezing and asthma were obtained by questionnaires. FeNO and Rint were measured at the research center. Statistical analyses were performed using logistic and linear regression models. Results At age 6 years, 9% (456/5084) of the children had wheezing symptoms and 7% (328/4953) had asthma. Children from parents with financial difficulties had an increased risk of wheezing (adjusted Odds Ratio (aOR) = 1.63, 95% Confidence Interval (CI):1.18–2.24). Parental low education, paternal unemployment and child's male sex were associated with asthma, independent of other socioeconomic or sociodemographic factors (aOR = 1.63, 95% CI:1.24–2.15, aOR = 1.85, 95% CI:1.11–3.09, aOR = 1.58, 95% CI:1.24–2.01, respectively). No socioeconomic or gender differences in FeNO were found. The risks of wheezing, asthma, FeNO and Rint measurements differed between ethnic groups (p<0.05). Associations between paternal unemployment, child's sex, ethnicity and asthma related outcomes remained largely unexplained. Conclusions This study showed differences between the socioeconomic and sociodemographic correlates of wheezing and asthma compared to the correlates of FeNO and Rint at age 6 years. Several socioeconomic and sociodemographic factors were independently associated with wheezing and asthma. Child's ethnicity was the only factor independently associated with FeNO. We encourage further studies on underlying pathways and public health intervention programs, focusing on reducing socioeconomic or sociodemographic inequalities in asthma. PMID:24244299

Tooth fracture risk analysis based on a new finite element dental structure models using micro-CT data.

PubMed

Chen, G; Fan, W; Mishra, S; El-Atem, A; Schuetz, M A; Xiao, Y

2012-10-01

The finite element (FE) analysis is an effective method to study the strength and predict the fracture risk of endodontically-treated teeth. This paper presents a rapid method developed to generate a comprehensive tooth FE model using data retrieved from micro-computed tomography (μCT). With this method, the inhomogeneity of material properties of teeth was included into the model without dividing the tooth model into different regions. The material properties of the tooth were assumed to be related to the mineral density. The fracture risk at different tooth portions was assessed for root canal treatments. The micro-CT images of a tooth were processed by a Matlab software programme and the CT numbers were retrieved. The tooth contours were obtained with thresholding segmentation using Amira. The inner and outer surfaces of the tooth were imported into Solidworks and a three-dimensional (3D) tooth model was constructed. An assembly of the tooth model with the periodontal ligament (PDL) layer and surrounding bone was imported into ABAQUS. The material properties of the tooth were calculated from the retrieved CT numbers via ABAQUS user's subroutines. Three root canal geometries (original and two enlargements) were investigated. The proposed method in this study can generate detailed 3D finite element models of a tooth with different root canal enlargements and filling materials, and would be very useful for the assessment of the fracture risk at different tooth portions after root canal treatments. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Heat generation of surface-modified magnetic γ-Fe2O3 nanoparticles in applied alternating magnetic field

NASA Astrophysics Data System (ADS)

Babič, Michal; Horák, Daniel; Molčan, Matúš; Timko, Milan

2017-08-01

In this report, we show preparation of colloidally stable poly(N,N-dimethylacrylamide-co-acrylic acid) (DMA)- and D-mannose (MAN)-coated maghemite nanoparticles and their ability to generate heat in an alternating magnetic field, which could make the particles applicable for hyperthermic therapy of cancer. The particles are obtained by coprecipitation reaction and characterized by transmission electron microscopy, dynamic light scattering, and AC calorimetric measurement of heat generated by the particles. While the dry particles were ca. 10 nm in diameter, their hydrodynamic size in water was within the range of 100 nm. Heating characteristics were measured in an LC circuit with a maximum field intensity of 6.8 kA · m-1 and frequency 190 kHz. The specific absorption rates of γ-Fe2O3, PDM@γ-Fe2O3, and MAN@γ-Fe2O3 nanoparticles were extrapolated to 10 kA · m-1, reaching about 15 W · g-1.

Assessing the link between recent supernovae near Earth and the iron-60 anomaly in a deep-sea crust

NASA Astrophysics Data System (ADS)

Schulreich, Michael M.; Breitschwerdt, Dieter

2016-06-01

Some time ago, an enhanced concentration of the radionuclide 60Fe was discovered in a deep-sea ferromanganese crust, isolated in layers dating from about 2.2, Myr ago. Since 60Fe (half-life of 2.6, Myr) is not naturally produced on Earth, such an excess can only be attributed to extraterrestrial sources, particularly one or several nearby supernovae in the recent past. It has been speculated that these supernovae might have been involved in the formation of the Local Superbubble, our Galactic habitat. The aim of this talk is to provide a quantitative evidence for this scenario. For that purpose, I will present results from high-resolution hydrodynamical simulations of the Local Superbubble and its neighbour Loop I in different environments, including a self-consistently evolved supernova-driven interstellar medium. For the superbubble modelling, the time sequence and locations of the generating core-collapse supernova explosions are taken into account, which are derived from the mass spectrum of the perished members of certain, carefully preselected stellar moving groups. The release and turbulent mixing of 60Fe is followed via passive scalars, where the yields of the decaying radioisotope were adjusted according to recent stellar evolution calculations. The models are able to reproduce both the timing and the intensity of the 60Fe excess observed with rather high precision.

Characterization of a heterobimetallic nonheme Fe(III)-O-Cr(III) species formed by O2 activation.

PubMed

Zhou, Ang; Kleespies, Scott T; Van Heuvelen, Katherine M; Que, Lawrence

2015-10-01

We report the generation and spectroscopic characterization of a heterobimetallic [(TMC)Fe(III)-O-Cr(III)(OTf)4] species (1) by bubbling O2 into a mixture of Fe(TMC)(OTf)2 and Cr(OTf)2 in NCCH3. Complex 1 also formed quantitatively by adding Cr(OTf)2 to [Fe(IV)(O)(TMC)(NCCH3)](2+). The proposed O2 activation mechanism involves the trapping of a Cr-O2 adduct by Fe(TMC)(OTf)2.

Characterization of a Heterobimetallic Nonheme Fe(III)-O-Cr(III) Species Formed by O2 Activation

PubMed Central

Zhou, Ang; Kleespies, Scott T.; Van Heuvelen, Katherine M.; Que, Lawrence

2015-01-01

We report the generation and spectroscopic characterization of a heterobimetallic [(TMC)FeIII-O-CrIII(OTf)4] species (1) by O2 bubbling into a mixture of Fe(TMC)(OTf)2 and Cr(OTf)2 in NCCH3. Complex 1 also formed quantitatively by adding Cr(OTf)2 to [FeIV(O)(TMC)(NCCH3)]2+. The proposed O2 activation mechanism involves the trapping by a Cr-O2 adduct by Fe(TMC)(OTf)2. PMID:26265081

Triple point fcc-hcp-liquid in the Fe phase diagram determined by in-situ XANES diagnostic and post-mortem XRD and FIB-SEM analysis.

NASA Astrophysics Data System (ADS)

Morard, G.; Boccato, S.; Rosa, A. D.; Anzellini, S.; Miozzi Ferrini, F.; Laura, H.; Garbarino, G.; Harmand, M.; Guyot, F. J.; Boulard, E.; Kantor, I.; Irifune, T.; Torchio, R.

2017-12-01

Iron is the main constituent of planetary cores. Studying its phase diagram under high pressure is necessary to constrain properties of planetary interiors, and to model key parameters such as the generation of magnetic field. Though, strong controversy on the melting curve of pure Fe still remains. Recently, Aquilanti et al, (PNAS, 2015) reported a Fe melting curved based on XANES measurements which is in open disagreement with previous X-ray diffraction results (Anzellini et al, Science, 2013). Discrepancies in the melting temperature exceed several hundred degrees close to Mbar pressures, which may be related to differences in temperature measurement techniques, melting diagnostics, or to chemical reactions of the sample with the surrounding medium. We therefore performed new in situ high P/T XANES experiments on pure Fe (up to 115 GPa and 4000 K) at the ESRF beamline ID24, combining the energy dispersive absorption set up with laser heated diamond anvil cells. X-ray diffraction maps were collected from all recovered samples in order to identify and characterize laser-heated spots. The XANES melting criterion was further cross checked by analyzing the recovered sample textures using FIB cutting techniques and SEM imaging. We found systematically that low melting temperatures are related to the presence of Fe3C, implying that in those cases chemical reactions occurred during heating resulting in carbon contamination from the diamonds. These low melting points fall onto the melting line reported by Aquilanti et al, (2015). Uncontaminated points are in agreement with the melting curve of Anzellini et al, (2013) within their uncertainties. Moreover, this data set allowed us to refine the location of the triple point in the Fe phase diagram at 105 (±10) GPa and 3600 (±200) K, which may imply a small kink in the melting curve around this point. This refined Fe phase diagram could be then used to compute thermodynamic models for planetary cores.

Numerical studies on the link between radioisotopic signatures on Earth and the formation of the Local Bubble. I. 60Fe transport to the solar system by turbulent mixing of ejecta from nearby supernovae into a locally homogeneous interstellar medium

NASA Astrophysics Data System (ADS)

Schulreich, M. M.; Breitschwerdt, D.; Feige, J.; Dettbarn, C.

2017-08-01

Context. The discovery of radionuclides like 60Fe with half-lives of million years in deep-sea crusts and sediments offers the unique possibility to date and locate nearby supernovae. Aims: We want to quantitatively establish that the 60Fe enhancement is the result of several supernovae which are also responsible for the formation of the Local Bubble, our Galactic habitat. Methods: We performed three-dimensional hydrodynamic adaptive mesh refinement simulations (with resolutions down to subparsec scale) of the Local Bubble and the neighbouring Loop I superbubble in different homogeneous, self-gravitating environments. For setting up the Local and Loop I superbubble, we took into account the time sequence and locations of the generating core-collapse supernova explosions, which were derived from the mass spectrum of the perished members of certain stellar moving groups. The release of 60Fe and its subsequent turbulent mixing process inside the superbubble cavities was followed via passive scalars, where the yields of the decaying radioisotope were adjusted according to recent stellar evolution calculations. Results: The models are able to reproduce both the timing and the intensity of the 60Fe excess observed with rather high precision, provided that the external density does not exceed 0.3 cm-3 on average. Thus the two best-fit models presented here were obtained with background media mimicking the classical warm ionised and warm neutral medium. We also found that 60Fe (which is condensed onto dust grains) can be delivered to Earth via two physical mechanisms: either through individual fast-paced supernova blast waves, which cross the Earth's orbit sometimes even twice as a result of reflection from the Local Bubble's outer shell, or, alternatively, through the supershell of the Local Bubble itself, injecting the 60Fe content of all previous supernovae at once, but over a longer time range.

Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor.

PubMed

Li, Yue; Machala, Libor; Yan, Weile

2016-02-02

Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

A statistical motion model based on biomechanical simulations for data fusion during image-guided prostate interventions.

PubMed

Hu, Yipeng; Morgan, Dominic; Ahmed, Hashim Uddin; Pendsé, Doug; Sahu, Mahua; Allen, Clare; Emberton, Mark; Hawkes, David; Barratt, Dean

2008-01-01

A method is described for generating a patient-specific, statistical motion model (SMM) of the prostate gland. Finite element analysis (FEA) is used to simulate the motion of the gland using an ultrasound-based 3D FE model over a range of plausible boundary conditions and soft-tissue properties. By applying principal component analysis to the displacements of the FE mesh node points inside the gland, the simulated deformations are then used as training data to construct the SMM. The SMM is used to both predict the displacement field over the whole gland and constrain a deformable surface registration algorithm, given only a small number of target points on the surface of the deformed gland. Using 3D transrectal ultrasound images of the prostates of five patients, acquired before and after imposing a physical deformation, to evaluate the accuracy of predicted landmark displacements, the mean target registration error was found to be less than 1.9 mm.

Using SpaceClaimTD Direct for Modeling Components with Complex Geometries for the Thermal Desktop-Based Advanced Stirling Radioisotope Generator Model

NASA Technical Reports Server (NTRS)

Fabanich, William A., Jr.

2014-01-01

SpaceClaim/TD Direct has been used extensively in the development of the Advanced Stirling Radioisotope Generator (ASRG) thermal model. This paper outlines the workflow for that aspect of the task and includes proposed best practices and lessons learned. The ASRG thermal model was developed to predict component temperatures and power output and to provide insight into the prime contractor's thermal modeling efforts. The insulation blocks, heat collectors, and cold side adapter flanges (CSAFs) were modeled with this approach. The model was constructed using mostly TD finite difference (FD) surfaces/solids. However, some complex geometry could not be reproduced with TD primitives while maintaining the desired degree of geometric fidelity. Using SpaceClaim permitted the import of original CAD files and enabled the defeaturing/repair of those geometries. TD Direct (a SpaceClaim add-on from CRTech) adds features that allowed the "mark-up" of that geometry. These so-called "mark-ups" control how finite element (FE) meshes are to be generated through the "tagging" of features (e.g. edges, solids, surfaces). These tags represent parameters that include: submodels, material properties, material orienters, optical properties, and radiation analysis groups. TD aliases were used for most tags to allow analysis to be performed with a variety of parameter values. "Domain-tags" were also attached to individual and groups of surfaces and solids to allow them to be used later within TD to populate objects like, for example, heaters and contactors. These tools allow the user to make changes to the geometry in SpaceClaim and then easily synchronize the mesh in TD without having to redefine the objects each time as one would if using TDMesher. The use of SpaceClaim/TD Direct helps simplify the process for importing existing geometries and in the creation of high fidelity FE meshes to represent complex parts. It also saves time and effort in the subsequent analysis.

Using SpaceClaim/TD Direct for Modeling Components with Complex Geometries for the Thermal Desktop-Based Advanced Stirling Radioisotope Generator Model

NASA Technical Reports Server (NTRS)

Fabanich, William

2014-01-01

SpaceClaim/TD Direct has been used extensively in the development of the Advanced Stirling Radioisotope Generator (ASRG) thermal model. This paper outlines the workflow for that aspect of the task and includes proposed best practices and lessons learned. The ASRG thermal model was developed to predict component temperatures and power output and to provide insight into the prime contractors thermal modeling efforts. The insulation blocks, heat collectors, and cold side adapter flanges (CSAFs) were modeled with this approach. The model was constructed using mostly TD finite difference (FD) surfaces solids. However, some complex geometry could not be reproduced with TD primitives while maintaining the desired degree of geometric fidelity. Using SpaceClaim permitted the import of original CAD files and enabled the defeaturing repair of those geometries. TD Direct (a SpaceClaim add-on from CRTech) adds features that allowed the mark-up of that geometry. These so-called mark-ups control how finite element (FE) meshes were generated and allowed the tagging of features (e.g. edges, solids, surfaces). These tags represent parameters that include: submodels, material properties, material orienters, optical properties, and radiation analysis groups. TD aliases were used for most tags to allow analysis to be performed with a variety of parameter values. Domain-tags were also attached to individual and groups of surfaces and solids to allow them to be used later within TD to populate objects like, for example, heaters and contactors. These tools allow the user to make changes to the geometry in SpaceClaim and then easily synchronize the mesh in TD without having to redefine these objects each time as one would if using TD Mesher.The use of SpaceClaim/TD Direct has helped simplify the process for importing existing geometries and in the creation of high fidelity FE meshes to represent complex parts. It has also saved time and effort in the subsequent analysis.

Negative Capacitance in BaTiO3/BiFeO3 Bilayer Capacitors.

PubMed

Hou, Ya-Fei; Li, Wei-Li; Zhang, Tian-Dong; Yu, Yang; Han, Ren-Lu; Fei, Wei-Dong

2016-08-31

Negative capacitances provide an approach to reduce heat generations in field-effect transistors during the switch processes, which contributes to further miniaturization of the conventional integrated circuits. Although there are many studies about negative capacitances using ferroelectric materials, the direct observation of stable ferroelectric negative capacitances has rarely been reported. Here, we put forward a dc bias assistant model in bilayer capacitors, where one ferroelectric layer with large dielectric constant and the other ferroelectric layer with small dielectric constant are needed. Negative capacitances can be obtained when external dc bias electric fields are larger than a critical value. Based on the model, BaTiO3/BiFeO3 bilayer capacitors are chosen as study objects, and negative capacitances are observed directly. Additionally, the upward self-polarization effect in the ferroelectric layer reduces the critical electric field, which may provide a method for realizing zero and/or small dc bias assistant negative capacitances.

Superoxide reductase from the syphilis spirochete Treponema pallidum: crystallization and structure determination using soft X-rays

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

Santos-Silva, Teresa; Trincão, José; Carvalho, Ana L.

2005-11-01

Superoxide reductase is a non-haem iron-containing protein involved in resistance to oxidative stress. The oxidized form of the protein has been crystallized and its three-dimensional structure solved. A highly redundant X-ray diffraction data set was collected on a rotating-anode generator using Cu Kα X-ray radiation. Four Fe atoms were located in the asymmetric unit corresponding to four protein molecules arranged as a dimer of homodimers. Superoxide reductase is a 14 kDa metalloprotein containing a catalytic non-haem iron centre [Fe(His){sub 4}Cys]. It is involved in defence mechanisms against oxygen toxicity, scavenging superoxide radicals from the cell. The oxidized form of Treponemamore » pallidum superoxide reductase was crystallized in the presence of polyethylene glycol and magnesium chloride. Two crystal forms were obtained depending on the oxidizing agents used after purification: crystals grown in the presence of K{sub 3}Fe(CN){sub 6} belonged to space group P2{sub 1} (unit-cell parameters a = 60.3, b = 59.9, c = 64.8 Å, β = 106.9°) and diffracted beyond 1.60 Å resolution, while crystals grown in the presence of Na{sub 2}IrCl{sub 6} belonged to space group C2 (a = 119.4, b = 60.1, c = 65.6 Å, β = 104.9°) and diffracted beyond 1.55 Å. A highly redundant X-ray diffraction data set from the C2 crystal form collected on a copper rotating-anode generator (λ = 1.542 Å) clearly defined the positions of the four Fe atoms present in the asymmetric unit by SAD methods. A MAD experiment at the iron absorption edge confirmed the positions of the previously determined iron sites and provided better phases for model building and refinement. Molecular replacement using the P2{sub 1} data set was successful using a preliminary trace as a search model. A similar arrangement of the four protein molecules could be observed.« less

Renewable Bio-Solar Hydrogen Production: The Second Generation (Part C)

DTIC Science & Technology

2014-11-28

enzymes in the green alga Chlamydomonas reinhardtii, (b) increasing the levels of algal cellular starch , (c) understanding the mechanism of [FeFe... starch hyperaccumulation in Chlamydomonas reinhardtii, which can be used to make a variety of glucose based products. The Nannochloropsis genus of...Another significant advance was the generation of starch hyperaccumulating mutants. By overexpressing the isoamlyase gene in Chlamydomonas, central

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

PubMed

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

Electro-optically Induced and Manipulated Terahertz Waves from Fe-doped InGaAs Surfaces

NASA Astrophysics Data System (ADS)

Hatem, O.

2018-03-01

We demonstrate the presence of dual simultaneous nonlinear mechanisms: field-induced optical rectification (FIOR) and field-induced surge current (FISC) for the generation of terahertz (THz) pulses from p-type and n-type Fe:In0.53Ga0.47As surfaces upon excitation with femtosecond laser pulses centered at 800 nm wavelength. Experimental investigations of the dependence of the generated THz waves on the incident angular optical polarization, optical irradiance, and the direction and magnitude of applied electric DC fields give confirming results to the proposed THz generation mechanisms. Applying external DC electric fields in the plane of the incident optical field shows efficient capability in manipulating the direction and phase of the generated THz waves, and controlling the refractive index of Fe:In0.53Ga0.47As material in the THz range, in addition to enhancing the emitted THz power up to two orders of magnitude. The fast and reliable response of Fe:In0.53Ga0.47As to the changes in the direction and magnitude of the optical and electrical fields suggests its use in amplitude and phase modulators, and ultrafast optoelectronic systems.

Mechanism of oxidative DNA damage induction in a strict anaerobe, Prevotella melaninogenica.

PubMed

Takeuchi, T; Kato, N; Watanabe, K; Morimoto, K

2000-11-01

We investigated the mechanism of the oxidative DNA damage induction by exposure to O(2) in Prevotella melaninogenica, a strict anaerobe. Flow cytometry with hydroethidine and dichlorofluorescein diacetate showed that O(2) exposure generated O(2)*-) and H(2)O(2). Results of electron spin resonance with alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone and ethanol showed that O(2) exposure also induced *OH radical generation in P. melaninogenica loaded with FeCl(2) but not in samples without FeCl(2) loading. In P. melaninogenica, O(2) exposure increased 8-hydroxydeoxyguanosine (8OHdG), typical of oxidative DNA damage. Catalase inhibited the increase, but the *OH radical scavengers did not. Phenanthroline, a membrane-permeable Fe and Cu chelator, increased the 8OHdG induction. In FeCl(2)-loaded samples, induction of 8OHdG decreased. Addition of H(2)O(2) markedly increased 8OHdG levels. These results indicate that in P. melaninogenica, exposure to O(2) generated and accumulated O(2)* and H(2)O(2), and that a crypto-OH radical generated through H(2)O(2) was the active species in the 8OHdG induction.

A multi-scale model of dislocation plasticity in α-Fe: Incorporating temperature, strain rate and non-Schmid effects

DOE PAGES

Lim, H.; Hale, L. M.; Zimmerman, J. A.; ...

2015-01-05

In this study, we develop an atomistically informed crystal plasticity finite element (CP-FE) model for body-centered-cubic (BCC) α-Fe that incorporates non-Schmid stress dependent slip with temperature and strain rate effects. Based on recent insights obtained from atomistic simulations, we propose a new constitutive model that combines a generalized non-Schmid yield law with aspects from a line tension (LT) model for describing activation enthalpy required for the motion of dislocation kinks. Atomistic calculations are conducted to quantify the non-Schmid effects while both experimental data and atomistic simulations are used to assess the temperature and strain rate effects. The parameterized constitutive equationmore » is implemented into a BCC CP-FE model to simulate plastic deformation of single and polycrystalline Fe which is compared with experimental data from the literature. This direct comparison demonstrates that the atomistically informed model accurately captures the effects of crystal orientation, temperature and strain rate on the flow behavior of siangle crystal Fe. Furthermore, our proposed CP-FE model exhibits temperature and strain rate dependent flow and yield surfaces in polycrystalline Fe that deviate from conventional CP-FE models based on Schmid's law.« less

Evolution of structural distortion in BiFeO3 thin films probed by second-harmonic generation

NASA Astrophysics Data System (ADS)

Jin, Kuijuan; Wang, Jiesu; Gu, Junxing; L03 Group in Institute of Physics, Chinese Academy of Sciences Team

BiFeO3 thin films have drawn much attention due to its potential applications for novel magnetoelectric devices and fundamental physics in magnetoelectric coupling. However, the structural evolution of BiFeO3 films with thickness remains controversial. Here we use an optical second-harmonic generation technique to explore the phase-related symmetry evolution of BiFeO3 thin films with the variation of thickness. The crystalline structures for 60 and 180-nm-thick BiFeO3 thin films were characterized by high-resolution X-ray diffractometry reciprocal space mapping and the local piezoelectric response for 60-nm-thick BiFeO3 thin films was characterized by piezoresponse force microscopy. The present results show that the symmetry of BiFeO3 thin films with a thickness below 60 nm belongs to the point group 4mm. We conclude that the disappearance of fourfold rotational symmetry in SHG s-out pattern implies for the appearance of R-phase. The fact that the thinner the film is, the closer to 1 the tensor element ratio χ31/ χ15 tends, indicates an increase of symmetry with the decrease of thickness for BiFeO3 thin films. email: kjjin@iphy.ac.cn

Analysis of the FeCrAl Accident Tolerant Fuel Concept Benefits during BWR Station Blackout Accidents

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

Robb, Kevin R

2015-01-01

Iron-chromium-aluminum (FeCrAl) alloys are being considered for fuel concepts with enhanced accident tolerance. FeCrAl alloys have very slow oxidation kinetics and good strength at high temperatures. FeCrAl could be used for fuel cladding in light water reactors and/or as channel box material in boiling water reactors (BWRs). To estimate the potential safety gains afforded by the FeCrAl concept, the MELCOR code was used to analyze a range of postulated station blackout severe accident scenarios in a BWR/4 reactor employing FeCrAl. The simulations utilize the most recently known thermophysical properties and oxidation kinetics for FeCrAl. Overall, when compared to the traditionalmore » Zircaloy-based cladding and channel box, the FeCrAl concept provides a few extra hours of time for operators to take mitigating actions and/or for evacuations to take place. A coolable core geometry is retained longer, enhancing the ability to stabilize an accident. Finally, due to the slower oxidation kinetics, substantially less hydrogen is generated, and the generation is delayed in time. This decreases the amount of non-condensable gases in containment and the potential for deflagrations to inhibit the accident response.« less

Evolution of structural distortion in BiFeO3 thin films probed by second-harmonic generation.

PubMed

Wang, Jie-Su; Jin, Kui-Juan; Guo, Hai-Zhong; Gu, Jun-Xing; Wan, Qian; He, Xu; Li, Xiao-Long; Xu, Xiu-Lai; Yang, Guo-Zhen

2016-12-01

BiFeO 3 thin films have drawn much attention due to its potential applications for novel magnetoelectric devices and fundamental physics in magnetoelectric coupling. However, the structural evolution of BiFeO 3 films with thickness remains controversial. Here we use an optical second-harmonic generation technique to explore the phase-related symmetry evolution of BiFeO 3 thin films with the variation of thickness. The crystalline structures for 60 and 180-nm-thick BiFeO 3 thin films were characterized by high-resolution X-ray diffractometry reciprocal space mapping and the local piezoelectric response for 60-nm-thick BiFeO 3 thin films was characterized by piezoresponse force microscopy. The present results show that the symmetry of BiFeO 3 thin films with a thickness below 60 nm belongs to the point group 4 mm. We conclude that the disappearance of fourfold rotational symmetry in SHG s-out pattern implies for the appearance of R-phase. The fact that the thinner the film is, the closer to 1 the tensor element ratio χ 31 /χ 15 tends, indicates an increase of symmetry with the decrease of thickness for BiFeO 3 thin films.

Evolution of structural distortion in BiFeO3 thin films probed by second-harmonic generation

PubMed Central

Wang, Jie-su; Jin, Kui-juan; Guo, Hai-zhong; Gu, Jun-xing; Wan, Qian; He, Xu; Li, Xiao-long; Xu, Xiu-lai; Yang, Guo-zhen

2016-01-01

BiFeO3 thin films have drawn much attention due to its potential applications for novel magnetoelectric devices and fundamental physics in magnetoelectric coupling. However, the structural evolution of BiFeO3 films with thickness remains controversial. Here we use an optical second-harmonic generation technique to explore the phase-related symmetry evolution of BiFeO3 thin films with the variation of thickness. The crystalline structures for 60 and 180-nm-thick BiFeO3 thin films were characterized by high-resolution X-ray diffractometry reciprocal space mapping and the local piezoelectric response for 60-nm-thick BiFeO3 thin films was characterized by piezoresponse force microscopy. The present results show that the symmetry of BiFeO3 thin films with a thickness below 60 nm belongs to the point group 4 mm. We conclude that the disappearance of fourfold rotational symmetry in SHG s-out pattern implies for the appearance of R-phase. The fact that the thinner the film is, the closer to 1 the tensor element ratio χ31/χ15 tends, indicates an increase of symmetry with the decrease of thickness for BiFeO3 thin films. PMID:27905565

Immobilization of uranium into magnetite from aqueous solution by electrodepositing approach.

PubMed

Lu, Bing-Qing; Li, Mi; Zhang, Xiao-Wen; Huang, Chun-Mei; Wu, Xiao-Yan; Fang, Qi

2018-02-05

Immobilization of uranium into magnetite (Fe 3 O 4 ), which was generated from metallic iron by electrochemical method, was proposed to rapidly remove uranium from aqueous solution. The effects of electrochemical parameters such as electrode materials, voltage, electrode gap, reaction time and pH value on the crystallization of Fe 3 O 4 and uranium removal efficiencies were investigated. More than 90% uranium in the solution was precipitated with Fe 3 O 4 under laboratory conditions when uranium concentration range from 0.5mg/L to 10mg/L. The Fe 3 O 4 crystallization mechanism and immobilization of uranium was proved by XPS, XRD, TEM, FTIR and VSM methods. The results indicated that the cationic (including Fe 2+ , Fe 3+ and U(VI)) migrate to cathode side under the electric field and the uranium was incorporated or adsorbed by Fe 3 O 4 which was generated at cathode while the pH ranges between 2-7. The uranium-containing precipitate of Fe 3 O 4 can exist stably at the acid concentration below 60g/L. Furthermore, the precipitate may be used as valuable resources for uranium or iron recycling, which resulted in no secondary pollution in the removal of uranium from aqueous solution. Copyright © 2017. Published by Elsevier B.V.

Status of FeCrAl ODS Irradiations in the High Flux Isotope Reactor

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

Field, Kevin G.; Howard, Richard H.

2016-08-19

FeCrAl oxide-dispersion strengthened (ODS) alloys are an attractive sub-set alloy class of the more global FeCrAl material class for nuclear applications due to their high-temperature steam oxidation resistance and hypothesized enhanced radiation tolerance. A need currently exists to determine the radiation tolerance of these newly developed alloys. To address this need, a preliminary study was conducted using the High Flux Isotope Reactor (HFIR) to irradiate an early generation FeCrAl ODS alloy, 125YF. Preliminary post-irradiation examination (PIE) on these irradiated specimens have shown good radiation tolerance at elevated temperatures (≥330°C) but possible radiation-induced hardening and embrittlement at irradiations of 200°C tomore » a damage level of 1.9 displacement per atom (dpa). Building on this experience, a new series of irradiations are currently being conceptualized. This irradiation series called the FCAD irradiation program will irradiate the latest generation FeCrAl ODS and FeCr ODS alloys to significantly higher doses. These experiments will provide the necessary information to determine the mechanical performance of irradiated FeCrAl ODS alloys at light water reactor and fast reactor conditions.« less

Emergence of high-mobility minority holes in the electrical transport of the Ba (Fe1 -xMnxAs )2 iron pnictides

NASA Astrophysics Data System (ADS)

Urata, T.; Tanabe, Y.; Huynh, K. K.; Heguri, S.; Oguro, H.; Watanabe, K.; Tanigaki, K.

2015-05-01

In Fe pnictide (Pn) superconducting materials, neither Mn nor Cr doping to the Fe site induces superconductivity, even though hole carriers are generated. This is in strong contrast with the superconductivity appearing when holes are introduced by alkali-metal substitution on the insulating blocking layers. We investigate in detail the effects of Mn doping on magnetotransport properties in Ba (Fe1 -xMnxAs )2 for elucidating the intrinsic reason. The negative Hall coefficient for x =0 estimated in the low magnetic field (B ) regime gradually increases as x increases, and its sign changes to a positive one at x =0.020 . Hall resistivities as well as simultaneous interpretation using the magnetoconductivity tensor including both longitudinal and transverse transport components clarify that minority holes with high mobility are generated by the Mn doping via spin-density wave transition at low temperatures, while original majority electrons and holes residing in the paraboliclike Fermi surfaces of the semimetallic Ba (FeAs )2 are negligibly affected. Present results indicate that the mechanism of hole doping in Ba (Fe1 -xMnxAs )2 is greatly different from that of the other superconducting FePn family.

Application of thin-plate spline transformations to finite element models, or, how to turn a bog turtle into a spotted turtle to analyze both.

PubMed

Stayton, C Tristan

2009-05-01

Finite element (FE) models are popular tools that allow biologists to analyze the biomechanical behavior of complex anatomical structures. However, the expense and time required to create models from specimens has prevented comparative studies from involving large numbers of species. A new method is presented for transforming existing FE models using geometric morphometric methods. Homologous landmark coordinates are digitized on the FE model and on a target specimen into which the FE model is being transformed. These coordinates are used to create a thin-plate spline function and coefficients, which are then applied to every node in the FE model. This function smoothly interpolates the location of points between landmarks, transforming the geometry of the original model to match the target. This new FE model is then used as input in FE analyses. This procedure is demonstrated with turtle shells: a Glyptemys muhlenbergii model is transformed into Clemmys guttata and Actinemys marmorata models. Models are loaded and the resulting stresses are compared. The validity of the models is tested by crushing actual turtle shells in a materials testing machine and comparing those results to predictions from FE models. General guidelines, cautions, and possibilities for this procedure are also presented.

Next-Generation Magnetic Nanocomposites: Cytotoxic and Genotoxic Effects of Coated and Uncoated Ferric Cobalt Boron (FeCoB) Nanoparticles In Vitro.

PubMed

Netzer, Katharina; Jordakieva, Galateja; Girard, Angelika M; Budinsky, Alexandra C; Pilger, Alexander; Richter, Lukas; Kataeva, Nadezhda; Schotter, Joerg; Godnic-Cvar, Jasminka; Ertl, Peter

2018-03-01

Metal nanoparticles (NPs) have unique physicochemical properties and a widespread application scope depending on their composition and surface characteristics. Potential biomedical applications and the growing diversity of novel nanocomposites highlight the need for toxicological hazard assessment of next-generation magnetic nanomaterials. Our study aimed to evaluate the cytotoxic and genotoxic properties of coated and uncoated ferric cobalt boron (FeCoB) NPs (5-15 nm particle size) in cultured normal human dermal fibroblasts. Cell proliferation was assessed via ATP bioluminescence kit, and DNA breakage and chromosomal damage were measured by alkaline comet assay and micronucleus test. Polyacryl acid-coated FeCoB NPs [polyacrylic acid (PAA)-FeCoB NPs) and uncoated FeCoB NPs inhibited cell proliferation at 10 μg/ml. DNA strand breaks were significantly increased by PAA-coated FeCoB NPs, uncoated FeCoB NPs and l-cysteine-coated FeCoB NPs (Cys-FeCoB NPs), although high concentrations (10 μg/ml) of coated NPs (Cys- and PAA-FeCoB NPs) showed significantly more DNA breakage when compared to uncoated ones. Uncoated FeCoB NPs and coated NPs (PAA-FeCoB NPs) also induced the formation of micronuclei. Additionally, PAA-coated NPs and uncoated FeCoB NPs showed a negative correlation between cell proliferation and DNA strand breaks, suggesting a common pathomechanism, possibly by oxidation-induced DNA damage. We conclude that uncoated FeCoB NPs are cytotoxic and genotoxic at in vitro conditions. Surface coating of FeCoB NPs with Cys and PAA does not prevent but rather aggravates DNA damage. Further safety assessment and a well-considered choice of surface coating are needed prior to application of FeCoB nanocomposites in biomedicine. © 2017 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

Chemoselectivity-induced multiple interfaces in MWCNT/Fe3O4@ZnO heterotrimers for whole X-band microwave absorption.

PubMed

Wang, Zhijiang; Wu, Lina; Zhou, Jigang; Jiang, Zhaohua; Shen, Baozhong

2014-11-07

A chemoselective route to induce Fe3O4@ZnO core-shell nanoparticles decorating carbon nanotubes to form MWCNT/Fe3O4@ZnO heterotrimers has been developed. Charges are redistributed in the heterotrimers through C-O-Zn, C-O-Fe and Fe-O-Zn bondings, giving rise to multiple electronic phases. The generated significant interfacial polarization and synergetic interaction between dielectric and magnetic absorbers result in the MWCNT/Fe3O4@ZnO heterotrimers with high-performance microwave absorption in an entire X band.

Fenton-like oxidation of 4-chlorophenol using H2O2 in situ generated by Zn-Fe-CNTs composite.

PubMed

Liu, Yong; Fan, Qing; Liu, Yanlan; Wang, Jianlong

2018-05-15

In this paper, a zinc-iron-carbon nanotubes (Zn-Fe-CNTs) composite was prepared, characterized and used to develop a Fenton-like system of Zn-Fe-CNTs/O 2 for the degradation of 4-chlorophenol (4-CP), in which H 2 O 2 was generated in situ from zinc-carbon galvanic cells and oxygen in aqueous solution was activated by iron attached on the surface of CNTs to produce ·OH radicals for the oxidation of 4-CP. The experimental results showed that the particles of Zn and Fe in Zn-Fe-CNTs composite were adhered to the surface of CNTs, which accelerated the electron transfer process. The BET area of Zn-Fe-CNTs composite was 32.9 m 2 /g. The contents of Zn and Fe (% w) in the composite were 44.7% and 4.2%, respectively. The removal efficiency of 4-CP and TOC in Zn-Fe-CNTs/O 2 system was 90.8% and 52.9%, respectively, with the initial pH of 2.0, O 2 flow rate of 800 mL/min, Zn-Fe-CNTs dosage of 1.0 g/L, 4-CP concentration of 50 mg/L and reaction time of 20 min. Based on the analysis of the degradation intermediate products with LC-MS and IC, a possible degradation pathway of 4-CP in Zn-Fe-CNTs/O 2 system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

"Negative capacitance" in resistor-ferroelectric and ferroelectric-dielectric networks: Apparent or intrinsic?

NASA Astrophysics Data System (ADS)

Saha, Atanu K.; Datta, Suman; Gupta, Sumeet K.

2018-03-01

In this paper, we describe and analytically substantiate an alternate explanation for the negative capacitance (NC) effect in ferroelectrics (FE). We claim that the NC effect previously demonstrated in resistance-ferroelectric (R-FE) networks does not necessarily validate the existence of "S" shaped relation between polarization and voltage (according to Landau theory). In fact, the NC effect can be explained without invoking the "S"-shaped behavior of FE. We employ an analytical model for FE (Miller model) in which the steady state polarization strictly increases with the voltage across the FE and show that despite the inherent positive FE capacitance, reduction in FE voltage with the increase in its charge is possible in a R-FE network as well as in a ferroelectric-dielectric (FE-DE) stack. This can be attributed to a large increase in FE capacitance near the coercive voltage coupled with the polarization lag with respect to the electric field. Under certain conditions, these two factors yield transient NC effect. We analytically derive conditions for NC effect in R-FE and FE-DE networks. We couple our analysis with extensive simulations to explain the evolution of NC effect. We also compare the trends predicted by the aforementioned Miller model with Landau-Khalatnikov (L-K) model (static negative capacitance due to "S"-shape behaviour) and highlight the differences between the two approaches. First, with an increase in external resistance in the R-FE network, NC effect shows a non-monotonic behavior according to Miller model but increases according to L-K model. Second, with the increase in ramp-rate of applied voltage in the FE-DE stack, NC effect increases according to Miller model but decreases according to L-K model. These results unveil a possible way to experimentally validate the actual reason of NC effect in FE.

Preliminary Phase Field Computational Model Development

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

Li, Yulan; Hu, Shenyang Y.; Xu, Ke

2014-12-15

This interim report presents progress towards the development of meso-scale models of magnetic behavior that incorporate microstructural information. Modeling magnetic signatures in irradiated materials with complex microstructures (such as structural steels) is a significant challenge. The complexity is addressed incrementally, using the monocrystalline Fe (i.e., ferrite) film as model systems to develop and validate initial models, followed by polycrystalline Fe films, and by more complicated and representative alloys. In addition, the modeling incrementally addresses inclusion of other major phases (e.g., martensite, austenite), minor magnetic phases (e.g., carbides, FeCr precipitates), and minor nonmagnetic phases (e.g., Cu precipitates, voids). The focus ofmore » the magnetic modeling is on phase-field models. The models are based on the numerical solution to the Landau-Lifshitz-Gilbert equation. From the computational standpoint, phase-field modeling allows the simulation of large enough systems that relevant defect structures and their effects on functional properties like magnetism can be simulated. To date, two phase-field models have been generated in support of this work. First, a bulk iron model with periodic boundary conditions was generated as a proof-of-concept to investigate major loop effects of single versus polycrystalline bulk iron and effects of single non-magnetic defects. More recently, to support the experimental program herein using iron thin films, a new model was generated that uses finite boundary conditions representing surfaces and edges. This model has provided key insights into the domain structures observed in magnetic force microscopy (MFM) measurements. Simulation results for single crystal thin-film iron indicate the feasibility of the model for determining magnetic domain wall thickness and mobility in an externally applied field. Because the phase-field model dimensions are limited relative to the size of most specimens used in experiments, special experimental methods were devised to create similar boundary conditions in the iron films. Preliminary MFM studies conducted on single and polycrystalline iron films with small sub-areas created with focused ion beam have correlated quite well qualitatively with phase-field simulations. However, phase-field model dimensions are still small relative to experiments thus far. We are in the process of increasing the size of the models and decreasing specimen size so both have identical dimensions. Ongoing research is focused on validation of the phase-field model. Validation is being accomplished through comparison with experimentally obtained MFM images (in progress), and planned measurements of major hysteresis loops and first order reversal curves. Extrapolation of simulation sizes to represent a more stochastic bulk-like system will require sampling of various simulations (i.e., with single non-magnetic defect, single magnetic defect, single grain boundary, single dislocation, etc.) with distributions of input parameters. These outputs can then be compared to laboratory magnetic measurements and ultimately to simulate magnetic Barkhausen noise signals.« less

One electron oxidation of 3-methylcholanthrene: A chemical model for its mechanism of carcinogenesis

NASA Astrophysics Data System (ADS)

Lehner, Andreas F.; Horn, Jamie; Flesher, James W.

2017-06-01

One electron transfer oxidation has long been proposed as a route to the ultimate electrophilic and carcinogenic metabolites of both methylated and non-methylated polycyclic aromatic hydrocarbons (PAH). The carcinogenic hydrocarbon 3-methylcholanthrene (3-MC) has a methyl-analogous function at its meso-anthracenic center in the form of a dimethylene bridge, and treatment of this compound with the one electron transfer oxidizing reagent ferric ferricyanide, FeIII(FeIII(CN)6), in mixed aqueous-organic media generated multiple oxygenated species, many of which duplicate those found in mammalian metabolism including known carcinogens 1-hydroxy-3MC and 1-keto-3MC. These results are in agreement with a Unified Theory for PAH Carcinogenicity which predicts in vivo generation of a proximate benzylic alcohol metabolite from the 3-MC procarcinogen and conjugation with a moiety such as sulfate intended for rapid urinary excretion. The sulfate instead acts as a leaving group and generates an electrophilic carbocation capable of reacting with sensitive nucleophiles such as DNA in cellular nuclei. The products of one electron transfer oxidation align well with predictions of the Unified Theory since in many cases these products provide substrates or precursors for conjugation reactions.

3D Computer Models of T- x- y Diagrams, Forming the Fe-Ni-Co-FeS-NiS-CoS Subsystem

NASA Astrophysics Data System (ADS)

Lutsyk, V. I.; Vorob'eva, V. P.

2017-12-01

3D computer models of Fe-Ni-Co, Fe-Ni-FeS-NiS, Fe-Co-FeS-CoS, Ni-Co-NiS-CoS T- x- y diagrams have been designed. The geometric structure (35 surfaces, two-phase surface of the reaction type change, 17 phase regions) of the Fe-Ni-FeS-NiS T- x- y diagram is investigated in detail. The liquidus hypersurfaces prediction of the Fe-Ni-Co-FeS-NiS-CoS subsystem is represented.

Gamma ray irradiated AgFeO{sub 2} nanoparticles with enhanced gas sensor properties

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

Wang, Xiuhua, E-mail: xhwang@mail.ahnu.edu.cn; Shi, Zhijie; Yao, Shangwu

2014-11-15

AgFeO{sub 2} nanoparticles were synthesized via a facile hydrothermal method and irradiated by various doses of gamma ray. The products were characterized with X-ray powder diffraction, UV–vis absorption spectrum and transmission electron microscope. The results revealed that the crystal structure, morphology and size of the samples remained unchanged after irradiation, while the intensity of UV–Vis spectra increased with irradiation dose increasing. In addition, gamma ray irradiation improved the performance of gas sensor based on the AgFeO{sub 2} nanoparticles including the optimum operating temperature and sensitivity, which might be ascribed to the generation of defects. - Graphical abstract: Gamma ray irradiationmore » improved the performance of gas sensor based on the AgFeO{sub 2} nanoparticles including sensitivity and optimum operating temperature, which might be ascribed to the generation of defects. - Highlights: • AgFeO{sub 2} nanoparticles were synthesized and irradiated with gamma ray. • AgFeO{sub 2} nanoparticles were employed to fabricate gas sensors to detect ethanol. • Gamma ray irradiation improved the sensitivity and optimum operating temperature.« less

Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

PubMed

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.

Evolution of displacement cascades in Fe-Cr structures with different [001] tilt grain boundaries

NASA Astrophysics Data System (ADS)

Abu-Shams, M.; Haider, W.; Shabib, I.

2017-06-01

Reduced-activation ferritic/martensitic steels of Cr concentration between 2.25 and 12 wt% are candidate structural materials for next-generation nuclear reactors. In this study, molecular dynamics (MD) simulation is used to generate the displacement cascades in Fe-Cr structures with different Cr concentrations by using different primary knock-on atom (PKA) energies between 2 and 10 keV. A concentration-dependent model potential has been used to describe the interactions between Fe and Cr. Single crystals (SCs) of three different coordinate bases (e.g. [310], [510], and [530]) and bi-crystal (BC) structures with three different [001] tilt grain boundaries (GBs) (e.g. Σ5, Σ13, and Σ17) have been simulated. The Wigner-Seitz cell criterion has been used to identify the produced Frenkel pairs. The results show a marked difference between collisions observed in SCs and those in BC structures. The numbers of vacancies and interstitials are found to be significantly higher in BC structures than those found in SCs. The number of point defects exhibits a power relationship with the PKA energies; however, the Cr concentration does not seem to have any influence on the number of survived point defects. In BC models, a large fraction of the total survived point defects (between 59% and 93%) tends accumulate at the GBs, which seem to trap the generated point defects. The BC structure with Σ17 GB is found to trap more defects than Σ5 and Σ13 GBs. The defect trapping is found to be dictated by the crystallographic parameters of the GBs. For all studied GBs, self-interstitial atoms (SIAs) are easily trapped within the GB region than vacancies. An analysis of defect composition reveals an enrichment of Cr in SIAs, and in BC cases, more than half of the Cr-SIAs are found to be located within the GB region.

Initial 60Fe Abundance in the Solar Nebula Constrained by Delayed Onset of a Planetesimal Dynamo

NASA Astrophysics Data System (ADS)

Wang, H.; Weiss, B. P.; Crowley, J.

2017-12-01

The paleomagnetism of meteorites provides evidence for advecting metallic core dynamos and large-scale differentiation on their parent planetesimals. Their small sizes relative to planets enable new opportunities to understand the physics of dynamo generation. Wang et al. [2017] studied the paleomagnetism of three volcanic angrites (D'Orbigny, 4563.37±0.12 Ma; Sahara 99555, 4563.54±0.14 Ma; Asuka 881371, 4562.4±1.6 Ma) and one plutonic angrite (Angra dos Reis, 4556.51±0.11 Ma). Their results show that the older volcanic angrites recorded no detectable paleomagnetic field, while the younger plutonic angrite recorded a paleomagnetic field of 17 µT interpreted as evidence of a core dynamo on the angrite parent body (APB). This indicates that the initiation of the APB dynamo was delayed until sometime between 4 and 11 My after the formation of calcium aluminum-rich inclusions (CAIs) at 4567.30 ± 0.16 Ma. This late timing is consistent with recent planetesimal thermal evolution models invoking shallow magma oceans [Neumann et al. 2014], which predict that planetesimal dynamos would not initiate until the core began to crystallize. It is also consistent with thermal evolution models invoking large-scale magma oceans that considered thermal blanketing of the core by 26Al decay in the mantle [Roberts et al. 2013, Sterenborg and Crowley 2013], which would delay thermal convection dynamos until several My after accretion (occurred <0.25 My after CAIs for the APB [Schiller et al. 2015]) and differentiation. Because the presence of even a small amount of 60Fe in the core could effectively remove the thermal blanketing effect of mantle 26Al, we can use the delay in timing of the dynamo to constrain the abundance of 60Fe on the APB. Our planetesimal thermal evolution models show that if the initial solar nebula 60Fe/56Fe ratio was greater than 5×10-9, the APB core dynamo would have to start earlier than 4 My after CAIs, in contradiction to the paleomagnetic constraints. Thus, we argue that 5×10-9 is an upper limit of the initial 60Fe/56Fe ratio in the solar nebula. This upper limit is consistent with independent isotopic measurements of the Sahara 99555 angrite, which found 60Fe/56Fe ratio of (6.96 ± 1.60)×10-9 [Tang and Dauphas, 2015].

Electron emission from ferroelectrics - a review

NASA Astrophysics Data System (ADS)

Riege, H.

1994-02-01

The strong pulsed emission of electrons from the surface of ferroelectric (FE) materials was discovered at CERN in 1987. Since then many aspects and properties of the method of generation and propagation of electron beams from FE have been studied experimentally. The method is based on macroscopic charge separation and self-emission of electrons under the influence of their own space-charge fields. Hence, this type of emission is not limited by the Langmuir-Child law as are conventional emission methods. Charge separation and electron emission can be achieved by rapid switching of the spontaneous, ferroelectric polarization. Polarization switching may be induced by application of electrical-field or mechanical-pressure pulses, as well as by thermal heating or laser illumination of the ferroelectric emitter. At higher emission intensities plasma formation assists the FE emission and leads to a strong growth of emitted current amplitude, which is no longer limited by the FE material and the surface properties. The most attractive features of FE emission are robustness and ease of manipulation of the emitter cathodes which can be transported through atmospheric air and used without any problems in vacuum, low-pressure gas or plasma environments. Large-area arrangements of multiple emitters, switched in interleaved mode, can produce electron beams of any shape, current amplitude or time structure. The successful application of FE emission in accelerator technology has been demonstrated experimentally in several cases, e.g. for triggering high-power gas switches, for photocathodes in electron guns, and for electron-beam generators intended to generate, neutralize and enhance ion beams in ion sources and ion linacs. Other applications can be envisaged in microwave power generators and in the fields of electronics and vacuum microelectronics.

Kinetic model to explain the effect of ocean warming and acidification on the Fe(II) oxidation rate in oligotrophic and eutrophic natural waters

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Samperio-Ramos, G.; Santana-Casiano, J. M.; Gonzallez, A. G.; Pérez-Almeida, N.

2016-12-01

The speciation of inorganic Fe(II) as a function of the pH and temperature have been modeled in order to elucidate the inorganic Fe(II) redox behavior over a wide range of scenarios of acidification and global warming of the upper ocean, as well as, changes due to natural ambient fluctuations of pH and temperature. In addition, a kinetic modeling approach has been carried out to elucidate the fractional contribution of most kinetically active Fe(II) species to the overall oxidation rate to improve our future and present knowledge with respect to redox iron chemistry in the marine systems. The kinetic model considers the interactions of Fe(II) with the major ions in seawater, including phosphate and silicate and the competition with copper with the ROS. The model has been applied to the experimental results in order to describe the effect of temperature and pH in the speciation of Fe(II) and to compute the fractional contribution of each Fe(II)-specie to the overall oxidation rate. The oxidation rates (kapp) of nanomolar levels of Fe(II) have been studied in seawater enriched with nutrients (SWEN) in air saturated conditions. The nutrient effect (nitrate, phosphate and silicate), on the oxidation of Fe(II), has been evaluated as a function of pH (7.2-8.2), temperature (5-35 ºC) and salinity (10-37.09). The oxidation of Fe(II) was faster in the presence of nutrient with the change in the Fe(II) oxidation rates (Δlogkapp) more intensive at higher temperatures over the entire pH range studied. From the model it can be observed that the inorganic speciation of Fe(II) is controlled largely by pH, either in SW or in SWEN. A greater presence of Fe-nutrient reactive species (FeH3SiO4+ and FePO4-) in SWEN at higher temperatures explained the changes in the oxidation process. The individual oxidation rates by oxygen, for the Fe(II) most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3(OH)-, FeCO3, Fe(CO3)22-, FeH3SiO3+, FePO4-), were fitted as a function of the temperature.

Phylogenetic and Structural Diversity in the Feline Leukemia Virus Env Gene

PubMed Central

Watanabe, Shinya; Kawamura, Maki; Odahara, Yuka; Anai, Yukari; Ochi, Haruyo; Nakagawa, So; Endo, Yasuyuki; Tsujimoto, Hajime; Nishigaki, Kazuo

2013-01-01

Feline leukemia virus (FeLV) belongs to the genus Gammaretrovirus, and causes a variety of neoplastic and non-neoplastic diseases in cats. Alteration of viral env sequences is thought to be associated with disease specificity, but the way in which genetic diversity of FeLV contributes to the generation of such variants in nature is poorly understood. We isolated FeLV env genes from naturally infected cats in Japan and analyzed the evolutionary dynamics of these genes. Phylogenetic reconstructions separated our FeLV samples into three distinct genetic clusters, termed Genotypes I, II, and III. Genotype I is a major genetic cluster and can be further classified into Clades 1–7 in Japan. Genotypes were correlated with geographical distribution; Genotypes I and II were distributed within Japan, whilst FeLV samples from outside Japan belonged to Genotype III. These results may be due to geographical isolation of FeLVs in Japan. The observed structural diversity of the FeLV env gene appears to be caused primarily by mutation, deletion, insertion and recombination, and these variants may be generated de novo in individual cats. FeLV interference assay revealed that FeLV genotypes did not correlate with known FeLV receptor subgroups. We have identified the genotypes which we consider to be reliable for evaluating phylogenetic relationships of FeLV, which embrace the high structural diversity observed in our sample. Overall, these findings extend our understanding of Gammaretrovirus evolutionary patterns in the field, and may provide a useful basis for assessing the emergence of novel strains and understanding the molecular mechanisms of FeLV transmission in cats. PMID:23593376

Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

PubMed

Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

2017-08-22

It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

Numerical fatigue 3D-FE modeling of indirect composite-restored posterior teeth.

PubMed

Ausiello, Pietro; Franciosa, Pasquale; Martorelli, Massimo; Watts, David C

2011-05-01

In restored teeth, stresses at the tooth-restoration interface during masticatory processes may fracture the teeth or the restoration and cracks may grow and propagate. The aim was to apply numerical methodologies to simulate the behavior of a restored tooth and to evaluate fatigue lifetimes before crack failure. Using a CAD-FEM procedure and fatigue mechanic laws, the fatigue damage of a restored molar was numerically estimated. Tessellated surfaces of enamel and dentin were extracted by applying segmentation and classification algorithms, to sets of 2D image data. A user-friendly GUI, which enables selection and visualization of 3D tessellated surfaces, was developed in a MatLab(®) environment. The tooth-boundary surfaces of enamel and dentin were then created by sweeping operations through cross-sections. A class II MOD cavity preparation was then added into the 3D model and tetrahedral mesh elements were generated. Fatigue simulation was performed by combining a preliminary static FEA simulation with classical fatigue mechanical laws. Regions with the shortest fatigue-life were located around the fillets of the class II MOD cavity, where the static stress was highest. The described method can be successfully adopted to generate detailed 3D-FE models of molar teeth, with different cavities and restorative materials. This method could be quickly implemented for other dental or biomechanical applications. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Comparisons of node-based and element-based approaches of assigning bone material properties onto subject-specific finite element models.

PubMed

Chen, G; Wu, F Y; Liu, Z C; Yang, K; Cui, F

2015-08-01

Subject-specific finite element (FE) models can be generated from computed tomography (CT) datasets of a bone. A key step is assigning material properties automatically onto finite element models, which remains a great challenge. This paper proposes a node-based assignment approach and also compares it with the element-based approach in the literature. Both approaches were implemented using ABAQUS. The assignment procedure is divided into two steps: generating the data file of the image intensity of a bone in a MATLAB program and reading the data file into ABAQUS via user subroutines. The node-based approach assigns the material properties to each node of the finite element mesh, while the element-based approach assigns the material properties directly to each integration point of an element. Both approaches are independent from the type of elements. A number of FE meshes are tested and both give accurate solutions; comparatively the node-based approach involves less programming effort. The node-based approach is also independent from the type of analyses; it has been tested on the nonlinear analysis of a Sawbone femur. The node-based approach substantially improves the level of automation of the assignment procedure of bone material properties. It is the simplest and most powerful approach that is applicable to many types of analyses and elements. Copyright © 2015 IPEM. Published by Elsevier Ltd. All rights reserved.

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

PubMed

Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

2015-05-06

The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

Seasonal and spatial variabilities in northern Gulf of Alaska surface water iron concentrations driven by shelf sediment resuspension, glacial meltwater, a Yakutat eddy, and dust

NASA Astrophysics Data System (ADS)

Crusius, John; Schroth, Andrew W.; Resing, Joseph A.; Cullen, Jay; Campbell, Robert W.

2017-06-01

Phytoplankton growth in the Gulf of Alaska (GoA) is limited by iron (Fe), yet Fe sources are poorly constrained. We examine the temporal and spatial distributions of Fe, and its sources in the GoA, based on data from three cruises carried out in 2010 from the Copper River (AK) mouth to beyond the shelf break. April data are the first to describe late winter Fe behavior before surface water nitrate depletion began. Sediment resuspension during winter and spring storms generated high "total dissolvable Fe" (TDFe) concentrations of 1000 nmol kg-1 along the entire continental shelf, which decreased beyond the shelf break. In July, high TDFe concentrations were similar on the shelf, but more spatially variable, and driven by low-salinity glacial meltwater. Conversely, dissolved Fe (DFe) concentrations in surface waters were far lower and more seasonally consistent, ranging from 4 nmol kg-1 in nearshore waters to 0.6-1.5 nmol kg-1 seaward of the shelf break during April and July, despite dramatic depletion of nitrate over that period. The reasonably constant DFe concentrations are likely maintained during the year across the shelf by complexation by strong organic ligands, coupled with ample supply of labile particulate Fe. The April DFe data can be simulated using a simple numerical model that assumes a DFe flux from shelf sediments, horizontal transport by eddy diffusion, and removal by scavenging. Given how global change is altering many processes impacting the Fe cycle, additional studies are needed to examine controls on DFe in the Gulf of Alaska.

A Structural Molar Volume Model for Oxide Melts Part III: Fe Oxide-Containing Melts

NASA Astrophysics Data System (ADS)

Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

2016-04-01

As part III of this series, the model is extended to iron oxide-containing melts. All available experimental data in the FeO-Fe2O3-Na2O-K2O-MgO-CaO-MnO-Al2O3-SiO2 system were critically evaluated based on the experimental condition. The variations of FeO and Fe2O3 in the melts were taken into account by using FactSage to calculate the Fe2+/Fe3+ distribution. The molar volume model with unary and binary model parameters can be used to predict the molar volume of the molten oxide of the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-FeO-Fe2O3-Al2O3-SiO2 system in the entire range of compositions, temperatures, and oxygen partial pressures from Fe saturation to 1 atm pressure.

Ab Initio Structural Modeling of and Experimental Validation for Chlamydia trachomatis Protein CT296 Reveal Structural Similarity to Fe(II) 2-Oxoglutarate-Dependent Enzymes▿

PubMed Central

Kemege, Kyle E.; Hickey, John M.; Lovell, Scott; Battaile, Kevin P.; Zhang, Yang; Hefty, P. Scott

2011-01-01

Chlamydia trachomatis is a medically important pathogen that encodes a relatively high percentage of proteins with unknown function. The three-dimensional structure of a protein can be very informative regarding the protein's functional characteristics; however, determining protein structures experimentally can be very challenging. Computational methods that model protein structures with sufficient accuracy to facilitate functional studies have had notable successes. To evaluate the accuracy and potential impact of computational protein structure modeling of hypothetical proteins encoded by Chlamydia, a successful computational method termed I-TASSER was utilized to model the three-dimensional structure of a hypothetical protein encoded by open reading frame (ORF) CT296. CT296 has been reported to exhibit functional properties of a divalent cation transcription repressor (DcrA), with similarity to the Escherichia coli iron-responsive transcriptional repressor, Fur. Unexpectedly, the I-TASSER model of CT296 exhibited no structural similarity to any DNA-interacting proteins or motifs. To validate the I-TASSER-generated model, the structure of CT296 was solved experimentally using X-ray crystallography. Impressively, the ab initio I-TASSER-generated model closely matched (2.72-Å Cα root mean square deviation [RMSD]) the high-resolution (1.8-Å) crystal structure of CT296. Modeled and experimentally determined structures of CT296 share structural characteristics of non-heme Fe(II) 2-oxoglutarate-dependent enzymes, although key enzymatic residues are not conserved, suggesting a unique biochemical process is likely associated with CT296 function. Additionally, functional analyses did not support prior reports that CT296 has properties shared with divalent cation repressors such as Fur. PMID:21965559

Ab initio structural modeling of and experimental validation for Chlamydia trachomatis protein CT296 reveal structural similarity to Fe(II) 2-oxoglutarate-dependent enzymes

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

Kemege, Kyle E.; Hickey, John M.; Lovell, Scott

2012-02-13

Chlamydia trachomatis is a medically important pathogen that encodes a relatively high percentage of proteins with unknown function. The three-dimensional structure of a protein can be very informative regarding the protein's functional characteristics; however, determining protein structures experimentally can be very challenging. Computational methods that model protein structures with sufficient accuracy to facilitate functional studies have had notable successes. To evaluate the accuracy and potential impact of computational protein structure modeling of hypothetical proteins encoded by Chlamydia, a successful computational method termed I-TASSER was utilized to model the three-dimensional structure of a hypothetical protein encoded by open reading frame (ORF)more » CT296. CT296 has been reported to exhibit functional properties of a divalent cation transcription repressor (DcrA), with similarity to the Escherichia coli iron-responsive transcriptional repressor, Fur. Unexpectedly, the I-TASSER model of CT296 exhibited no structural similarity to any DNA-interacting proteins or motifs. To validate the I-TASSER-generated model, the structure of CT296 was solved experimentally using X-ray crystallography. Impressively, the ab initio I-TASSER-generated model closely matched (2.72-{angstrom} C{alpha} root mean square deviation [RMSD]) the high-resolution (1.8-{angstrom}) crystal structure of CT296. Modeled and experimentally determined structures of CT296 share structural characteristics of non-heme Fe(II) 2-oxoglutarate-dependent enzymes, although key enzymatic residues are not conserved, suggesting a unique biochemical process is likely associated with CT296 function. Additionally, functional analyses did not support prior reports that CT296 has properties shared with divalent cation repressors such as Fur.« less

Improved Reversibility of Fe3+ /Fe4+ Redox Couple in Sodium Super Ion Conductor Type Na3 Fe2 (PO4 )3 for Sodium-Ion Batteries.

PubMed

Rajagopalan, Ranjusha; Chen, Bo; Zhang, Zhicheng; Wu, Xing-Long; Du, Yonghua; Huang, Ying; Li, Bing; Zong, Yun; Wang, Jie; Nam, Gwang-Hyeon; Sindoro, Melinda; Dou, Shi Xue; Liu, Hua Kun; Zhang, Hua

2017-03-01

The methodology employed here utilizes the sodium super ion conductor type sodium iron phosphate wrapped with conducting carbon network to generate a stable Fe 3+ /Fe 4+ redox   couple, thereby exhibiting higher operating voltage and energy density of sodium-ion batteries. This new class of sodium iron phosphate wrapped by carbon also displays a cycling stability with >96% capacity retention after 200 cycles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

NASA Technical Reports Server (NTRS)

Johnson, M. S.; Meskhidze, N.

2013-01-01

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.

Giant Polarization Rotation in BiFeO3/SrTiO3 Thin Films.

NASA Astrophysics Data System (ADS)

Langner, M. C.; Chu, Y. H.; Martin, L. M.; Gajek, M.; Ramesh, R.; Orenstein, J.

2008-03-01

We use optical second harmonic generation to probe dynamics of the ferroelectric polarization in (111) oriented BiFeO3 thin films grown on SrTiO3 substrates. The second harmonic response indicates 3m point group symmetry and is consistent with a spontaneous polarization normal to the surface of the film. We measure large changes in amplitude and lowering of symmetry, consistent with polarization rotation, when modest electric fields are applied in the plane of the film. At room temperature the rotation is an order of magnitude larger than expected from reported values of the dielectric constant and increases further (as 1/T) as temperature is lowered. We propose a substrate interaction model to explain these results.

Experimental Verification of Modeled Thermal Distribution Produced by a Piston Source in Physiotherapy Ultrasound

PubMed Central

Lopez-Haro, S. A.; Leija, L.

2016-01-01

Objectives. To present a quantitative comparison of thermal patterns produced by the piston-in-a-baffle approach with those generated by a physiotherapy ultrasonic device and to show the dependency among thermal patterns and acoustic intensity distributions. Methods. The finite element (FE) method was used to model an ideal acoustic field and the produced thermal pattern to be compared with the experimental acoustic and temperature distributions produced by a real ultrasonic applicator. A thermal model using the measured acoustic profile as input is also presented for comparison. Temperature measurements were carried out with thermocouples inserted in muscle phantom. The insertion place of thermocouples was monitored with ultrasound imaging. Results. Modeled and measured thermal profiles were compared within the first 10 cm of depth. The ideal acoustic field did not adequately represent the measured field having different temperature profiles (errors 10% to 20%). Experimental field was concentrated near the transducer producing a region with higher temperatures, while the modeled ideal temperature was linearly distributed along the depth. The error was reduced to 7% when introducing the measured acoustic field as the input variable in the FE temperature modeling. Conclusions. Temperature distributions are strongly related to the acoustic field distributions. PMID:27999801

Ferric iron amendment increases Fe(III)-reducing microbial diversity and carbon oxidation in on-site wastewater systems.

PubMed

Azam, Hossain M; Finneran, Kevin T

2013-01-01

Onsite wastewater systems, or septic tanks, serve approximately 25% of the United States population; they are therefore a critical component of the total carbon balance for natural water bodies. Septic tanks operate under strictly anaerobic conditions, and fermentation is the dominant process driving carbon transformation. Nitrate, Fe(III), and sulfate reduction may be operating to a limited extent in any given septic tank. Electron acceptor amendments will increase carbon oxidation, but nitrate is toxic and sulfate generates corrosive sulfides, which may damage septic system infrastructure. Fe(III) reducing microorganisms transform all major classes of organic carbon that are dominant in septic wastewater: low molecular weight organic acids, carbohydrate monomers and polymers, and lipids. Fe(III) is not toxic, and the reduction product Fe(II) is minimally disruptive if the starting Fe(III) is added at 50-150 mg L(-1). We used (14)C radiolabeled acetate, lactate, propionate, butyrate, glucose, starch, and oleic acid to demonstrate that short and long-term carbon oxidation is increased when different forms of Fe(III) are amended to septic wastewater. The rates of carbon mineralization to (14)CO(2) increased 2-5 times (relative to unamended systems) in the presence of Fe(III). The extent of mineralization reached 90% for some carbon compounds when Fe(III) was present, compared to levels of 50-60% in the absence of Fe(III). (14)CH(4) was not generated when Fe(III) was added, demonstrating that this strategy can limit methane emissions from septic systems. Amplified 16S rDNA restriction analysis indicated that unique Fe(III)-reducing microbial communities increased significantly in Fe(III)-amended incubations, with Fe(III)-reducers becoming the dominant microbial community in several incubations. The form of Fe(III) added had a significant impact on the rate and extent of mineralization; ferrihydrite and lepidocrocite were favored as solid phase Fe(III) and chelated Fe(III) (with nitrilotriacetic acid or EDTA) as soluble Fe(III) forms. Copyright © 2012 Elsevier Ltd. All rights reserved.

The effects of redox fluctuation on iron-organic matter interactions in wet tropical soils

NASA Astrophysics Data System (ADS)

Bhattacharyya, A.; Campbell, A.; Lin, Y.; Nico, P. S.; Silver, W. L.; Pett-Ridge, J.

2016-12-01

Two-thirds of the C in the terrestrial biosphere is stored as soil organic C, and much of this is stabilized via iron (Fe) mineral-organic matter (OM) associations that are susceptible to redox effects. The rapid C cycling typical of wet tropical ecosystems- driven by ample moisture and temperature- may also be fueled by a characteristically dynamic redox environment. Yet the net result of altered tropical soil climate and fluctuating soil redox regimes on Fe-organic matter associations is poorly understood. In this study, we hypothesized that the timing of redox transitions (frequency of O2 introduction and ferrous iron (Fe2+) generation) will lead to differences in Fe (oxyhydr)oxide mineral crystallinity and C degradation rates and alter the proportion of organic C associated with iron minerals. Surface soils from a humid tropical forest in Puerto Rico were incubated for 44 days under four redox regimes: (1) static anoxic, (2) static oxic, (3) 4 days anoxic, 4 days oxic, and (4) 4 days anoxic, 8 days oxic. Replicate microcosms were harvested at multiple time points, including before and after a redox switch (oxic to anoxic or vice versa). Selective chemical extractions, bulk Fe K-edge EXAFS and STXM/NEXAFS spectromicroscopy were used to comprehensively probe treatment effects on Fe and C speciation. Static redox conditions had a significant effect on Fe2+ and dissolved organic carbon (DOC) concentrations, and prolonged anoxia promoted reductive dissolution of Fe-oxides and an increase in amorphous or short-range ordered (SRO) Fe oxides. Preferential dissolution of this less-crystalline Fe pool was more prominent during rapid redox switches from oxic to anoxic conditions, and coincided with increased DOC. Bulk Fe K-edge EXAFS spectroscopy identified Fe3+ as the dominant Fe species in all treatments and indicated O/N atoms in the first Fe co-ordination sphere and features similar to SRO Fe-oxide phases (e.g. ferrihydrite or nano-goethite) in the second co-ordination sphere. STXM/NEXAFS analyses indicated an increase in lignin-like biomolecules under static anoxic conditions, and a potential role of Fe-lignin interactions under strong reducing conditions. Our current findings highlight the necessity to explore natural redox-dynamic systems in greater detail in order to develop a better model for climate change.

Biogeochemical Activity of Siderophilic Cyanobacteria and Insights from their Genomes Implications for the Development of New Biosignatures

NASA Technical Reports Server (NTRS)

Brown, I. I.; Bryant, D. A.; Thomas,-Keprta, K. L.; Tringe, S. G.; Sarkisova, S. A.; Galindo, C., Jr.; Malley, K.; Sosa, O.; Garrison, D. H.; McKay, David S.

2010-01-01

Verifying the links between genomie features in living organisms and their mineralization/demineralization activity will help to reveal traces of life on Earth and beyond. Among contemporary environments, iron-depositing hot springs (IDHS) may represent one of the most appropriate natural models for insights into ancient life since organisms may have originated on Earth and possibly Mars in association with hydrothennal activity and high [Fe(2+)]. Siderophilic or "iron-loving" cyanobacteria (CB) inhabiting IDHS may have genomic features and properties similar to those of ancient organisms because abundant Fe(2+) in IDHS has a strong potential to increase the magnitude of oxidative stress. That is why specific and/or additional proteins involved in Fe mineralization by siderophilic CB are expected. Inorganic polyphosphates (PPi) are known to increase the viability of prokaryotes Linder heavy metal concentrations and UV stress conditions. PPi have also been proposed as biosignatures. Ancient CB could have also been stressed by occasional migrations from the Fe(2+) rich Ocean to the basaltic land which was almost devoid of dissolved Fe(2+). Thus, the study of the adaptation reactions of siderophilic CB to fluctuation of dissolved Fe level may shed light on the paleophysiology of ancient oxygenic prokaryotes. Moreover, bioweathered Fe, Al, P, Cu, Ti and rare earth elements can be thought of as candidate organomarkers that document the effects of or ganic molecules in weathered rocks. However, the molecular mechanisms of the maintenance of Fe homeostasis in siderophilic CB, the role of PPi for this process and bioweathering activities are poorly understood. Here we present preliminary results describing a new mechanism of Fe mineralization in siderophilic CB, the effect of Fe on the generation of PPi bodies in siderophilic CB, their bioweathering activity and preliminary analysis of the diversity of proteins involved in the prevention of oxidative stress in phototrophs inhabiting IDHS.

Database on Performance of Neutron Irradiated FeCrAl Alloys

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

Field, Kevin G.; Briggs, Samuel A.; Littrell, Ken

The present report summarizes and discusses the database on radiation tolerance for Generation I, Generation II, and commercial FeCrAl alloys. This database has been built upon mechanical testing and microstructural characterization on selected alloys irradiated within the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL) up to doses of 13.8 dpa at temperatures ranging from 200°C to 550°C. The structure and performance of these irradiated alloys were characterized using advanced microstructural characterization techniques and mechanical testing. The primary objective of developing this database is to enhance the rapid development of a mechanistic understanding on the radiation tolerancemore » of FeCrAl alloys, thereby enabling informed decisions on the optimization of composition and microstructure of FeCrAl alloys for application as an accident tolerant fuel (ATF) cladding. This report is structured to provide a brief summary of critical results related to the database on radiation tolerance of FeCrAl alloys.« less

Sulfide mineralization: Its role in chemical weathering of Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1988-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.

Weathering of sulfides on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.; Fisher, Duncan S.

1987-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

Roles of the distinct electronic structures of the {Fe(NO)(2)}(9) and {Fe(NO)(2)}(10) dinitrosyliron complexes in modulating nitrite binding modes and nitrite activation pathways.

PubMed

Tsai, Fu-Te; Chen, Pei-Lin; Liaw, Wen-Feng

2010-04-14

Nitrosylation of [PPN](2)[(ONO)(2)Fe(eta(2)-ONO)(2)] [1; PPN = bis(triphenylphosphoranylidene)ammonium] yields the nitrite-containing {Fe(NO)}(7) mononitrosyliron complex (MNIC) [PPN](2)[(NO)Fe(ONO)(3)(eta(2)-ONO)] (2). At 4 K, complex 2 exhibits an S = (3)/(2) axial EPR spectrum with principal g values of g( perpendicular) = 3.971 and g( parallel) = 2.000, suggestive of the {Fe(III)(NO(-))}(7) electronic structure. Addition of 1 equiv of PPh(3) to complex 2 triggers O-atom transfer of the chelating nitrito ligand under mild conditions to yield the {Fe(NO)(2)}(9) dinitrosyliron complex (DNIC) [PPN][(ONO)(2)Fe(NO)(2)] (3). These results demonstrate that both electronic structure [{Fe(III)(NO(-))}(7), S = (3)/(2)] and redox-active ligands ([RS](-) for [(RS)(3)Fe(NO)](-) and [NO(-)] for complex 2) are required for the transformation of {Fe(NO)}(7) MNICs into {Fe(NO)(2)}(9) DNICs. In comparison with the PPh(3)-triggered O-atom abstraction of the chelating nitrito ligand of the {Fe(NO)(2)}(9) DNIC [(1-MeIm)(2)(eta(2)-ONO)Fe(NO)(2)] (5; 1-MeIm = 1-methylimidazole) to generate the {Fe(NO)(2)}(10) DNIC [(1-MeIm)(PPh(3))Fe(NO)(2)] (6), glacial acetic acid protonation of the N-bound nitro ligand in the {Fe(NO)(2)}(10) DNIC [PPN][(eta(1)-NO(2))(PPh(3))Fe(NO)(2)] (7) produced the {Fe(NO)(2)}(9) DNIC [PPN][(OAc)(2)Fe(NO)(2)] (8), nitric oxide, and H(2)O. These results demonstrate that the distinct electronic structures of {Fe(NO)(2)}(9/10) motifs [{Fe(NO)(2)}(9) vs {Fe(NO)(2)}(10)] play crucial roles in modulating nitrite binding modes (O-bound chelating/monodentate nitrito for {Fe(NO)(2)}(9) DNICs vs N-bound nitro as a pi acceptor for {Fe(NO)(2)}(10) DNICs) and regulating nitrite activation pathways (O-atom abstraction by PPh(3) leading to the intermediate with a nitroxyl-coordinated ligand vs protonation accompanied by dehydration leading to the intermediate with a nitrosonium-coordinated ligand). That is, the redox shuttling between the {Fe(NO)(2)}(9) and {Fe(NO)(2)}(10) DNICs modulates the nitrite binding modes and then triggers nitrite activation to generate nitric oxide.

Modelling deformation and fracture in confectionery wafers

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

Mohammed, Idris K.; Charalambides, Maria N.; Williams, J. Gordon

2015-01-22

The aim of this research is to model the deformation and fracture behaviour of brittle wafers often used in chocolate confectionary products. Three point bending and compression experiments were performed on beam and circular disc samples respectively to determine the 'apparent' stress-strain curves in bending and compression. The deformation of the wafer for both these testing types was observed in-situ within an SEM. The wafer is modeled analytically and numerically as a composite material with a core which is more porous than the skins. X-ray tomography was used to generate a three dimensional volume of the wafer microstructure which wasmore » then meshed and used for quantitative analysis. A linear elastic material model, with a damage function and element deletion, was used and the XMT generated architecture was loaded in compression. The output from the FE simulations correlates closely to the load-deflection deformation observed experimentally.« less

Quantitative validation of an air-coupled ultrasonic probe model by Interferometric laser tomography

NASA Astrophysics Data System (ADS)

Revel, G. M.; Pandarese, G.; Cavuto, A.

2012-06-01

The present paper describes the quantitative validation of a finite element (FE) model of the ultrasound beam generated by an air coupled non-contact ultrasound transducer. The model boundary conditions are given by vibration velocities measured by laser vibrometry on the probe membrane. The proposed validation method is based on the comparison between the simulated 3D pressure field and the pressure data measured with interferometric laser tomography technique. The model details and the experimental techniques are described in paper. The analysis of results shows the effectiveness of the proposed approach and the possibility to quantitatively assess and predict the generated acoustic pressure field, with maximum discrepancies in the order of 20% due to uncertainty effects. This step is important for determining in complex problems the real applicability of air-coupled probes and for the simulation of the whole inspection procedure, also when the component is designed, so as to virtually verify its inspectability.

Modelling deformation and fracture in confectionery wafers

NASA Astrophysics Data System (ADS)

Mohammed, Idris K.; Charalambides, Maria N.; Williams, J. Gordon; Rasburn, John

2015-01-01

The aim of this research is to model the deformation and fracture behaviour of brittle wafers often used in chocolate confectionary products. Three point bending and compression experiments were performed on beam and circular disc samples respectively to determine the 'apparent' stress-strain curves in bending and compression. The deformation of the wafer for both these testing types was observed in-situ within an SEM. The wafer is modeled analytically and numerically as a composite material with a core which is more porous than the skins. X-ray tomography was used to generate a three dimensional volume of the wafer microstructure which was then meshed and used for quantitative analysis. A linear elastic material model, with a damage function and element deletion, was used and the XMT generated architecture was loaded in compression. The output from the FE simulations correlates closely to the load-deflection deformation observed experimentally.

Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model

NASA Astrophysics Data System (ADS)

Bonneville, Steeve; Behrends, Thilo; van Cappellen, Philippe; Hyacinthe, Christelle; Röling, Wilfred F. M.

2006-12-01

A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, Mmax, the attachment constant, KP, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, Km∗, on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.

Synthesis of FeCo magnetic nanoalloys and investigation of heating properties for magnetic fluid hyperthermia

NASA Astrophysics Data System (ADS)

Çelik, Özer; Fırat, Tezer

2018-06-01

In this study, size controlled FeCo colloidal magnetic nanoalloys in the range of 11.5-37.2 nm were synthesized by surfactant assistant ball milling method. Magnetic separation technique was performed subsequent to synthesis process so as to obtain magnetic nanoalloy fluid with narrow size distribution. Particle distribution was determined by transmission electron microscope (TEM) while X-ray diffraction (XRD) measurements verified FeCo alloy formation as BCC structure. Vibrating sample magnetometer (VSM) method was used to investigate magnetic properties of nanoalloys. Maximum saturation magnetization and maximum coercivity were obtained as 172 Am2/kg for nanoparticles with the mean size of 37.2 nm and 19.4 mT for nanoparticles with the mean size of 13.3 nm, respectively. The heating ability of FeCo magnetic nanoalloys was determined through calorimetrical measurements for magnetic fluid hyperthermia (MFH) applications. Heat generation mechanisms were investigated by using linear response theory and Stoner-Wohlfarth (S-W) model. Specific absorption rate (SAR) values were obtained in the range of 2-15 W/g for magnetic field frequency of 171 kHz and magnetic field strength in between 6 and 14 mT.

The Magnetorheological Finishing (MRF) of Potassium Dihydrogen Phosphate (KDP) Crystal with Fe3O4 Nanoparticles

NASA Astrophysics Data System (ADS)

Ji, Fang; Xu, Min; Wang, Chao; Li, Xiaoyuan; Gao, Wei; Zhang, Yunfei; Wang, Baorui; Tang, Guangping; Yue, Xiaobin

2016-02-01

The cubic Fe3O4 nanoparticles with sharp horns that display the size distribution between 100 and 200 nm are utilized to substitute the magnetic sensitive medium (carbonyl iron powders, CIPs) and abrasives (CeO2/diamond) simultaneously which are widely employed in conventional magnetorheological finishing fluid. The removal rate of this novel fluid is extremely low compared with the value of conventional one even though the spot of the former is much bigger. This surprising phenomenon is generated due to the small size and low saturation magnetization ( M s) of Fe3O4 and corresponding weak shear stress under external magnetic field according to material removal rate model of magnetorheological finishing (MRF). Different from conventional D-shaped finishing spot, the low M s also results in a shuttle-like spot because the magnetic controllability is weak and particles in the fringe of spot are loose. The surface texture as well as figure accuracy and PSD1 (power spectrum density) of potassium dihydrogen phosphate (KDP) is greatly improved after MRF, which clearly prove the feasibility of substituting CIP and abrasive with Fe3O4 in our novel MRF design.

The Magnetorheological Finishing (MRF) of Potassium Dihydrogen Phosphate (KDP) Crystal with Fe3O4 Nanoparticles.

PubMed

Ji, Fang; Xu, Min; Wang, Chao; Li, Xiaoyuan; Gao, Wei; Zhang, Yunfei; Wang, Baorui; Tang, Guangping; Yue, Xiaobin

2016-12-01

The cubic Fe3O4 nanoparticles with sharp horns that display the size distribution between 100 and 200 nm are utilized to substitute the magnetic sensitive medium (carbonyl iron powders, CIPs) and abrasives (CeO2/diamond) simultaneously which are widely employed in conventional magnetorheological finishing fluid. The removal rate of this novel fluid is extremely low compared with the value of conventional one even though the spot of the former is much bigger. This surprising phenomenon is generated due to the small size and low saturation magnetization (M s) of Fe3O4 and corresponding weak shear stress under external magnetic field according to material removal rate model of magnetorheological finishing (MRF). Different from conventional D-shaped finishing spot, the low M s also results in a shuttle-like spot because the magnetic controllability is weak and particles in the fringe of spot are loose. The surface texture as well as figure accuracy and PSD1 (power spectrum density) of potassium dihydrogen phosphate (KDP) is greatly improved after MRF, which clearly prove the feasibility of substituting CIP and abrasive with Fe3O4 in our novel MRF design.

Molecular details of the yeast frataxin-Isu1 interaction during mitochondrial Fe-S cluster assembly

PubMed Central

Cook, Jeremy D.; Kondapalli, Kalyan C.; Rawat, Swati; Childs, William C.; Murugesan, Yogapriya; Dancis, Andrew; Stemmler, Timothy L.

2010-01-01

Frataxin, a conserved nuclear encoded mitochondrial protein, plays a direct role in iron-sulfur cluster biosynthesis within the ISC assembly pathway. Humans with frataxin deficiency have Friedreich’s ataxia, a neurodegenerative disorder characterized by mitochondrial iron overload and disruption in Fe-S cluster synthesis. Biochemical and genetic studies have shown frataxin interacts with the iron-sulfur cluster assembly scaffold protein (in yeast, there are two: Isu1 and Isu2), indicating frataxin plays a direct role in cluster assembly, possibly by serving as an iron chaperone n the assembly pathway. Here we provide molecular details of how yeast frataxin (Yfh1) interacts with Isu1 as a structural module to better understand the multiprotein complex assembly that completes Fe-S cluster assembly; this complex also includes the cysteine desulfurase (Nfs1 in yeast) and the accessory protein (Isd11), together in the mitochondria. Thermodynamic binding parameters for protein partner and iron binding were measured for the yeast orthologs using isothermal titration calorimetry (ITC). Nuclear magnetic resonance spectroscopy was used to provide the molecular details to understand how Yfh1 interacts with Isu1. X-ray absorption studies were used to electronically and structurally characterize how iron is transferred to Isu1 and then incorporated into a Fe-S cluster. These results were combined with previously published data to generate a structural model for how the Fe-S cluster protein assembly complex can come together to accomplish Fe-S cluster assembly. PMID:20815377

Molecular Details of the Yeast Frataxin-Isu1 Interaction during Mitochondrial Fe-S Cluster Assembly

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

Cook, J.; Kondapalli, K; Rawat, S

2010-01-01

Frataxin, a conserved nuclear-encoded mitochondrial protein, plays a direct role in iron-sulfur cluster biosynthesis within the ISC assembly pathway. Humans with frataxin deficiency have Friedreich's ataxia, a neurodegenerative disorder characterized by mitochondrial iron overload and disruption in Fe-S cluster synthesis. Biochemical and genetic studies have shown frataxin interacts with the iron-sulfur cluster assembly scaffold protein (in yeast, there are two, Isu1 and Isu2), indicating frataxin plays a direct role in cluster assembly, possibly by serving as an iron chaperone in the assembly pathway. Here we provide molecular details of how yeast frataxin (Yfh1) interacts with Isu1 as a structural modulemore » to improve our understanding of the multiprotein complex assembly that completes Fe-S cluster assembly; this complex also includes the cysteine desulfurase (Nfs1 in yeast) and the accessory protein (Isd11), together in the mitochondria. Thermodynamic binding parameters for protein partner and iron binding were measured for the yeast orthologs using isothermal titration calorimetry. Nuclear magnetic resonance spectroscopy was used to provide the molecular details to understand how Yfh1 interacts with Isu1. X-ray absorption studies were used to electronically and structurally characterize how iron is transferred to Isu1 and then incorporated into an Fe-S cluster. These results were combined with previously published data to generate a structural model for how the Fe-S cluster protein assembly complex can come together to accomplish Fe-S cluster assembly.« less

Molecular details of the yeast frataxin-Isu1 interaction during mitochondrial Fe-S cluster assembly.

PubMed

Cook, Jeremy D; Kondapalli, Kalyan C; Rawat, Swati; Childs, William C; Murugesan, Yogapriya; Dancis, Andrew; Stemmler, Timothy L

2010-10-12

Frataxin, a conserved nuclear-encoded mitochondrial protein, plays a direct role in iron-sulfur cluster biosynthesis within the ISC assembly pathway. Humans with frataxin deficiency have Friedreich's ataxia, a neurodegenerative disorder characterized by mitochondrial iron overload and disruption in Fe-S cluster synthesis. Biochemical and genetic studies have shown frataxin interacts with the iron-sulfur cluster assembly scaffold protein (in yeast, there are two, Isu1 and Isu2), indicating frataxin plays a direct role in cluster assembly, possibly by serving as an iron chaperone in the assembly pathway. Here we provide molecular details of how yeast frataxin (Yfh1) interacts with Isu1 as a structural module to improve our understanding of the multiprotein complex assembly that completes Fe-S cluster assembly; this complex also includes the cysteine desulfurase (Nfs1 in yeast) and the accessory protein (Isd11), together in the mitochondria. Thermodynamic binding parameters for protein partner and iron binding were measured for the yeast orthologs using isothermal titration calorimetry. Nuclear magnetic resonance spectroscopy was used to provide the molecular details to understand how Yfh1 interacts with Isu1. X-ray absorption studies were used to electronically and structurally characterize how iron is transferred to Isu1 and then incorporated into an Fe-S cluster. These results were combined with previously published data to generate a structural model for how the Fe-S cluster protein assembly complex can come together to accomplish Fe-S cluster assembly.

System analysis tools for an ELT at ESO

NASA Astrophysics Data System (ADS)

Mueller, Michael; Koch, Franz

2006-06-01

Engineering of complex, large scale systems like the ELT designs currently investigated and developed in Europe and Northern America require powerful and sophisticated tools within specific technical disciplines such as mechanics, optics and control engineering. However, even analyzing a certain component of the telescope like the telescope structure necessitates a system approach to evaluate the structural effects onto the optical performance. This paper shows several software tools developed by the European Southern Observatory (ESO) which focus onto the system approach in the analyses: Using modal results of a finite element analysis the SMI-toolbox allows an easy generation of structural models with different sizes and levels of accuracy for the control design and closed-loop simulations. The optical modeling code BeamWarrior was developed by ESO and Astrium GmbH, Germany) especially for integrated modeling and interfering with a structural model. Within BeamWarrior displacements and deformations can be applied in an arbitrary coordinate system, and hence also in the global coordinates of the FE model avoiding error prone transformations. In addition to this, a sparse state space model object was developed for Matlab to gain in computational efficiency and reduced memory requirements due to the sparsity pattern of both the structural models and the control architecture. As one result these tools allow building an integrated model in order to reliably simulate interactions, cross-coupling effects, system responses, and to evaluate global performance. In order to evaluate disturbance effects on the optical performance in openloop more efficiently, an optical evaluation toolbox was built in the FE software ANSYS which performs Zernike decomposition and best-fit computation of the deformations directly in the FE analysis.

β-FeSi II as a Kankyo (environmentally friendly) semiconductor for solar cells in the space application

NASA Astrophysics Data System (ADS)

Makita, Yunosuke; Ootsuka, Teruhisa; Fukuzawa, Yasuhiro; Otogawa, Naotaka; Abe, Hironori; Liu, Zhengxin; Nakayama, Yasuhiko

2006-04-01

β-FeSi II defined as a Kankyo (Environmentally Friendly) semiconductor is regarded as one of the 3-rd generation semiconductors after Si and GaAs. Versatile features about β-FeSi II are, i) high optical absorption coefficient (>10 5cm -1), ii) chemical stability at temperatures as high as 937°C, iii) high thermoelectric power (Seebeck coefficient of k ~ 10 -4/K), iv) a direct energy band-gap of 0.85 eV, corresponding to 1.5μm of quartz optical fiber communication, v) lattice constant nearly well-matched to Si substrate, vi) high resistance against the humidity, chemical attacks and oxidization. Using β-FeSi II films, one can fabricate various devices such as Si photosensors, solar cells and thermoelectric generators that can be integrated basically on Si-LSI circuits. β-FeSi II has high resistance against the exposition of cosmic rays and radioactive rays owing to the large electron-empty space existing in the electron cloud pertinent to β-FeSi II. Further, the specific gravity of β-FeSi II (4.93) is placed between Si (2.33) and GaAs ((5.33). These features together with the aforementioned high optical absorption coefficient are ideal for the fabrication of solar cells to be used in the space. To demonstrate fascinating capabilities of β-FeSi II, one has to prepare high quality β-FeSi II films. We in this report summarize the current status of β-FeSi II film preparation technologies. Modified MBE and facing-target sputtering (FTS) methods are principally discussed. High quality β-FeSi II films have been formed on Si substrates by these methods. Preliminary structures of n-β-FeSi II /p-Si and p-β-FeSi II /n-Si solar cells indicated an energy conversion efficiency of 3.7%, implying that β-FeSi II is practically a promising semiconductor for a photovoltaic device.

Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation.

PubMed

Tran, Camly T; Williard, Paul G; Kim, Eunsuk

2014-08-27

The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H(•) (e(-)/H(+)). Nitrosylation of (NEt4)2[Fe2S2(SPh)4] (1) in the presence of PhSH or (t)Bu3PhOH results in the formation of (NEt4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or (t)Bu3PhO(•). The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H(•) donor. Employment of clusters with electron-donating groups or H(•) donors from thiols leads to a larger amount of H2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology.

Oxidation of aquatic pollutants by ferrous-oxalate complexes under dark aerobic conditions.

PubMed

Lee, Jaesang; Kim, Jungwon; Choi, Wonyong

2014-06-15

This study evaluates the ability of Fe(II)-oxalate complexes for the generation of OH through oxygen reduction and the oxidative degradation of aquatic pollutants under dark aerobic conditions (i.e., with oxygen but without light). The degradation of 4-chlorophenol (4-CP) was rapid in the mixture of Fe(2+) and oxalate prepared using ultrapure water, but was absent without either Fe(2+) or oxalate. The formation of Fe(II)-oxalate complexes enables two-electron reduction of oxygen to generate H2O2 and subsequent production of OH. The significant inhibition of 4-CP degradation in the presence of H2O2 and OH scavenger confirms such mechanisms. The degradation experiments with varying [Fe(2+)], [oxalate], and initial pH demonstrated that the degradation rate depends on [Fe(II)(Ox)2(2-)], but the degree of degradation is primarily determined by [Fe(II)(Ox)2(2-)]+[Fe(II)(Ox)(0)]. Efficient degradation of diverse aquatic pollutants, especially phenolic pollutants, was observed in the Fe(II)-oxalate complexes system, wherein the oxidation efficacy was primarily correlated with the reaction rate constant between pollutant and OH. The effect of various organic ligands (oxalate, citrate, EDTA, malonate, and acetate) on the degradation kinetics of 4-CP was investigated. The highest efficiency of oxalate for the oxidative degradation is attributed to its high capability to enhance the reducing power and low reactivity with OH. Copyright © 2014 Elsevier B.V. All rights reserved.

Microstructure and mechanical properties of Al-3Fe alloy processed by equal channel angular extrusion

NASA Astrophysics Data System (ADS)

Fuxiao, Yu; Fang, Liu; Dazhi, Zhao; Toth, Laszlo S.

2014-08-01

Al-Fe alloys are attractive for applications at temperatures beyond those normally associated with the conventional aluminum alloys. Under proper solidification condition, a full eutectic microstructure can be generated in Al-Fe alloys at Fe concentration well in excess of the eutectic composition of 1.8 wt.% Fe. The microstructure in this case is characterized by the metastable regular eutectic Al-Al6Fe fibers of nano-scale in diameter, instead of the equilibrium eutectic Al-Al3Fe phase. In this study, the microstructure and mechanical properties of the Al-3Fe alloy with metastable Al6Fe particles deformed by equal channel angular extrusion were investigated. Severe plastic deformation results in a microstructure consisting of submicron equiaxed Al grains with a uniform distribution of submicron Al6Fe particles on the grain boundaries. The room temperature tensile properties of the alloy with this microstructure will be presented.

Ferrate(VI) as a greener oxidant: Electrochemical generation and treatment of phenol.

PubMed

Sun, Xuhui; Zhang, Qi; Liang, He; Ying, Li; Xiangxu, Meng; Sharma, Virender K

2016-12-05

Ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) is a greener oxidant in the treatment of drinking water and wastewater. The electrochemical synthesis of Fe(VI) may be considered environmentally friendly because it involves one-step process to convert Fe(0) to Fe(VI) without using harmful chemicals. Electrolysis was performed by using a sponge iron as an anode in NaOH solution at different ionic strengths. The cyclic voltammetric (CV) curves showed that the sponge iron had higher electrical activity than the grey cast iron. The optimum current density was 0.054mAcm(-2) in 10M NaOH solution, which is much lower than the electrolyte concentrations used in other electrode materials. A comparison of current efficiency and energy consumption was conducted and is briefly discussed. The generated ferrate solution was applied to degrade phenol in water at two levels (2mgL(-1) and 5mgL(-1)). The maximum removal efficiency was ∼70% and the optimum pH for phenol treatment was 9.0. Experiments on phenol removal using conventional coagulants (ferric chloride (FeCl3) and polyaluminium chloride (PAC)) were performed independently to demonstrate that removal of phenol by Fe(VI) occurred mainly by oxidative transformation. A combination of Fe(VI) and coagulant may be advantageous in enhancing removal efficiency, adjusting pH, and facilitating flocculation. Copyright © 2015 Elsevier B.V. All rights reserved.

Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite

DOE PAGES

Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R.; ...

2017-08-17

Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe 2O 3, in contact with one of the fastest known water oxidation catalysts, Ni 0.8Fe 0.2O x, by directly measuring/controlling the current and/or voltage at the Ni 0.8Fe 0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe 2O 3 directly transfer to the catalyst film over a wide rangemore » of conditions and that the Ni 0.8Fe 0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe 2O 3. The Ni 0.8Fe 0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe 2O 3|Ni 0.8Fe 0.2O x interface is significantly decreased by the oxidation of Ni 2+ to Ni 3+ and the associated increase in the Ni 0.8Fe 0.2O x electrical conductivity. Finally, in sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.« less

The anthropogenic influence on Iron deposition over the oceans: a 3-D global modeling

NASA Astrophysics Data System (ADS)

Myriokefalitakis, Stelios; Mihalopoulos, Nikos; Baker, Alex; Kanakidou, Maria

2014-05-01

Iron (Fe) deposition over oceans is directly linked to the marine biological productivity and consequently to atmospheric CO2 concentrations. Experimental and modeling results support that both inorganic (sulphate, ammonium and nitrate) and organic (e.g. oxalate) ligands can increase the Fe mobilization. Mineral dust deposition is considered as the most important supply of bioavailable Fe in the oceans. Although, due to the low soil soluble iron fractions, atmospheric processes which are also related to anthropogenic emissions, can convert iron to more soluble forms in the atmosphere. Recent studies also support that anthropogenic emissions of Fe from combustion sources also significantly contribute to the dissolved Fe atmospheric pool. The evaluation of the impact of humans on atmospheric soluble or bioavailable Fe deposition remains challenging, since Fe mobilization due to changes in anthropogenic emissions is largely uncertain. In the present study, the global atmospheric Fe cycle is parameterized in the 3-D chemical transport global model TM4-ECPL and the model is used to calculate the Fe deposition over the oceans. The model considers explicitly organic, sulfur and nitrogen gas-phase chemistry, aqueous-phase organic chemistry, including oxalate and all major aerosol constituents. TM4-ECPL simulates the organic and inorganic ligand-promoted mineral Fe dissolution and also aqueous-phase photochemical reactions between different forms of Fe (III/II). Primary emissions of Fe associated with dust and soluble Fe from combustion processes as well as atmospheric processing of the emitted Fe is taken into account in the model Sensitivity simulations are performed to study the impact of anthropogenic emissions on Fe deposition. For this preindustrial, present and future emission scenarios are used in the model in order to examine the response of chemical composition of iron-containing aerosols to environmental changes. The release of soluble iron associated with mineral dust and with the emissions of combustion aerosols is investigated. Model results are compared with available observations to evaluate their robustness. This work is supported by the ESF-NSRF ARISTEIA grant PANOPLY (Pollution Alters Natural Aerosol Composition: implications for Ocean Productivity, cLimate and air qualitY).

Generation of Elliptically Polarized Terahertz Waves from Antiferromagnetic Sandwiched Structure.

PubMed

Zhou, Sheng; Zhang, Qiang; Fu, Shu-Fang; Wang, Xuan-Zhang; Song, Yu-Ling; Wang, Xiang-Guang; Qu, Xiu-Rong

2018-04-01

The generation of elliptically polarized electromagnetic wave of an antiferromagnetic (AF)/dielectric sandwiched structure in the terahertz range is studied. The frequency and external magnetic field can change the AF optical response, resulting in the generation of elliptical polarization. An especially useful geometry with high levels of the generation of elliptical polarization is found in the case where an incident electromagnetic wave perpendicularly illuminates the sandwiched structure, the AF anisotropy axis is vertical to the wave-vector and the external magnetic field is pointed along the wave-vector. In numerical calculations, the AF layer is FeF2 and the dielectric layers are ZnF2. Although the effect originates from the AF layer, it can be also influenced by the sandwiched structure. We found that the ZnF2/FeF2/ZnF2 structure possesses optimal rotation of the principal axis and ellipticity, which can reach up to about thrice that of a single FeF2 layer.

Characterization of a high-spin non-heme Fe(III)-OOH intermediate and its quantitative conversion to an Fe(IV)═O complex.

PubMed

Li, Feifei; Meier, Katlyn K; Cranswick, Matthew A; Chakrabarti, Mrinmoy; Van Heuvelen, Katherine M; Münck, Eckard; Que, Lawrence

2011-05-18

We have generated a high-spin Fe(III)-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This Fe(III)-OOH species can be converted quantitatively to an Fe(IV)═O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong Fe(III)-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin Fe(III)-peroxo intermediates of non-heme iron enzymes may be promoted. © 2011 American Chemical Society

Enhanced orbital magnetic moment in FeCo nanogranules observed by Barnett effect

NASA Astrophysics Data System (ADS)

Ogata, Y.; Chudo, H.; Gu, B.; Kobayashi, N.; Ono, M.; Harii, K.; Matsuo, M.; Saitoh, E.; Maekawa, S.

2017-11-01

The gyroscopic g factor, g‧ , of FeCo nanogranules embedded in a matrix of MgF2 (FeCo-MgF2) was determined by measuring the magnetic-field generation from a rotating sample due to the Barnett effect. The g‧ value of the FeCo-MgF2 is estimated to be 1.76 ± 0.11. The orbital contribution to the magnetic moment in the FeCo nanogranules was found to be quite large compared with that in bulk FeCo, being consistent with a density-functional-theory calculation that shows that the orbital magnetic moment may increase at the FeCo/MgF2 interfaces. The result suggests that the orbital magnetic moment is enhanced by symmetry breaking at the surface of the FeCo nanogranules.

Ordering, nanostructure and high-field magnetization of quenched and annealed metastable ilmenite-hematite solid solutions

NASA Astrophysics Data System (ADS)

Fabian, Karl; Thomas, Christopher I.; McEnroe, Suzanne A.; Robinson, Peter; Mukai, Hiroki

2013-04-01

The ilmenite-hematite solid solution series xFeTiO3-(1 - x)Fe2O3 can generate extremely unusual magnetic properties in natural rocks and has been investigated for more than fifty years. Both, ilmenite (FeTiO3) and hematite (Fe2O3) are antiferromagnetic, but intermediate compositions are either antiferromagnetic or ferrimagnetic, depending on their chemical order. Within a single sample, nano-scale variations in local composition x and ordering state Q depend on minute details of the cooling and annealing history, and have large effects on the magnetic properties, which include self-reversal of thermoremanent magnetization and large exchange bias. We present a systematic study of magnetic properties of samples in the composition range of 0.6 ˜ x ˜ 0.7 with differing nanostructure and consequently differing magnetic properties. Using high-field measurements up to 7 T, together with TEM images and theoretical models we classify nanostructure formation in terms of x, Q, and characteristic size d. These characteristics are then linked to the magnetic properties. The sample characterization relies on average mean-field models of Ms(T). To implement the varying Fe and Ti densities, and the distribution of Fe ions in the variably ordered solid solutions, the models either use statistical interactions between sites, whereby they effectively average over all possible configurations, or they describe specific random configurations. Statistical mean field models are successful in predicting the Curie temperatures TC and Ms(T) curves of the Ilmx solid solutions. The results depend on the interaction coefficients, which either had been determined by neutron diffraction measurements (Samuelson and Shirane, 1979), by Monte-Carlo model fits (Harrison, 2006), or by density-functional theoretic calculations (Nabi et al. 2010). Hysteresis branches have been measured for a wide variety of samples at different temperatures 40 K, 100 K and 300 K. None of them saturate at 7 T, the strongest field available to us so far. Some of the samples show the beginnings of a pseudo-metamagnetic transition at the upper limits of the measurements. In previous models this is explained by anti-phase boundaries and exchange coupling between ordered and disordered regions with differing sizes and hence differing responses to an external field. These effects will be studied further up to 60 T using a European high-field laboratory within the EuroMagNET II/EMFL scheme.

Thermodynamic and kinetic modeling of grain boundary equilibrium segregation of P in α-Fe

DOE PAGES

Yang, Y.; Chen, S. -L.

2017-04-18

Phosphorus is a primary contributor to interface fracture and embrittlement in steels because of its strong segregation tendency at grain boundaries (GBs). The lack of consistency in literature data imposes great difficulties in performing segregation modeling that is compatible with both the Langmuir-Mclean segregation theory and the thermodynamic description of the Bcc(Fe,P) phase. Our work carefully evaluated experimental data for phosphorus segregation at GBs in -Fe and provided a new formula for converting the auger electron spectroscopy (AES) peak height ratio to GBs. Furthermore, based on newly assessed literature data, this work proposes that the major driving force for phosphorusmore » segregation is the formation of Fe 3P-type clusters at GBs, which is supported not only by the almost equivalent Gibbs energy of _Fe using the Bcc(Fe,P) substitutional model and the Bcc(Fe,Fe 3P, P) associate model, but also by the good agreement between thermodynamic/kinetic modeling results and experimental data.« less

Controllable construction of flower-like FeS/Fe2O3 composite for lithium storage

NASA Astrophysics Data System (ADS)

Wang, Jie; He, Huan; Wu, Zexing; Liang, Jianing; Han, Lili; Xin, Huolin L.; Guo, Xuyun; Zhu, Ye; Wang, Deli

2018-07-01

Transitions metal sulfides/oxides have been considered as promising anode candidates for next generation lithium-ion batteries (LIBs) due to high theoretical capacities. However, the large volume change during lithiation/delithiation process and poor electronic conductivity often result in a poor charging/discharging performance. Herein, we design a flower-like FeS/Fe2O3 composite via a simple "solvothermal-oxidation" method, in which the Fe2O3 is most distributed on the surface of the flower. The unique porous structure and synergistic effect between FeS and Fe2O3 not only accommodate the large volume expansion, but also facilitate Li ion and electron transport. The Fe2O3 shell effectively reduce the dissolution of Li2Sx during discharge/charge process. When serving as the anode material in lithium ion battery, FeS/Fe2O3 exhibits superior specific capacity, rate capacity and cycling stability compared with pure FeS and Fe2O3.

Finite-element modeling of compression and gravity on a population of breast phantoms for multimodality imaging simulation.

PubMed

Sturgeon, Gregory M; Kiarashi, Nooshin; Lo, Joseph Y; Samei, E; Segars, W P

2016-05-01

The authors are developing a series of computational breast phantoms based on breast CT data for imaging research. In this work, the authors develop a program that will allow a user to alter the phantoms to simulate the effect of gravity and compression of the breast (craniocaudal or mediolateral oblique) making the phantoms applicable to multimodality imaging. This application utilizes a template finite-element (FE) breast model that can be applied to their presegmented voxelized breast phantoms. The FE model is automatically fit to the geometry of a given breast phantom, and the material properties of each element are set based on the segmented voxels contained within the element. The loading and boundary conditions, which include gravity, are then assigned based on a user-defined position and compression. The effect of applying these loads to the breast is computed using a multistage contact analysis in FEBio, a freely available and well-validated FE software package specifically designed for biomedical applications. The resulting deformation of the breast is then applied to a boundary mesh representation of the phantom that can be used for simulating medical images. An efficient script performs the above actions seamlessly. The user only needs to specify which voxelized breast phantom to use, the compressed thickness, and orientation of the breast. The authors utilized their FE application to simulate compressed states of the breast indicative of mammography and tomosynthesis. Gravity and compression were simulated on example phantoms and used to generate mammograms in the craniocaudal or mediolateral oblique views. The simulated mammograms show a high degree of realism illustrating the utility of the FE method in simulating imaging data of repositioned and compressed breasts. The breast phantoms and the compression software can become a useful resource to the breast imaging research community. These phantoms can then be used to evaluate and compare imaging modalities that involve different positioning and compression of the breast.

Nickel(0) nanoparticles supported on bare or coated cobalt ferrite as highly active, magnetically isolable and reusable catalyst for hydrolytic dehydrogenation of ammonia borane.

PubMed

Manna, Joydev; Akbayrak, Serdar; Özkar, Saim

2017-12-15

Nickel(0) nanoparticles supported on cobalt ferrite (Ni 0 /CoFe 2 O 4 ), polydopamine coated cobalt ferrite (Ni 0 /PDA-CoFe 2 O 4 ) or silica coated cobalt ferrite (Ni 0 /SiO 2 -CoFe 2 O 4 ) are prepared and used as catalysts in hydrogen generation from the hydrolysis of ammonia borane at room temperature. Ni 0 /CoFe 2 O 4 (4.0% wt. Ni) shows the highest catalytic activity with a TOF value of 38.3min -1 in hydrogen generation from the hydrolysis of ammonia borane at 25.0±0.1°C. However, the initial catalytic activity of Ni 0 /CoFe 2 O 4 catalyst is not preserved in subsequent runs of hydrolysis. Coating the surface of cobalt ferrite support with polydopamine or silica leads to a significant improvement in the stability of catalysts. The TOF values of Ni 0 /PDA-CoFe 2 O 4 and Ni 0 /SiO 2 -CoFe 2 O 4 are found to be 7.6 and 5.3min -1 , respectively, at 25.0±0.1°C. Ni 0 /PDA-CoFe 2 O 4 catalyst shows high reusability as compared to the Ni 0 /CoFe 2 O 4 and Ni 0 /SiO 2 -CoFe 2 O 4 catalysts in hydrolytic dehydrogenation of ammonia borane at room temperature. All the catalysts are characterized by using a combination of various advanced analytical techniques. The results reveal that nickel nanoparticles with an average size of 12.3±0.7nm are well dispersed on the surface of PDA-CoFe 2 O 4 . . Copyright © 2017 Elsevier Inc. All rights reserved.

Acoustic design criteria in a general system for structural optimization

NASA Technical Reports Server (NTRS)

Brama, Torsten

1990-01-01

Passenger comfort is of great importance in most transport vehicles. For instance, in the new generation of regional turboprop aircraft, a low noise level is vital to be competitive on the market. The possibilities to predict noise levels analytically has improved rapidly in recent years. This will make it possible to take acoustic design criteria into account in early project stages. The development of the ASKA FE-system to include also acoustic analysis has been carried out at Saab Aircraft Division and the Aeronautical Research Institute of Sweden in a joint project. New finite elements have been developed to model the free fluid, porous damping materials, and the interaction between the fluid and structural degrees of freedom. The FE approach to the acoustic analysis is best suited for lower frequencies up to a few hundred Hz. For accurate analysis of interior cabin noise, large 3-D FE-models are built, but 2-D models are also considered to be useful for parametric studies and optimization. The interest is here focused on the introduction of an acoustic design criteria in the general structural optimization system OPTSYS available at the Saab Aircraft Division. The first implementation addresses a somewhat limited class of problems. The problems solved are formulated: Minimize the structural weight by modifying the dimensions of the structure while keeping the noise level in the cavity and other structural design criteria within specified limits.

An integrated approach to investigate the hydrological behavior of the Santa Fe River Basin, north central Florida

NASA Astrophysics Data System (ADS)

Vibhava, F.; Graham, W. D.; De Rooij, R.; Maxwell, R. M.; Martin, J. B.; Cohen, M. J.

2011-12-01

The Santa Fe River Basin (SFRB) consists of three linked hydrologic units: the upper confined region (UCR), semi-confined transitional region (Cody Escarpment, CE) and lower unconfined region (LUR). Contrasting geological characteristics among these units affect streamflow generation processes. In the UCR, surface runoff and surficial stores dominate whereas in the LCR minimal surface runoff occurs and flow is dominated by groundwater sources and sinks. In the CE region the Santa Fe River (SFR) is captured entirely by a sinkhole into the Floridan aquifer, emerging as a first magnitude spring 6 km to the south. In light of these contrasting hydrological settings, developing a predictive, basin scale, physically-based hydrologic simulation model remains a research challenge. This ongoing study aims to assess the ability of a fully-coupled, physically-based three-dimensional hydrologic model (PARFLOW-CLM), to predict hydrologic conditions in the SFRB. The assessment will include testing the model's ability to adequately represent surface and subsurface flow sources, flow paths, and travel times within the basin as well as the surface-groundwater exchanges throughout the basin. In addition to simulating water fluxes, we also are collecting high resolution specific conductivity data at 10 locations throughout the river. Our objective is to exploit hypothesized strong end-member separation between riverine source water geochemistry to further refine the PARFLOW-CLM representation of riverine mixing and delivery dynamics.

Study on Emission Spectral Lines of Iron, Fe in Laser-Induced Breakdown Spectroscopy (LIBS) on Soil Samples

NASA Astrophysics Data System (ADS)

Idris, Nasrullah; Lahna, Kurnia; Fadhli; Ramli, Muliadi

2017-05-01

In this work, LIBS technique has been used for detection of heavy metal especially iron, Fe in soil sample. As there are a large number of emission spectral lines due to Fe and other constituents in soil, this study is intended to identify emission spectral lines of Fe and finally to find best fit emission spectral lines for carrying out a qualitative and quantitative analysis. LIBS apparatus used in this work consists of a laser system (Neodymium Yttrium Aluminum Garnet, Nd-YAG: Quanta Ray; LAB SERIES; 1,064 nm; 500 mJ; 8 ns) and an optical multichannel analyzer (OMA) system consisting of a spectrograph (McPherson model 2061; 1,000 mm focal length; f/8.6 Czerny- Turner) and an intensified charge coupled device (ICCD) 1024x256 pixels (Andor I*Star). The soil sample was collected from Banda Aceh city, Aceh, Indonesia. For spectral data acquisition, the soil sample has been prepared by a pressing machine in the form of pellet. The laser beam was focused using a high density lens (f=+150 mm) and irradiated on the surface of the pellet for generating luminous plasma under 1 atmosphere of air surrounding. The plasma emission was collected by an optical fiber and then sent to the optical multichannel analyzer (OMA) system for acquisition of the emission spectra. It was found that there are many Fe emission lines both atomic lines (Fe I) and ionic lines (Fe II) appeared in all detection windows in the wavelength regions, ranging from 200 nm to 1000 nm. The emission lines of Fe with strong intensities occurs together with emission lines due to other atoms such as Mg, Ca, and Si. Thus, the identification of emission lines from Fe is complicated by presence of many other lines due to other major and minor elements in soil. Considering the features of the detected emission lines, several emission spectral lines of Fe I (atomic emission line), especially Fe I 404.58 nm occurring at visible range are potential to be good candidate of analytical lines in relation to detection heavy metal pollution, Fe, in soil sample.

Comparison of Ab initio Low-Energy Models for LaFePO, LaFeAsO, BaFe2As2, LiFeAs, FeSe, and FeTe

NASA Astrophysics Data System (ADS)

Nakamura, Kazuma; Miyake, Takashi; Arita, Ryotaro; Imada, Masatoshi

2010-03-01

We present effective low-energy models for LaFePO and LaFeAsO (1111 family), BaFe2As2 (122), LiFeAs (111), and FeSe and FeTe (11) [1], based on ab initio downfolding scheme, a constrained random-phase-approximation method combined with maximally localized Wannier functions. Comparison among the effective models, derived for 5 Fe-3d bands, provides a basis for interpreting physics/chemistry; material dependences of electron correlations, a multiband character entangled by the 3d orbitals, and the geometrical frustration depending on hybridizations between iron and pnictogen/chalcogen orbitals. We found that LaFePO in the 1111 family resides in the weak correlation regime, while LaFeAsO and 111/122 compounds are the intermediate region and FeSe and FeTe in the 11 family are located in the strong correlation regime. A principal parameter relevant to the physics is clarified to be the pnictogen/chalcogen height from the iron layer. Implications in low-energy properties including magnetism and superconductivity are discussed. [1] T. Miyake, K. Nakamura, R. Arita, and M. Imada, arXiv:0911.3705.

Synthesis, characterization, and reactivity studies of heterodinuclear complexes modeling active sites in purple acid phospatases.

PubMed

Jarenmark, Martin; Haukka, Matti; Demeshko, Serhiy; Tuczek, Felix; Zuppiroli, Luca; Meyer, Franc; Nordlander, Ebbe

2011-05-02

To model the heterodinuclear active sites in plant purple acid phosphatases, a mononuclear synthon, [Fe(III)(H(2)IPCPMP)(Cl(2))][PF(6)] (1), has been generated in situ from the ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)amino methyl)-4-methylphenol (IPCPMP) and used to synthesize heterodinuclear complexes of the formulas [Fe(III)M(II)(IPCPMP)(OAc)(2)(CH(3)OH)][PF(6)] (M = Zn (2), Co (3), Ni (4), Mn (5)), [Fe(III)Zn(II)(IPCPMP)(mpdp)][PF(6)] (6) (mpdp = meta-phenylene-dipropionate), and [Fe(III)Cu(II)(IPCPMP) (OAc)}(2)(μ-O)][PF(6)] (7). Complexes 2-4, 6, and 7 have been crystallographically characterized. The structure of 6 is a solid state coordination polymer with heterodinuclear monomeric units, and 7 is a tetranuclear complex consisting of two heterodinuclear phenolate-bridged Fe(III)Cu(II) units bridged through a μ-oxido group between the two Fe(III) ions. Mössbauer spectra confirm the presence of high spin Fe(III) in an octahedral environment for 1, 3, and 5 while 2 and 4 display relaxation effects. Magnetic susceptibility measurements indicate weak antiferromagnetic coupling for 3, 4, and 5 and confirm the assignment of the metal centers in 2-5 as high spin Fe(III)-M(II) (M = Zn, Co (high spin), Ni (high spin), Mn (high spin)). Complexes 2-5 are intact in acetonitrile solution as indicated by IR spectroscopy (for 2-4) and electrospray ionization mass spectrometry (ESI-MS) but partly dissociate to hydroxide species and a mononuclear complex in water/acetonitrile solutions. UV-vis spectroscopy reveal pH-dependent behavior, and species that form upon increasing the pH have been assigned to μ-hydroxido-bridged Fe(III)M(II) complexes for 2-5 although 2 and 3 is further transformed into what is propsed to be a μ-oxido-bridged tetranuclear complex similar to 7. Complexes 2-5 enhance phosphodiester cleavage of 2-hydroxy-propyl-p-nitrophenyl phosphate (HPNP) and bis(2,4-dinitrophenyl)phosphate (BDNPP), but the reactivities are different for different complexes and generally show strong pH dependence. © 2011 American Chemical Society

Fe isotopes and the contrasting petrogenesis of A-, I- and S-type granite

NASA Astrophysics Data System (ADS)

Foden, John; Sossi, Paolo A.; Wawryk, Christine M.

2015-01-01

We present new Fe isotope data of 42 S-, I- and A-type (ferroan) granites from the Cambrian Delamerian orogen in South Australia, the Palaeozoic Lachlan Fold Belt and Western USA. Interpretation of these data, together with modelling suggests that magmatic processes do result in quite complex Fe-isotopic differentiation trends and can lead to granites with isotopically heavy iron with δ57Fe > 0.35‰. By comparison Mid-Ocean Ridge Basalts (MORBs) have δ57Fe = 0.15‰ (Teng et al., 2013). These variations are similar to those previously reported (Poitrasson and Freydier, 2005; Heimann et al., 2008; Telus et al., 2012), but, contrary to some interpretations (Beard and Johnson, 2006; Heimann et al., 2008), heavy values are not necessarily the product of late-stage hydrothermal fluid loss, though this process is undoubtedly also an important factor in some circumstances. A-type (ferroan) granites reach very heavy δ57Fe values (0.4-0.5‰) whereas I-types are systematically lighter (δ57Fe = 0.2‰). S-type granites show a range of intermediate values, but also tend to be isotopically heavy (δ57Fe ≈ 0.2-0.4‰). Our results show that the iron isotopic values and trends are signatures that reflect granite generation processes. A modelling using the Rhyolite-MELTS software suggests that contrasting trajectories and end-points in Fe isotope evolution towards granite depend on: oxidation state of the evolving magma and, whether or not the system is oxygen-buffered. Iron isotopic evolution supports an origin of ferroan A-type granite from protracted, closed magma chamber fractionation of moderately reduced mafic magmas. In these systems magnetite saturation is delayed and the ferric iron budget is finite. I-type systems originate with the supply of relatively oxidised, hydrous, subduction-related magmas from the mantle wedge to the upper plate crust. These then experience oxygen-buffered open-system AFC processes in lower crustal hot-zones. S-type magmas are crustal melts that crystallise under reduced conditions initially imposed at source by sulphidic or graphitic sedimentary protoliths. The composition of the resulting melts reflects the domination of partial melting where conditions are hence buffered (open system) followed by subsequent late-stage, closed system fractionation of these extracted, reduced magmas.

Thermal analysis of large-capacity LiFePO4 power batteries for electric vehicles

NASA Astrophysics Data System (ADS)

Lin, Chunjing; Xu, Sichuan; Li, Zhao; Li, Bin; Chang, Guofeng; Liu, Jinling

2015-10-01

Excellent design of a thermal management system requires good understanding of the thermal behaviors of power batteries. In this study, the electrochemical and heat performances of a prismatic 40 Ah C/LiFePO4 battery are investigated with a focus on the influence of temperature on cell capacity in a mixed charge-discharge cycle. In addition, the heat generation and energy efficiency of a battery are determined during charge and discharge at different current rates. The experimental results indicate that in certain temperature ranges, both the charging and discharging capacities increase significantly as the temperature increases. In addition, the energy efficiency reaches more than 95% when the battery runs at a current rate of 0.33 C-2 C and temperature of 25-45 °C. A thermal mathematical model based on experimentally obtained internal resistances and entropy coefficients is developed. Using this model, the increase in the battery temperature is simulated based on specific heat values that are measured experimentally and calculated theoretically. The results from the simulation indicate that the temperature increase agrees well with the experimental values, the measured specific heat provides better results than the calculated specific heat and the heat generated decreases as the temperature increases.

Ultrafast spintronics roadmap: from femtosecond spin current pulses to terahertz non-uniform spin dynamics via nano-confined spin transfer torques (Conference Presentation)

NASA Astrophysics Data System (ADS)

Melnikov, Alexey; Razdolski, Ilya; Alekhin, Alexandr; Ilin, Nikita; Meyburg, Jan; Diesing, Detlef; Roddatis, Vladimir; Rungger, Ivan; Stamenova, Maria; Sanvito, Stefano; Bovensiepen, Uwe

2016-10-01

Further development of spintronics requires miniaturization and reduction of characteristic timescales of spin dynamics combining the nanometer spatial and femtosecond temporal ranges. These demands shift the focus of interest towards the fundamental open question of the interaction of femtosecond spin current (SC) pulses with a ferromagnet (FM). The spatio-temporal properties of the spin transfer torque (STT) exerted by ultrashort SC pulses on the FM open the time domain for studying STT fingerprint on spatially non-uniform magnetization dynamics. Using the sensitivity of magneto-induced second harmonic generation to SC, we develop technique for SC monitoring. With 20 fs resolution, we demonstrate the generation of 250 fs-long SC pulses in Fe/Au/Fe/MgO(001) structures. Their temporal profile indicates (i) nearly-ballistic hot electron transport in Au and (ii) that the pulse duration is primarily determined by the thermalization time of laser-excited hot carriers in Fe. Together with strongly spin-dependent Fe/Au interface transmission calculated for these carriers, this suggests the non-thermal spin-dependent Seebeck effect dominating the generation of ultrashort SC pulses. The analysis of SC transmission/reflection at the Au/Fe interface shows that hot electron spins orthogonal to the Fe magnetization rotate gaining huge parallel (anti-parallel) projection in transmitted (reflected) SC. This is accompanied by a STT-induced perturbation of the magnetization localized at the interface, which excites the inhomogeneous high-frequency spin dynamics in the FM. Time-resolved magneto-optical studies reveal the excitation of several standing spin wave modes in the Fe film with their spectrum extending up to 0.6 THz and indicating the STT spatial confinement to 2 nm.

[Effect of muscle biofidelity on thoracic impact biomechanical response of a six-year-old child using finite element method].

PubMed

Cui, Shihai; Shan, Leilei; Li, Haiyan; Lu, Wenle; He, Lijuan; Ruan, Shijie

2017-02-01

Finite element(FE) model of thorax with high biofidelity is one of the most important methods to investigate thoracic injury mechanism because of the absence of pediatric cadaver experiments. Based on the validated thorax finite element model, the FE models with equivalent muscles and real geometric muscles were developed respectively, and the effect of muscle biofidelity on thoracic injury was analyzed with reconstructing pediatric cadaver thorax impact experiments. The simulation results showed that the thoracic impact force, the maximum displacement and the maximum von-Mises stress of FE models with equivalent muscles were slightly greater than those from FE models with real geometric muscles, and the maximum principal strains of heart and lung were a little lower. And the correlation coefficient between cadaver corridor and FE model with real muscles was also greater than that between cadaver corridor and FE model with equivalent muscles. As a conclusion, the FE models with real geometric muscles can accurately reflect the biomechanical response of thorax during the impact.

Sol–gel auto combustion synthesis of CoFe{sub 2}O{sub 4}/1-methyl-2-pyrrolidone nanocomposite with ethylene glycol: Its magnetic characterization

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

Topkaya, R., E-mail: rtopkaya@gyte.edu.tr; Kurtan, U.; Junejo, Y.

2013-09-01

Graphical abstract: - Highlights: • CoFe{sub 2}O{sub 4} was generated by sol–gel autocombustion using 1-methyl-2-pyrrolidone and ethylene glycol. • The presence of spin-disordered surface layer on magnetic core was established. • A linear dependence of the coercivity on temperature was fitted to Kneller's law. - Abstract: Magnetic nanoparticles were generated by sol–gel auto combustion synthesis of metal salts in the presence of 1-methyl-2-pyrrolidone, a functional solvent and ethylene glycol as usual solvent. The average crystallite size was obtained by using line profile fitting as 11 ± 5 nm. The saturation magnetization value decreases with usage of the ethylene glycol inmore » synthesis. The observed exchange bias effect further confirms the existence of the magnetically ordered core surrounded by spin-disordered surface layer and the ethylene glycol. Square-root temperature dependence of coercivity can be fitted to Kneller's law in the temperature range of 10–400 K. The reduced remanent magnetization values lower than the theoretical value of 0.5 for non-interacting single domain particles indicate the CoFe{sub 2}O{sub 4}-1-methyl-2-pyrrolidone nanocomposite to have uniaxial anisotropy instead of the expected cubic anisotropy according to the Stoner–Wohlfarth model.« less

Relationship between sample volumes and modulus of human vertebral trabecular bone in micro-finite element analysis.

PubMed

Wen, Xin-Xin; Xu, Chao; Zong, Chun-Lin; Feng, Ya-Fei; Ma, Xiang-Yu; Wang, Fa-Qi; Yan, Ya-Bo; Lei, Wei

2016-07-01

Micro-finite element (μFE) models have been widely used to assess the biomechanical properties of trabecular bone. How to choose a proper sample volume of trabecular bone, which could predict the real bone biomechanical properties and reduce the calculation time, was an interesting problem. Therefore, the purpose of this study was to investigate the relationship between different sample volumes and apparent elastic modulus (E) calculated from μFE model. 5 Human lumbar vertebral bodies (L1-L5) were scanned by micro-CT. Cubic concentric samples of different lengths were constructed as the experimental groups and the largest possible volumes of interest (VOI) were constructed as the control group. A direct voxel-to-element approach was used to generate μFE models and steel layers were added to the superior and inferior surface to mimic axial compression tests. A 1% axial strain was prescribed to the top surface of the model to obtain the E values. ANOVA tests were performed to compare the E values from the different VOIs against that of the control group. Nonlinear function curve fitting was performed to study the relationship between volumes and E values. The larger cubic VOI included more nodes and elements, and more CPU times were needed for calculations. E values showed a descending tendency as the length of cubic VOI decreased. When the volume of VOI was smaller than (7.34mm(3)), E values were significantly different from the control group. The fit function showed that E values approached an asymptotic values with increasing length of VOI. Our study demonstrated that apparent elastic modulus calculated from μFE models were affected by the sample volumes. There was a descending tendency of E values as the length of cubic VOI decreased. Sample volume which was not smaller than (7.34mm(3)) was efficient enough and timesaving for the calculation of E. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation and function of chromate conversion coating on aircraft aluminum alloy probed by vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Xia, Lin

2000-10-01

A Chromate Conversion Coating (CCC) is currently one of the most effective methods for protecting aluminum alloys from corrosion. Its unique "self-healing" property has been proved to be critical in corrosion prevention. During the formation process, CrVI, is "stored" in the CCC films. Under in-field conditions, most of the CrVI can leach out and diffuse to local defects, and stop corrosion. However, the involvement of highly toxic CrVI makes CCC system environmentally hazardous. In order to find less-toxic alternatives, the formation and protection mechanisms of CCC must be understood. Formation and function of CCC film are the focus of this study, and vibrational spectroscopy was chosen due to its superior structural sensitivity. First, the structure of CCC film was characterized. The structural similarity between CCC film and a synthetic Cr-mixed-oxide was found, and certain tests were conducted on the bulk synthetic powder which were not feasible on the thin film. All of the structural studies indicated that CCC film is mainly a CrIII-hydroxide gel layer, which adsorbs CrVI-oxy species through CrIII-O-Cr VI chemical bonds. Further analysis revealed the reversible Cr III-CrVI adsorption-desorption equilibrium, and a mathematical model ("Langmuir" model) was established to explain the Cr VI storage-release mechanism quantitatively. In addition, the function of Fe(CN)63-, an additive in the coating solution, was studied. The results indicate that Fe(CN)63- mediates the slow reaction between Al and CrVI, and the mediation mechanism can be illustrated as below: FeCN 3- 6+Al=FeCN 4-6+Al3+ ↑ FeCN 4- 6+CrVI=FeCN 3-6+CrIII In general, the formation of CCC is mediated by Fe(CN)63-, thus Al reduces CrVI quickly and generates CrIII-hydroxide on the alloy surface. The nascent CrIII-hydroxide is chemically active enough to form chemical bonds with CrVI from the solution, through Cr III-O-CrVI bonding. Such CrIII-O-Cr VI structure can form and break up reversibly according to the Langmuir model, providing mobile CrVI for in-field protection.

Enhancement of Fenton processes at initial circumneutral pH for the degradation of norfloxacin with Fe@Fe2O3 core-shell nanomaterials.

PubMed

Liu, Jingyi; Hu, Wenyong; Sun, Maogui; Xiong, Ouyang; Yu, Haibin; Feng, Haopeng; Wu, Xuan; Tang, Lin; Zhou, Yaoyu

2018-06-13

The degradation of norfloxacin by Fenton reagent with core-shell Fe@Fe 2 O 3 nanomaterials was studied under neutral conditions in a closed batch system. Norfloxacin was significantly degraded (90%) in the Fenton system with Fe@Fe 2 O 3 in 30 min at the initial pH 7.0, but slightly degraded in Fenton system without Fe@Fe 2 O 3 under the same experimental conditions. The intermediate products were investigated by gas chromatography-mass spectrometry, and the possible Fenton oxidation pathway of norfloxacin in the presence of Fe@Fe 2 O 3 nanowires was proposed. Electron spin resonance spectroscopy was used to identify and characterize the free radicals generated, and the mechanism for norfloxacin degradation was also revealed. Finally, the reusability and the stability of Fe@Fe 2 O 3 nanomaterials were studied using x-ray diffraction and scanning electron microscope, which indicated that Fe@Fe 2 O 3 is a stable catalyst and can be used repetitively in environmental pollution control.

Three-dimensional finite element models of the human pubic symphysis with viscohyperelastic soft tissues.

PubMed

Li, Zuoping; Alonso, Jorge E; Kim, Jong-Eun; Davidson, James S; Etheridge, Brandon S; Eberhardt, Alan W

2006-09-01

Three-dimensional finite element (FE) models of human pubic symphyses were constructed from computed tomography image data of one male and one female cadaver pelvis. The pubic bones, interpubic fibrocartilaginous disc and four pubic ligaments were segmented semi-automatically and meshed with hexahedral elements using automatic mesh generation schemes. A two-term viscoelastic Prony series, determined by curve fitting results of compressive creep experiments, was used to model the rate-dependent effects of the interpubic disc and the pubic ligaments. Three-parameter Mooney-Rivlin material coefficients were calculated for the discs using a heuristic FE approach based on average experimental joint compression data. Similarly, a transversely isotropic hyperelastic material model was applied to the ligaments to capture average tensile responses. Linear elastic isotropic properties were assigned to bone. The applicability of the resulting models was tested in bending simulations in four directions and in tensile tests of varying load rates. The model-predicted results correlated reasonably with the joint bending stiffnesses and rate-dependent tensile responses measured in experiments, supporting the validity of the estimated material coefficients and overall modeling approach. This study represents an important and necessary step in the eventual development of biofidelic pelvis models to investigate symphysis response under high-energy impact conditions, such as motor vehicle collisions.

Multiscale Modeling of Carbon Nanotube-Epoxy Nanocomposites

NASA Astrophysics Data System (ADS)

Fasanella, Nicholas A.

Epoxy-composites are widely used in the aerospace industry. In order to improve upon stiffness and thermal conductivity; carbon nanotube additives to epoxies are being explored. This dissertation presents multiscale modeling techniques to study the engineering properties of single walled carbon nanotube (SWNT)-epoxy nanocomposites, consisting of pristine and covalently functionalized systems. Using Molecular Dynamics (MD), thermomechanical properties were calculated for a representative polymer unit cell. Finite Element (FE) and orientation distribution function (ODF) based methods were used in a multiscale framework to obtain macroscale properties. An epoxy network was built using the dendrimer growth approach. The epoxy model was verified by matching the experimental glass transition temperature, density, and dilatation. MD, via the constant valence force field (CVFF), was used to explore the mechanical and dilatometric effects of adding pristine and functionalized SWNTs to epoxy. Full stiffness matrices and linear coefficient of thermal expansion vectors were obtained. The Green-Kubo method was used to investigate the thermal conductivity as a function of temperature for the various nanocomposites. Inefficient phonon transport at the ends of nanotubes is an important factor in the thermal conductivity of the nanocomposites, and for this reason discontinuous nanotubes were modeled in addition to long nanotubes. To obtain continuum-scale elastic properties from the MD data, multiscale modeling was considered to give better control over the volume fraction of nanotubes, and investigate the effects of nanotube alignment. Two methods were considered; an FE based method, and an ODF based method. The FE method probabilistically assigned elastic properties of elements from the MD lattice results based on the desired volume fraction and alignment of the nanotubes. For the ODF method, a distribution function was generated based on the desired amount of nanotube alignment; and the stiffness matrix was calculated. A rule of mixture approach was implemented in the ODF model to vary the SWNT volume fraction. Both the ODF and FE models are compared and contrasted. ODF analysis is significantly faster for nanocomposites and is a novel contribution in this thesis. Multiscale modeling allows for the effects of nanofillers in epoxy systems to be characterized without having to run costly experiments.

Calibration under uncertainty for finite element models of masonry monuments

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

Atamturktur, Sezer,; Hemez, Francois,; Unal, Cetin

2010-02-01

Historical unreinforced masonry buildings often include features such as load bearing unreinforced masonry vaults and their supporting framework of piers, fill, buttresses, and walls. The masonry vaults of such buildings are among the most vulnerable structural components and certainly among the most challenging to analyze. The versatility of finite element (FE) analyses in incorporating various constitutive laws, as well as practically all geometric configurations, has resulted in the widespread use of the FE method for the analysis of complex unreinforced masonry structures over the last three decades. However, an FE model is only as accurate as its input parameters, andmore » there are two fundamental challenges while defining FE model input parameters: (1) material properties and (2) support conditions. The difficulties in defining these two aspects of the FE model arise from the lack of knowledge in the common engineering understanding of masonry behavior. As a result, engineers are unable to define these FE model input parameters with certainty, and, inevitably, uncertainties are introduced to the FE model.« less

Ab Initio Ligand Field Molecular Mechanics and the Nature of Metal-Ligand π-Bonding in Fe(II) 2,6-di(pyrazol-1-yl)pyridine Spin Crossover Complexes.

PubMed

Deeth, Robert J; Halcrow, Malcolm A; Kershaw Cook, Laurence J; Raithby, Paul R

2018-04-06

A ligand field molecular mechanics (LFMM) force field has been constructed for the spin states of [Fe(bpp) 2 ] 2+ (bpp=2,6-di(pyrazol-1-yl)pyridine) and related complexes. A new charge scheme is employed which interpolates between partial charges for neutral bpp and protonated [H 3 bpp] 3+ to achieve a target metal charge. The LFMM angular overlap model (AOM) parameters are fitted to fully ab initio d orbital energies. However, several AOM parameter sets are possible. The ambiguity is resolved by calculating the Jahn-Teller distortion mode for high spin, which indicates that in [Fe(bpp) 2 ] 2+ pyridine is a π-acceptor and pyrazole a weak π-donor. The alternative fit, assumed previously, where both ligands act as π-donors leads to an inconsistent distortion. LFMM optimisations in the presence of [BF 4 ] - or [PF 6 ] - anions are in good agreement with experiment and the model also correctly predicts the spin state energetics for 3-pyrazolyl substituents where the interactions are mainly steric. However, for 4-pyridyl or 4-pyrazolyl substituents, LFMM only treats the electrostatic contribution which, for the pyridyl substituents, generates a fair correlation with the spin crossover transition temperatures, T 1/2 , but in the reverse sense to the dominant electronic effect. Thus, LFMM generates its smallest spin state energy difference for the substituent with the highest T 1/2 . One parameter set for all substituted bpp ligands is insufficient and further LFMM development will be required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of Iron Uptake Systems in Pseudomonas aeruginosa Virulence and Airway Infection

PubMed Central

Minandri, Fabrizia; Imperi, Francesco; Frangipani, Emanuela; Bonchi, Carlo; Visaggio, Daniela; Facchini, Marcella; Pasquali, Paolo; Bragonzi, Alessandra

2016-01-01

Pseudomonas aeruginosa is a leading cause of hospital-acquired pneumonia and chronic lung infections in cystic fibrosis patients. Iron is essential for bacterial growth, and P. aeruginosa expresses multiple iron uptake systems, whose role in lung infection deserves further investigation. P. aeruginosa Fe3+ uptake systems include the pyoverdine and pyochelin siderophores and two systems for heme uptake, all of which are dependent on the TonB energy transducer. P. aeruginosa also has the FeoB transporter for Fe2+ acquisition. To assess the roles of individual iron uptake systems in P. aeruginosa lung infection, single and double deletion mutants were generated in P. aeruginosa PAO1 and characterized in vitro, using iron-poor media and human serum, and in vivo, using a mouse model of lung infection. The iron uptake-null mutant (tonB1 feoB) and the Fe3+ transport mutant (tonB1) did not grow aerobically under low-iron conditions and were avirulent in the mouse model. Conversely, the wild type and the feoB, hasR phuR (heme uptake), and pchD (pyochelin) mutants grew in vitro and caused 60 to 90% mortality in mice. The pyoverdine mutant (pvdA) and the siderophore-null mutant (pvdA pchD) grew aerobically in iron-poor media but not in human serum, and they caused low mortality in mice (10 to 20%). To differentiate the roles of pyoverdine in iron uptake and virulence regulation, a pvdA fpvR double mutant defective in pyoverdine production but expressing wild-type levels of pyoverdine-regulated virulence factors was generated. Deletion of fpvR in the pvdA background partially restored the lethal phenotype, indicating that pyoverdine contributes to the pathogenesis of P. aeruginosa lung infection by combining iron transport and virulence-inducing capabilities. PMID:27271740

Biphasic Finite Element Modeling Reconciles Mechanical Properties of Tissue-Engineered Cartilage Constructs Across Testing Platforms.

PubMed

Meloni, Gregory R; Fisher, Matthew B; Stoeckl, Brendan D; Dodge, George R; Mauck, Robert L

2017-07-01

Cartilage tissue engineering is emerging as a promising treatment for osteoarthritis, and the field has progressed toward utilizing large animal models for proof of concept and preclinical studies. Mechanical testing of the regenerative tissue is an essential outcome for functional evaluation. However, testing modalities and constitutive frameworks used to evaluate in vitro grown samples differ substantially from those used to evaluate in vivo derived samples. To address this, we developed finite element (FE) models (using FEBio) of unconfined compression and indentation testing, modalities commonly used for such samples. We determined the model sensitivity to tissue radius and subchondral bone modulus, as well as its ability to estimate material parameters using the built-in parameter optimization tool in FEBio. We then sequentially tested agarose gels of 4%, 6%, 8%, and 10% weight/weight using a custom indentation platform, followed by unconfined compression. Similarly, we evaluated the ability of the model to generate material parameters for living constructs by evaluating engineered cartilage. Juvenile bovine mesenchymal stem cells were seeded (2 × 10 7 cells/mL) in 1% weight/volume hyaluronic acid hydrogels and cultured in a chondrogenic medium for 3, 6, and 9 weeks. Samples were planed and tested sequentially in indentation and unconfined compression. The model successfully completed parameter optimization routines for each testing modality for both acellular and cell-based constructs. Traditional outcome measures and the FE-derived outcomes showed significant changes in material properties during the maturation of engineered cartilage tissue, capturing dynamic changes in functional tissue mechanics. These outcomes were significantly correlated with one another, establishing this FE modeling approach as a singular method for the evaluation of functional engineered and native tissue regeneration, both in vitro and in vivo.

[Skeleton extractions and applications].

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

Quadros, William Roshan

2010-05-01

This paper focuses on the extraction of skeletons of CAD models and its applications in finite element (FE) mesh generation. The term 'skeleton of a CAD model' can be visualized as analogous to the 'skeleton of a human body'. The skeletal representations covered in this paper include medial axis transform (MAT), Voronoi diagram (VD), chordal axis transform (CAT), mid surface, digital skeletons, and disconnected skeletons. In the literature, the properties of a skeleton have been utilized in developing various algorithms for extracting skeletons. Three main approaches include: (1) the bisection method where the skeleton exists at equidistant from at leastmore » two points on boundary, (2) the grassfire propagation method in which the skeleton exists where the opposing fronts meet, and (3) the duality method where the skeleton is a dual of the object. In the last decade, the author has applied different skeletal representations in all-quad meshing, hex meshing, mid-surface meshing, mesh size function generation, defeaturing, and decomposition. A brief discussion on the related work from other researchers in the area of tri meshing, tet meshing, and anisotropic meshing is also included. This paper concludes by summarizing the strengths and weaknesses of the skeleton-based approaches in solving various geometry-centered problems in FE mesh generation. The skeletons have proved to be a great shape abstraction tool in analyzing the geometric complexity of CAD models as they are symmetric, simpler (reduced dimension), and provide local thickness information. However, skeletons generally require some cleanup, and stability and sensitivity of the skeletons should be controlled during extraction. Also, selecting a suitable application-specific skeleton and a computationally efficient method of extraction is critical.« less

Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

NASA Astrophysics Data System (ADS)

Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

2017-03-01

Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

Possible involvement of membrane lipids peroxidation and oxidation of catalytically essential thiols of the cerebral transmembrane sodium pump as component mechanisms of iron-mediated oxidative stress-linked dysfunction of the pump's activity

PubMed Central

Omotayo, T.I.; Akinyemi, G.S.; Omololu, P.A.; Ajayi, B.O.; Akindahunsi, A.A.; Rocha, J.B.T.; Kade, I.J.

2014-01-01

The precise molecular events defining the complex role of oxidative stress in the inactivation of the cerebral sodium pump in radical-induced neurodegenerative diseases is yet to be fully clarified and thus still open. Herein we investigated the modulation of the activity of the cerebral transmembrane electrogenic enzyme in Fe2+-mediated in vitro oxidative stress model. The results show that Fe2+ inhibited the transmembrane enzyme in a concentration dependent manner and this effect was accompanied by a biphasic generation of aldehydic product of lipid peroxidation. While dithiothreitol prevented both Fe2+ inhibitory effect on the pump and lipid peroxidation, vitamin E prevented only lipid peroxidation but not inhibition of the pump. Besides, malondialdehyde (MDA) inhibited the pump by a mechanism not related to oxidation of its critical thiols. Apparently, the low activity of the pump in degenerative diseases mediated by Fe2+ may involve complex multi-component mechanisms which may partly involve an initial oxidation of the critical thiols of the enzyme directly mediated by Fe2+ and during severe progression of such diseases; aldehydic products of lipid peroxidation such as MDA may further exacerbate this inhibitory effect by a mechanism that is likely not related to the oxidation of the catalytically essential thiols of the ouabain-sensitive cerebral electrogenic pump. PMID:25618580

Dithiolato-bridged nickel-iron complexes as models for the active site of [NiFe]-hydrogenases.

PubMed

Song, Li-Cheng; Yang, Xi-Yue; Cao, Meng; Gao, Xiu-Yun; Liu, Bei-Bei; Zhu, Liang; Jiang, Feng

2017-03-30

The structural and functional modeling of the active site of [NiFe]-hydrogenases has been proved to be challenging to a great extent. Herein, we report the synthesis, structures, and some properties of the NiFe-based dicarbonyl, terminal hydride, and μ-hydroxo models for the active site of [NiFe]-hydrogenases.

Integrating MRI-based geometry, composition and fiber architecture in a finite element model of the human intervertebral disc.

PubMed

Stadelmann, Marc A; Maquer, Ghislain; Voumard, Benjamin; Grant, Aaron; Hackney, David B; Vermathen, Peter; Alkalay, Ron N; Zysset, Philippe K

2018-05-17

Intervertebral disc degeneration is a common disease that is often related to impaired mechanical function, herniations and chronic back pain. The degenerative process induces alterations of the disc's shape, composition and structure that can be visualized in vivo using magnetic resonance imaging (MRI). Numerical tools such as finite element analysis (FEA) have the potential to relate MRI-based information to the altered mechanical behavior of the disc. However, in terms of geometry, composition and fiber architecture, current FE models rely on observations made on healthy discs and might therefore not be well suited to study the degeneration process. To address the issue, we propose a new, more realistic FE methodology based on diffusion tensor imaging (DTI). For this study, a human disc joint was imaged in a high-field MR scanner with proton-density weighted (PD) and DTI sequences. The PD image was segmented and an anatomy-specific mesh was generated. Assuming accordance between local principal diffusion direction and local mean collagen fiber alignment, corresponding fiber angles were assigned to each element. Those element-wise fiber directions and PD intensities allowed the homogenized model to smoothly account for composition and fibrous structure of the disc. The disc's in vitro mechanical behavior was quantified under tension, compression, flexion, extension, lateral bending and rotation. The six resulting load-displacement curves could be replicated by the FE model, which supports our approach as a first proof of concept towards patient-specific disc modeling. Copyright © 2018 Elsevier Ltd. All rights reserved.

THE SYNTHETIC-OVERSAMPLING METHOD: USING PHOTOMETRIC COLORS TO DISCOVER EXTREMELY METAL-POOR STARS

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

Miller, A. A., E-mail: amiller@astro.caltech.edu

2015-09-20

Extremely metal-poor (EMP) stars ([Fe/H] ≤ −3.0 dex) provide a unique window into understanding the first generation of stars and early chemical enrichment of the universe. EMP stars are exceptionally rare, however, and the relatively small number of confirmed discoveries limits our ability to exploit these near-field probes of the first ∼500 Myr after the Big Bang. Here, a new method to photometrically estimate [Fe/H] from only broadband photometric colors is presented. I show that the method, which utilizes machine-learning algorithms and a training set of ∼170,000 stars with spectroscopically measured [Fe/H], produces a typical scatter of ∼0.29 dex. Thismore » performance is similar to what is achievable via low-resolution spectroscopy, and outperforms other photometric techniques, while also being more general. I further show that a slight alteration to the model, wherein synthetic EMP stars are added to the training set, yields the robust identification of EMP candidates. In particular, this synthetic-oversampling method recovers ∼20% of the EMP stars in the training set, at a precision of ∼0.05. Furthermore, ∼65% of the false positives from the model are very metal-poor stars ([Fe/H] ≤ −2.0 dex). The synthetic-oversampling method is biased toward the discovery of warm (∼F-type) stars, a consequence of the targeting bias from the Sloan Digital Sky Survey/Sloan Extension for Galactic Understanding survey. This EMP selection method represents a significant improvement over alternative broadband optical selection techniques. The models are applied to >12 million stars, with an expected yield of ∼600 new EMP stars, which promises to open new avenues for exploring the early universe.« less

A [4Fe-4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly

NASA Astrophysics Data System (ADS)

Rao, Guodong; Tao, Lizhi; Suess, Daniel L. M.; Britt, R. David

2018-05-01

Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate—the first organometallic precursor to the H-cluster—validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster.

Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries

PubMed Central

Huang, Weifeng; Zhou, Jing; Li, Biao; Ma, Jin; Tao, Shi; Xia, Dingguo; Chu, Wangsheng; Wu, Ziyu

2014-01-01

Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V. PMID:24595232

A Retrospective Examination of Feline Leukemia Subgroup Characterization: Viral Interference Assays to Deep Sequencing.

PubMed

Chiu, Elliott S; Hoover, Edward A; VandeWoude, Sue

2018-01-10

Feline leukemia virus (FeLV) was the first feline retrovirus discovered, and is associated with multiple fatal disease syndromes in cats, including lymphoma. The original research conducted on FeLV employed classical virological techniques. As methods have evolved to allow FeLV genetic characterization, investigators have continued to unravel the molecular pathology associated with this fascinating agent. In this review, we discuss how FeLV classification, transmission, and disease-inducing potential have been defined sequentially by viral interference assays, Sanger sequencing, PCR, and next-generation sequencing. In particular, we highlight the influences of endogenous FeLV and host genetics that represent FeLV research opportunities on the near horizon.

A Global Atmospheric Model of Meteoric Iron

NASA Technical Reports Server (NTRS)

Feng, Wuhu; Marsh, Daniel R.; Chipperfield, Martyn P.; Janches, Diego; Hoffner, Josef; Yi, Fan; Plane, John M. C.

2013-01-01

The first global model of meteoric iron in the atmosphere (WACCM-Fe) has been developed by combining three components: the Whole Atmosphere Community Climate Model (WACCM), a description of the neutral and ion-molecule chemistry of iron in the mesosphere and lower thermosphere (MLT), and a treatment of the injection of meteoric constituents into the atmosphere. The iron chemistry treats seven neutral and four ionized iron containing species with 30 neutral and ion-molecule reactions. The meteoric input function (MIF), which describes the injection of Fe as a function of height, latitude, and day, is precalculated from an astronomical model coupled to a chemical meteoric ablation model (CABMOD). This newly developed WACCM-Fe model has been evaluated against a number of available ground-based lidar observations and performs well in simulating the mesospheric atomic Fe layer. The model reproduces the strong positive correlation of temperature and Fe density around the Fe layer peak and the large anticorrelation around 100 km. The diurnal tide has a significant effect in the middle of the layer, and the model also captures well the observed seasonal variations. However, the model overestimates the peak Fe+ concentration compared with the limited rocket-borne mass spectrometer data available, although good agreement on the ion layer underside can be obtained by adjusting the rate coefficients for dissociative recombination of Fe-molecular ions with electrons. Sensitivity experiments with the same chemistry in a 1-D model are used to highlight significant remaining uncertainties in reaction rate coefficients, and to explore the dependence of the total Fe abundance on the MIF and rate of vertical transport.

Biological effects of four iron-containing nanoremediation materials on the green alga Chlamydomonas sp.

PubMed

Nguyen, Nhung H A; Von Moos, Nadia R; Slaveykova, Vera I; Mackenzie, Katrin; Meckenstock, Rainer U; Thűmmler, Silke; Bosch, Julian; Ševců, Alena

2018-06-15

As nanoremediation strategies for in-situ groundwater treatment extend beyond nanoiron-based applications to adsorption and oxidation, ecotoxicological evaluations of newly developed materials are required. The biological effects of four new materials with different iron (Fe) speciations ([i] FerMEG12 - pristine flake-like milled Fe(0) nanoparticles (nZVI), [ii] Carbo-Iron ® - Fe(0)-nanoclusters containing activated carbon (AC) composite, [iii] Trap-Ox® Fe-BEA35 (Fe-zeolite) - Fe-doped zeolite, and [iv] Nano-Goethite - 'pure' FeOOH) were studied using the unicellular green alga Chlamydomonas sp. as a model test system. Algal growth rate, chlorophyll fluorescence, efficiency of photosystem II, membrane integrity and reactive oxygen species (ROS) generation were assessed following exposure to 10, 50 and 500 mg L -1 of the particles for 2 h and 24 h. The particles had a concentration-, material- and time-dependent effect on Chlamydomonas sp., with increased algal growth rate after 24 h. Conversely, significant intracellular ROS levels were detected after 2 h, with much lower levels after 24 h. All Fe-nanomaterials displayed similar Z-average sizes and zeta-potentials at 2 h and 24 h. Effects on Chlamydomonas sp. decreased in the order FerMEG12 > Carbo-Iron® > Fe-zeolite > Nano-Goethite. Ecotoxicological studies were challenged due to some particle properties, i.e. dark colour, effect of constituents and a tendency to agglomerate, especially at high concentrations. All particles exhibited potential to induce significant toxicity at high concentrations (500 mg L -1 ), though such concentrations would rapidly decrease to mg or µg L -1 in aquatic environments, levels harmless to Chlamydomonas sp. The presented findings contribute to the practical usage of particle-based nanoremediation in environmental restoration. Copyright © 2018. Published by Elsevier Inc.

Efficient recovery of nano-sized iron oxide particles from synthetic acid-mine drainage (AMD) water using fuel cell technologies.

PubMed

Cheng, Shaoan; Jang, Je-Hun; Dempsey, Brian A; Logan, Bruce E

2011-01-01

Acid mine drainage (AMD) is an important contributor to surface water pollution due to the release of acid and metals. Fe(II) in AMD reacts with dissolved oxygen to produce iron oxide precipitates, resulting in further acidification, discoloration of stream beds, and sludge deposits in receiving waters. It has recently been shown that new fuel cell technologies, based on microbial fuel cells, can be used to treat AMD and generate electricity. Here we show that this approach can also be used as a technique to generate spherical nano-particles of iron oxide that, upon drying, are transformed to goethite (α-FeOOH). This approach therefore provides a relatively straightforward way to generate a product that has commercial value. Particle diameters ranged from 120 to 700 nm, with sizes that could be controlled by varying the conditions in the fuel cell, especially current density (0.04-0.12 mA/cm(2)), pH (4-7.5), and initial Fe(II) concentration (50-1000 mg/L). The most efficient production of goethite and power occurred with pH = 6.3 and Fe(II) concentrations above 200 mg/L. These results show that fuel cell technologies can not only be used for simultaneous AMD treatment and power generation, but that they can generate useful products such as iron oxide particles having sizes appropriate for used as pigments and other applications. Copyright © 2010 Elsevier Ltd. All rights reserved.

Methamphetamine generates peroxynitrite and produces dopaminergic neurotoxicity in mice: protective effects of peroxynitrite decomposition catalyst.

PubMed

Imam, S Z; Crow, J P; Newport, G D; Islam, F; Slikker, W; Ali, S F

1999-08-07

Methamphetamine (METH)-induced dopaminergic neurotoxicity is believed to be produced by oxidative stress and free radical generation. The present study was undertaken to investigate if METH generates peroxynitrite and produces dopaminergic neurotoxicity. We also investigated if this generation of peroxynitrite can be blocked by a selective peroxynitrite decomposition catalyst, 5, 10,15, 20-tetrakis(N-methyl-4'-pyridyl)porphyrinato iron III (FeTMPyP) and protect against METH-induced dopaminergic neurotoxicity. Administration of METH resulted in the significant formation of 3-nitrotyrosine (3-NT), an in vivo marker of peroxynitrite generation, in the striatum and also caused a significant increase in the body temperature. METH injection also caused a significant decrease in the concentration of dopamine (DA), 3, 4-dihydroxyphenylacetic acid (DOPAC), and homovanillic acid (HVA) by 76%, 53% and 40%, respectively, in the striatum compared with the control group. Treatment with FeTMPyP blocked the formation of 3-NT by 66% when compared with the METH group. FeTMPyP treatment also provided significant protection against the METH-induced hyperthermia and depletion of DA, DOPAC and HVA. Administration of FeTMPyP alone neither resulted in 3-NT formation nor had any significant effect on DA or its metabolite concentrations. These findings indicate that peroxynitrite plays a role in METH-induced dopaminergic neurotoxicity and also suggests that peroxynitrite decomposition catalysts may be beneficial for the management of psychostimulant abuse. Copyright 1999 Published by Elsevier Science B.V.

BRUTUS and its paralogs, BTS LIKE1 and BTS LIKE2, encode important negative regulators of the iron deficiency response in Arabidopsis thaliana.

PubMed

Hindt, Maria N; Akmakjian, Garo Z; Pivarski, Kara L; Punshon, Tracy; Baxter, Ivan; Salt, David E; Guerinot, Mary Lou

2017-07-19

Iron (Fe) is required for plant health, but it can also be toxic when present in excess. Therefore, Fe levels must be tightly controlled. The Arabidopsis thaliana E3 ligase BRUTUS (BTS) is involved in the negative regulation of the Fe deficiency response and we show here that the two A. thaliana BTS paralogs, BTS LIKE1 (BTSL1) and BTS LIKE2 (BTSL2) encode proteins that act redundantly as negative regulators of the Fe deficiency response. Loss of both of these E3 ligases enhances tolerance to Fe deficiency. We further generated a triple mutant with loss of both BTS paralogs and a partial loss of BTS expression that exhibits even greater tolerance to Fe-deficient conditions and increased Fe accumulation without any resulting Fe toxicity effects. Finally, we identified a mutant carrying a novel missense mutation of BTS that exhibits an Fe deficiency response in the root when grown under both Fe-deficient and Fe-sufficient conditions, leading to Fe toxicity when plants are grown under Fe-sufficient conditions.

Improving sediment-quality guidelines for nickel: development and application of predictive bioavailability models to assess chronic toxicity of nickel in freshwater sediments

USGS Publications Warehouse

Vangheluwe, Marnix L. U.; Verdonck, Frederik A. M.; Besser, John M.; Brumbaugh, William G.; Ingersoll, Christopher G.; Schlekat, Christan E.; Rogevich Garman, Emily

2013-01-01

Within the framework of European Union chemical legislations an extensive data set on the chronic toxicity of sediment nickel has been generated. In the initial phase of testing, tests were conducted with 8 taxa of benthic invertebrates in 2 nickel-spiked sediments, including 1 reasonable worst-case sediment with low concentrations of acid-volatile sulfide (AVS) and total organic carbon. The following species were tested: amphipods (Hyalella azteca, Gammarus pseudolimnaeus), mayflies (Hexagenia sp.), oligochaetes (Tubifex tubifex, Lumbriculus variegatus), mussels (Lampsilis siliquoidea), and midges (Chironomus dilutus, Chironomus riparius). In the second phase, tests were conducted with the most sensitive species in 6 additional spiked sediments, thus generating chronic toxicity data for a total of 8 nickel-spiked sediments. A species sensitivity distribution was elaborated based on 10% effective concentrations yielding a threshold value of 94 mg Ni/kg dry weight under reasonable worst-case conditions. Data from all sediments were used to model predictive bioavailability relationships between chronic toxicity thresholds (20% effective concentrations) and AVS and Fe, and these models were used to derive site-specific sediment-quality criteria. Normalization of toxicity values reduced the intersediment variability in toxicity values significantly for the amphipod species Hyalella azteca and G. pseudolimnaeus, but these relationships were less clearly defined for the mayfly Hexagenia sp. Application of the models to prevailing local conditions resulted in threshold values ranging from 126 mg to 281 mg Ni/kg dry weight, based on the AVS model, and 143 mg to 265 mg Ni/kg dry weight, based on the Fe model

Iron Hydroperoxide Intermediate in Superoxide Reductase: Protonation or Dissociation First? MM Dynamics and QM/MM Metadynamics Study.

PubMed

David, Rolf; Jamet, Hélène; Nivière, Vincent; Moreau, Yohann; Milet, Anne

2017-06-13

Superoxide reductase is a mononuclear iron enzyme involved in superoxide radical detoxification in some bacteria. Its catalytic mechanism is associated with the remarkable formation of a ferric hydroperoxide Fe 3+ -OOH intermediate, which is specifically protonated on its proximal oxygen to generate the reaction product H 2 O 2 . Here, we present a computational study of the protonation mechanism of the Fe 3+ -OOH intermediate, at different levels of theory. This was performed on the whole system (solvated protein) using well-tempered metadynamics at the QM/MM (B3LYP/AmberFF99SB) level. Enabled by the development of a new set of force field parameters for the active site, a conformational MM study of the Fe 3+ -OOH species gave insights into its solvation pattern, in addition to generating the two starting conformations for the ab initio metadynamics setup. Two different protonation mechanisms for the Fe 3+ -OOH intermediate have been found depending on the starting structure. Whereas a possible mechanism involves at first the protonation of the hydroperoxide ligand and then dissociation of H 2 O 2 , the most probable one starts with an unexpected dissociation of the HOO - ligand from the iron, followed by its protonation. This favored reactivity was specifically linked to the influence of both the nearby conserved lysine 48 residue and the microsolvatation on the charge distribution of the oxygens of the HOO - ligand. These data highlight the crucial role of the whole environment, solvent, and protein, to describe accurately this second protonation step in superoxide reductase. This is clearly not possible with smaller models unable to reproduce correctly the mechanistically determinant charge distribution.

Assessment of kinetic models on Fe adsorption in groundwater using high-quality limestone

NASA Astrophysics Data System (ADS)

Akbar, N. A.; Kamil, N. A. F. Mohd; Zin, N. S. Md; Adlan, M. N.; Aziz, H. A.

2018-04-01

During the groundwater pumping process, dissolved Fe2+ is oxidized into Fe3+ and produce rust-coloured iron mineral. Adsorption kinetic models are used to evaluate the performance of limestone adsorbent and describe the mechanism of adsorption and the diffusion processes of Fe adsorption in groundwater. This work presents the best kinetic model of Fe adsorption, which was chosen based on a higher value of coefficient correlation, R2. A batch adsorption experiment was conducted for various contact times ranging from 0 to 135 minutes. From the results of the batch study, three kinetic models were analyzed for Fe removal onto limestone sorbent, including the pseudo-first order (PFO), pseudo-second order (PSO) and intra-particle diffusion (IPD) models. Results show that the adsorption kinetic models follow the sequence: PSO > PFO > IPD, where the values of R2 are 0.997 > 0.919 > 0.918. A high value of R2 (0.997) reveals better fitted experimental data. Furthermore, the value of qe cal in the PSO kinetic model is very near to qe exp rather than that in other models. This finding therefore suggests that the PSO kinetic model has the good fitted with the experimental data which involved chemisorption process of divalent Fe removal in groundwater solution. Thus, limestone adsorbent media found to be an alternative and effective treatment of Fe removal from groundwater.

Modeling the degradation mechanisms of C6/LiFePO4 batteries

NASA Astrophysics Data System (ADS)

Li, Dongjiang; Danilov, Dmitri L.; Zwikirsch, Barbara; Fichtner, Maximilian; Yang, Yong; Eichel, Rüdiger-A.; Notten, Peter H. L.

2018-01-01

A fundamental electrochemical model is developed, describing the capacity fade of C6/LiFePO4 batteries as a function of calendar time and cycling conditions. At moderate temperatures the capacity losses are mainly attributed to Li immobilization in Solid-Electrolyte-Interface (SEI) layers at the anode surface. The SEI formation model presumes the availability of an outer and inner SEI layers. Electron tunneling through the inner SEI layer is regarded as the rate-determining step. The model also includes high temperature degradation. At elevated temperatures, iron dissolution from the positive electrode and the subsequent metal sedimentation on the negative electrode influence the capacity loss. The SEI formation on the metal-covered graphite surface is faster than the conventional SEI formation. The model predicts that capacity fade during storage is lower than during cycling due to the generation of SEI cracks induced by the volumetric changes during (dis)charging. The model has been validated by cycling and calendar aging experiments and shows that the capacity loss during storage depends on the storage time, the State-of-Charge (SoC), and temperature. The capacity losses during cycling depend on the cycling current, cycling time, temperature and cycle number. All these dependencies can be explained by the single model presented in this paper.

Alternative solution model for the ternary carbonate system CaCO3 - MgCO3 - FeCO3 - I. A ternary Bragg-Williams ordering model

USGS Publications Warehouse

McSwiggen, P.L.

1993-01-01

The minerals of the ternary carbonate system CaCO3 - MgCO3 - FeCO3 represent a complex series of solid solutions and ordering states. An understanding of those complexities requires a solution model that can both duplicate the subsolidus phase relationships and generate correct values for the activities. Such a solution model must account for the changes in the total energy of the system resulting from a change in the ordering state of the individual constituents. Various ordering models have been applied to binary carbonate systems, but no attempts have previously been made to model the ordering in the ternary system. This study derives a new set of equations that allow for the equilibrium degree of order to be calculated for a system involving three cations mixing on two sites, as in the case of the ternary carbonates. The method is based on the Bragg-Williams approach. From the degree of order, the mole fractions of the three cations in each of the two sites can be determined. Once the site occupancies have been established, a Margules-type mixing model can be used to determine the free energy of mixing in the solid solution and therefore the activities of the various components. ?? 1993 Springer-Verlag.

Revisiting the magnetic structure and charge ordering in La1 /3Sr2 /3FeO3 by neutron powder diffraction and Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Li, F.; Pomjakushin, V.; Mazet, T.; Sibille, R.; Malaman, B.; Yadav, R.; Keller, L.; Medarde, M.; Conder, K.; Pomjakushina, E.

2018-05-01

The magnetic ordering of La1 /3Sr2 /3FeO3 perovskite has been studied by neutron powder diffraction and 57Fe Mössbauer spectroscopy down to 2 K. From symmetry analysis, a chiral helical model and a collinear model are proposed to describe the magnetic structure. Both are commensurate, with propagation vector k =(0 ,0 ,1 ) in R 3 ¯c space group. In the former model, the magnetic moments of Fe adopt the magnetic space group P 3221 and have helical and antiferromagnetic ordering propagating along the c axis. The model allows only a single Fe site, with a magnetic moment of 3.46(2)μB at 2 K. In the latter model, the magnetic moments of iron ions adopt the magnetic space group C 2 /c or C 2'/c' and are aligned collinearly. The model allows the presence of two inequivalent Fe sites with magnetic moments of amplitude 3.26(3)μB and 3.67(2)μB, respectively. The neutron-diffraction pattern is equally well fitted by either model. The Mössbauer spectroscopy study suggests a single charge state Fe3.66 + above the magnetic transition and a charge disproportionation into Fe(3.66 -ζ )+ and Fe(3.66 +2 ζ )+ below the magnetic transition. The compatibility of the magnetic structure models with the Mössbauer spectroscopy results is discussed.

Formation mechanisms of neutral Fe layers in the thermosphere at Antarctica studied with a thermosphere-ionosphere Fe/Fe+ (TIFe) model

NASA Astrophysics Data System (ADS)

Chu, Xinzhao; Yu, Zhibin

2017-06-01

With a thermosphere-ionosphere Fe/Fe+ (TIFe) model developed from first principles at the University of Colorado, we present the first quantitative investigation of formation mechanisms of thermospheric Fe layers observed by lidar in Antarctica. These recently discovered neutral metal layers in the thermosphere between 100 and 200 km provide unique tracers for studies of fundamental processes in the space-atmosphere interaction region. The TIFe model formulates and expands the TIFe theory originally proposed by Chu et al. that the thermospheric Fe layers are produced through the neutralization of converged Fe+ layers. Through testing mechanisms and reproducing the 28 May 2011 event at McMurdo, we conceive the lifecycle of meteoric metals via deposition, transport, chemistry, and wave dynamics for thermospheric Fe layers with gravity wave signatures. While the meteor injection of iron species is negligible above 120 km, the polar electric field transports metallic ions Fe+ upward from their main deposition region into the E-F regions, providing the major source of Fe+ (and accordingly Fe) in the thermosphere. Atmospheric wave-induced vertical shears of vertical and horizontal winds converge Fe+ to form dense Fe+ layers. Direct electron-Fe+ recombination is the major channel to neutralize Fe+ layers to form Fe above 120 km. Fe layer shapes are determined by multiple factors of neutral winds, electric field, and aurora activity. Gravity-wave-induced vertical wind plays a key role in forming gravity-wave-shaped Fe layers. Aurora particle precipitation enhances Fe+ neutralization by increasing electron density while accelerating Fe loss via charge transfer with enhanced NO+ and O2+ densities.