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At least 1,531 records · Page 85

Electrolyte Effects on the Stability of Ni-Mo Cathodes for the Hydrogen Evolution Reaction

Water electrolysis to form hydrogen as a solar fuel requires highly effective catalysts. In this work, theoretical and experimental studies are performed on the activity and stability of Ni-Mo cathodes for this reaction. Density functional theory studies show various Ni-Mo facets to be active for the hydrogen evolution reaction, Ni segregation to be thermodynamically favorable, and Mo vacancy formation to be favorable even without an applied potential. Electrolyte effects on the long-term stability of Ni-Mo cathodes are determined. Ni-Mo is compared before and after up to 100 h of continuous operation. It is shown that Ni-Mo is unstable in alkaline media, owing to Mo leaching in the form of MoO 4 2- , ultimately leading to a decrease in absolute overpotential. It is found that the electrolyte, the alkali cations, and the pH all influence Mo leaching. Changing the cation in the electrolyte from Li to Na to K influences the surface segregation of Mo and pushes the reaction towards Mo dissolution. Decreasing the pH decreases the OH - concentration and in this manner inhibits Mo leaching. Of the electrolytes studied, in terms of stability, the best to use is LiOH at pH 13. Thus, a mechanism for Mo leaching is presented alongside ways to influence the stability and make the Ni-Mo material more viable for renewable energy storage in chemical bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal Structures of Diaryl Hydrazone and Sulfone Stabilizers in Complex with an Amyloidogenic Light Chain Reveal an Alternate Ligand‐Binding Cavity

Abstract Stabilization of amyloidogenic immunoglobulin light chains (LCs) by binding of small molecule “kinetic stabilizers” is under development as a novel treatment for light chain amyloidosis. From a high‐throughput screen, we previously identified 16 full‐length (FL) LC stabilizers from five distinct chemotypes. We then obtained structural biological information on two classes of hits, coumarins and hydantoins, revealing that both chemotypes bind to a pocket at the V L −V L interface of the FL LC dimer. Here, we report crystal structures of three screening hits from two other chemotypes, diaryl hydrazones and sulfones, in complex with an amyloidogenic FL LC. While two of these hits bind to the previously identified pocket, one diaryl hydrazone binds to a different pocket bisected by the C 2 symmetry axis of the dimer. These data further expand on the FL LC stabilizer‐binding surface that could be used in design of more potent FL LC aggregation inhibitors.

Chemistry↗

Partial substitution of rice husks for manure in greenhouse vegetable fields: Insight from soil carbon stock and aggregate stability

Abstract Soil aggregate stability and C stock are key factors in greenhouse vegetable production, which are influenced by the application of different organic materials. However, the responses of soil aggregate stability and C stock to organic amendment in greenhouse vegetable fields are not well understood. A 5‐year study was carried out in greenhouse vegetable fields to investigate the effect of partial substitution of rice husks for manure on soil aggregate stability, C compositions, and their relationships. Four treatments included: (a) no organic fertilization (control), (b) 30 t ha −1 chicken manure (CM), (c) 30 t ha −1 rice husks (RH), and (d) 10 t ha −1 chicken manure plus 20 t ha −1 rice husks (MR). Rice husks addition significantly increased the proportion of >2 mm aggregates and mean weight diameter (MWD), while manure addition showed no difference with control. Polysaccharide and humin (HM) were increased with rice husks addition (RH and MR) compared with that in CM treatment. Polysaccharide and HM caused 86.03% variation of soil aggregate, in which polysaccharide and HM contributed 76.3 and 9.7%, respectively. The soil C stock in CM, RH, and MR treatments was increased by 146, 175, and 164% compared with control, respectively. Aliphatic‐C and amorphous Fe‐oxides (Fe‐ox) content were as higher in MR added soil than those in RH treatment. Partial substitution of rice husk for manure improved soil aggregation stability and thus enhanced C stock by suppling more polysaccharide, HM and liberated soil minerals, which was conducive to the sustainable development in greenhouse vegetable production.

Fei, Chao↗

An embedded mesh method using piecewise constant multipliers with stabilization: mathematical and numerical aspects

An embedded mesh method using piecewise constant multipliers originally proposed by Puso et al. (CMAME, 2012) is analyzed here to determine effects of the pressure stabilization term and small cut cells. The approach is implemented for transient dynamics using the central difference scheme for the time discretization. It is shown that the resulting equations of motion are a stable linear system with a condition number independent of mesh size. Furthermore, we show that the constraints and the stabilization terms can be recast as non-proportional damping such that the time integration of the scheme is provably stable with a critical time step computed from the undamped equations of motion. Effects of small cuts are discussed throughout the presentation. A mesh study is conducted to evaluate the effects of the stabilization on the discretization error and conditioning and is used to recommend an optimal value for stabilization scaling parameter. Several nonlinear problems are also analyzed and compared with comparable conforming mesh results. Finally, we show several demanding problems highlighting the robustness of the proposed approach.

42 ENGINEERING↗

Cover crops and poultry litter impact on soil structural stability in dryland soybean production in southeastern United States

Abstract This study explored the efficacy of soil aggregate indices in quantifying soil structural development, utilizing 5‐year field experiment data from the Southeastern United States. The experiment utilized a split‐plot design with cover crops (native vegetation as control, cereal rye (Secale cerealeL.), winter wheat (Triticum aestivum), hairy vetch (Vicia villosa), and mustard (Brassica rapa) plus cereal rye as the main factor and fertilizer source (no fertilizer as control, inorganic fertilizer with phosphorus, potassium, and elemental sulfur, and poultry litter) as the secondary factor. Aggregate size fractions were determined using the wet‐sieving method, and aggregate stability index (ASI), mean weight diameter (MWD), geometric mean diameter (GMD), and fractal dimension (FD) were calculated to assess soil structural stability. Main effects results indicated that cereal rye (55.11%) and poultry litter (50.97%) exhibited the highest ASI values. The highest MWD, GMD, and FD were observed under mustard plus cereal rye (1.187 mm), cereal rye (0.462 mm), and hairy vetch (2.573), respectively. Principal component analysis revealed that cover crops significantly improved soil aggregate structure and stability, overcoming limitations of sole fertilization practices. Regression analysis suggested that ASI, MWD, and GWD positively correlated with soil organic carbon, whereas FD negatively correlated with MWD, GMD, and ASI. Principal component analysis exhibited that FD decreased with increasing soil organic carbon, ASI, MWD, and GMD, demonstrating that lower FD values indicate enhanced soil aggregation and structure. Assessed indices, FD included, effectively gauged soil structural stability. These metrics should be prioritized in managerial decisions to support soil productivity and health in agricultural systems.

Agriculture↗

Novel catalysts with multivalence copper for organic pollutants removal from wastewater with excellent selectivity and stability in Fenton‐like process under neutral pH conditions

Abstract Fenton‐like reaction has been widely used for organics degradation. However, most Fenton‐like reaction works at low pH range (pH < 4) with uncontrollable selectivity of hydroxyl radicals from H 2 O 2 activation, and unsatisfied catalyst stability, which is compromised advanced oxidation performance for water/wastewater treatments. In this work, to solve the drawbacks, novel copper catalysts were fabricated via hydrogen reduction/calcination of Cu 2+ ‐supported Al/MCM‐41 with precisely controllable copper valence state. Compared with catalysts with monovalence copper (i.e., CuO, Cu, and Cu 2+ ), the obtained catalysts with multivalence copper present higher selectivity, excellent stability towards •OH radical pathways, and outperformance in p CBA degradation efficiency at neutral state. In addition, the fabricated catalysts also exhibited excellent phenol removal efficiency (75.5%) and H 2 O 2 utilization efficiency (47.9%) within neutral environment. Moreover, the degradation efficiency of phenol approaches to 100% within only 2 h. The catalyst also shows good stability for organic pollutants removal, which shows good potential in catalytic oxidation for phenolic compounds‐containing wastewater in Fenton‐like reaction, especially under neutral pH conditions. Practitioner Points Multivalence copper presents great potentials for organic compounds removal at neutral condition. Multivalence copper shows higher selectivity toward •OH and good stability at neutral condition. Multivalence copper exhibiters outperformed phenol removal efficiency at neutral condition.

Li, Haitao↗

Vacuum stability in inert higgs doublet model with right-handed neutrinos

We analyze the vacuum stability in the inert Higgs doublet extension of the Standard Model (SM), augmented by right-handed neutrinos (RHNs) to explain neutrino masses at tree level by the seesaw mechanism. We make a comparative study of the high- and low-scale seesaw scenarios and the effect of the Dirac neutrino Yukawa couplings on the stability of the Higgs potential. Bounds on the scalar quartic couplings and Dirac Yukawa couplings are obtained from vacuum stability and perturbativity considerations. These bounds are found to be relevant only for low-scale seesaw scenarios with relatively large Yukawa couplings. The regions corresponding to stability, metastability and instability of the electroweak vacuum are identified. These theoretical constraints give a very predictive parameter space for the couplings and masses of the new scalars and RHNs which can be tested at the LHC and future colliders. The lightest non-SM neutral CP-even/odd scalar can be a good dark matter candidate and the corresponding collider signatures are also predicted for the model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural-Phase Features of Low-Stability Pre-Transitional States of BCC-Alloys with Complexes of Planar Defects (Antiphase Boundaries)

Using the Monte Carlo method, the influence of the complexes of antiphase boundaries (APBs) (a pair of shear APBs and a pair of thermal APBs) on the low-stability, pre-transitional states of BCC-alloys is considered by the example of a conventional copper alloy CuZn and an intermetallic compound NiAl. It is shown that in the region of low-stability structural-phase states the energy of formation of a complex of thermal APBs is higher than that of shear APBs. The contribution of APBs into disordering is appreciable up to the structural-phase transition temperature. The most significant factor in terms of the long-range order is the formation of the defect itself; the differences in the APB type or the plane of their occurrence do not so much affect the longrange order behavior with the temperature variation. The type of APBs however appreciably affects the structural-energy characteristics of the system at the temperatures below the phase transformation temperature. Logically, a system with structural defects is less ordered than a defect-free system. The presence of a defect favors the onset of disordering at lower temperatures: it starts at lower temperatures in the case of thermal APBs (TAPBs) compared to shear APBs (TAPBs). In a BCC-system with a complex of TAPBs the first signs of disordering invariably appear near the phase boundary in the neighborhood of large atoms (Zn–Zn in the CuZn alloy or Al–Al in the NiAl intermetallide). In the alloy with a complex of shear APBs the distortion of ordering at low temperatures is observed in the regions where the boundaries cross. The presence of antiphase boundaries affects the alloy stability under heating. It is shown that disordering is accompanied by smearing of the boundaries and their faceting. It follows from a comparative analysis of the peculiarities of disordering in the BCC-system under study (classical alloy CuZn and intermetallide NiAl) under conditions of higher temperatures in the region of low-stability, pre-transitional states that the order – disorder phase transition in the CuZn alloy takes place as a result of disordering of the system, while in the intermetallide NiAl the change of long-range order results from the structural-phase transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermal stability of intermetallic phases in Fe-rich Fe-Cr-Ni-Mo alloys

Understanding the stability of precipitate phases in the Fe-rich Fe-Cr-Ni-Mo alloys is critical to the alloy design and application of Mo-containing Austenitic steels. Coupled with thermodynamic modeling, stability of the chi and Laves phases in two Fe-Cr-Ni-Mo alloys were investigated at 1000, 850 and 700 °C for different annealing time. The morphologies, compositions and crystal structures of the matrix and precipitate phases were carefully examined by Scanning Electron Microscopy, Electron Probe Microanalysis, X-ray diffraction and Transmission Electron Microscopy. The two key findings resulted from this work. One is that the chi phase is stable at high temperature and transformed into the Laves phase at low temperature. The other is that both the chi and Laves phases have large solubilites of Cr, Mo and Ni, among which the Mo solubility has a major role on the relative stability of the precipitate phases. The developed thermodynamic models were then applied to evaluating the Mo effect on the stability of precipitate phases in AISI 316 and NF709 alloys.

36 MATERIALS SCIENCE↗

Thermal stability comparison of nanocrystalline Fe-based binary alloy pairs

Here, the widely recognized property improvements of nanocrystalline (NC) materials have generated significant interest, yet have been difficult to realize in engineering applications due to the propensity for grain growth in these interface-dense systems. While traditional pathways to thermal stabilization can slow the mobility of grain boundaries, recent theories suggest that solute segregation in NC alloy can reduce the grain boundary energy such that thermodynamic stabilization is achieved. Following the predictions of Murdock et al., here we compare for the first time the thermal stability of a predicted NC stable alloy (Fe-10at.% Mg) with a predicted non-NC stable alloy (Fe-10at.% Cu) using the same processing and characterization methodologies. Results indicate improved thermal stability of the Fe-Mg alloy in comparison to the Fe-Cu, and observed microstructures are consistent with those predicted by Monte Carlo simulations.

36 MATERIALS SCIENCE↗

Relative effects of enthalpy and entropy on the phase stability of equiatomic high-entropy alloys

High configurational entropies have been hypothesized to stabilize solid solutions in equiatomic, multi-element alloys which have attracted much attention recently as high-entropy alloys with potentially interesting properties. To evaluate the usefulness of configurational entropy as a predictor of single-phase (solid solution) stability, we prepared five new equiatomic, quinary alloys by replacing individual elements one at a time in a CoCrFeMnNi alloy that was previously shown to be single-phase [1]. An implicit assumption here is that, if any one element is replaced by another, while keeping the total number of elements constant, the configurational entropy of the alloy is unchanged; therefore, the new alloys should also be single-phase. Additionally, the substitute elements that we chose, Ti for Co, Mo or V for Cr, V for Fe, and Cu for Ni, had the same room-temperature crystal structure and comparable size/electronegativity as the elements being replaced to maximize solid solubility consistent with the Hume-Rothery rules. For comparison, the base CoCrFeMnNi alloy was also prepared. After three-day anneals at elevated temperatures, multiple phases were observed in all but the base CoCrFeMnNi alloy suggesting that, by itself, configurational entropy is generally not able to override competing driving forces that also govern phase stability. Thermodynamic analyses were carried out for each of the constituent binaries in the investigated alloys (Co-Cr, Fe-Ni, Mo-Mn, etc,). Experimental results combined with the thermodynamic analyses suggest that, in general, enthalpy and non-configurational entropy have bigger influences on phase stability in equiatomic, multi-component alloys. Only when the alloy microstructure is a single-phase, approximately ideal solid solution does the contribution of configurational entropy to the total Gibbs free energy become dominant. Thus, high configurational entropy provides a way to rationalize, after the fact, why a solid solution forms (if it forms) but it is not a useful a priori predictor of which of the so-called high-entropy alloys will form single-phase solid solutions.

High-entropy alloys↗

9R phase enabled superior radiation stability of nanotwinned Cu alloys via in situ radiation at elevated temperature

Nanotwinned metals exhibit outstanding radiation tolerance as twin boundaries effectively engage, transport and eliminate radiation-induced defects. However, radiation-induced detwinning may reduce the radiation tolerance associated with twin boundaries, especially at elevated temperatures. Here we show, via in-situ Kr ion irradiation inside a transmission electron microscope, that 3 at. % Fe in epitaxial nanotwinned Cu (Cu 97 Fe 3 ) significantly improves the thermal and radiation stability of nanotwins during radiation up to 5 displacements-per-atom at 200 °C. Such enhanced stability of nanotwins is attributed to a diffuse 9R phase resulted from the dissociation of incoherent twin boundaries in nanotwinned Cu 97 Fe 3 . The mechanisms for the enhanced stability of twin boundaries in irradiated nanotwinned alloys are discussed. As a result, the stabilization of nano-twins opens up opportunity for the application of nanotwinned alloys for aggressive radiation environments.

36 MATERIALS SCIENCE↗

Gauge structures: From stabilizer codes to continuum models

Stabilizer codes are a powerful method for implementing fault-tolerant quantum memory and in the case of topological codes, they form useful models for topological phases of matter. In this paper, we discuss the theory of stabilizer codes as a discrete version of a linear gauge structure, a concept we introduce here. A linear gauge structure captures all the familiar ingredients of U(1) gauge theory including a generalization of charge conservation, Maxwell equations and topological terms. Using this connection, we prove some important results for stabilizer codes which can be used to characterize their error-correction properties. However, this perspective does not depend on any particular Hamiltonian or Lagrangian, which as a consequence is agnostic to the source of the gauge redundancy. Based upon the connection to stabilizer codes, we view the source of the gauge redundancy as an ambiguity in the tensor product structure of the Hilbert space. That is, the gauge provides a set of equivalent but arbitrary ways to factorize the Hilbert space. We apply this formalism to the d=2 and 3 toric code as well as the paradigm fracton models, X-Cube and Haah’s cubic code. From this perspective, we are able to map all these models to some continuum version which captures all or some of the fractonic and topological features of their parent discrete models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Biodistribution and stability of CdSe core quantum dots in mouse digestive tract following per os administration: Advantages of double polymer/silica coated nanocrystals

Highlights: Black-Right-Pointing-Pointer New QDs coated with combination of polythiol ligands and silica shell were synthesized. Black-Right-Pointing-Pointer We examine the QDs stability in digestive tract of mice after per os administration. Black-Right-Pointing-Pointer The polymer/silica shell prevents QDs degradation and fluorescence quenching in vivo. -- Abstract: CdSe-core, ZnS-capped semiconductor quantum dots (QDs) are of great potential for biomedical applications. However, applications in the gastrointestinal tract for in vivo imaging and therapeutic purposes are hampered by their sensitivity to acidic environments and potential toxicity. Here we report the use of coatings with a combination of polythiol ligands and silica shell (QDs PolyT-APS) to stabilize QDs fluorescence under acidic conditions. We demonstrated the stability of water-soluble QDs PolyT-APS both in vitro, in strong acidic solutions, and in vivo. The biodistribution, stability and photoluminescence properties of QDs in the gastrointestinal tract of mice after per os administration were assessed. We demonstrated that QDs coated with current traditional materials - mercapto compounds (QDs MPA) and pendant thiol group (QDs PolyT) - are not capable of protecting QDs from chemically induced degradation and surface modification. Polythiol ligands and silica shell quantum dots (QDs PolyT-APS) are suitable for biological and biomedical applications in the gastrointestinal tract.

60 APPLIED LIFE SCIENCES↗

PPAR-γ agonist stabilizes KLF4 protein via activating Akt signaling and reducing KLF4 ubiquitination

Highlights: •PPAR-γ increases KLF4 protein level but does not influence KLF4 gene transcription. •The increase of KLF4 protein levels induced by pioglitazone is PPAR-γ-dependent. •Pioglitazone stabilizes KLF4 protein via activating Akt signaling and reducing KLF4 ubiquitination. -- Abstract: Peroxisome proliferator activated receptor γ (PPAR-γ) plays important roles in cell cycle regulation, differentiation and apoptosis. Krüppel-like factor 4 (KLF4) modulates vascular smooth muscle cell (VSMC) phenotype. Both KLF4 and PPAR-γ are involved in VSMC proliferation and differentiation. However, the actual relationship between KLF4 and PPAR-γ in VSMCs is not clear. In this study, we found that PPAR-γ agonist pioglitazone increases KLF4 protein levels but does not influence KLF4 gene transcription. PPAR-γ overexpression increases, while PPAR-γ knockdown reduces KLF4 expression, suggesting that the increase in KLF4 protein levels induced by pioglitazone is PPAR-γ-dependent. Further study showed that pioglitazone enhances KLF4 protein stability through reducing KLF4 ubiquitination. Furthermore, we demonstrated that stabilization of KLF4 by pioglitazone was related to the activation of Akt signaling pathway. Taken together, we revealed that PPAR-γ agonist pioglitazone stabilizes KLF4 protein via activating Akt signaling and reducing KLF4 ubiquitination, providing further insights into PPAR-γ and KLF4 in regulating each other’s expression in VSMCs.

60 APPLIED LIFE SCIENCES↗

Role of N-myristoylation in stability and subcellular localization of the CLPABP protein

Highlights: • N-myristoylation of the CLPABP protein was predicted to affect its stability. • N-myristoylation of CLPABP was not related to its mitochondrial localization. • Both PH domains of CLPABP may be necessary to colocalize with mitochondria. Cardiolipin and phosphatidic acid-binding protein (CLPABP) controls the stability of the mRNA harboring an AU-rich element (ARE) in the 3′ UTR with the help of the RNA stabilizer, human antigen R (HuR). Although CLPABP is localized on the mitochondrial surface as a large protein-RNA complex, its precise role is not yet known. Recently, CLPABP was identified as an N-myristoylated protein. Here, we demonstrate the effects of N-myristoylation on the functions of CLPABP. In the present study, compared to the wild-type protein that possessed the “MG” motif at the N-terminus for N-myristoylation, the mutant CLPABP protein that lacked N-myristoylation modification site was unstable. Furthermore, the expression of the G/A mutant of CLPABP, which lacked N-myristoylation site, induced morphological alterations in mitochondria. Because pleckstrin homology domain-deleted mutant, which was fused with the N-myristoylation site derived from intact CLPABP, could not colocalize with mitochondria, N-myristoylation of CLPABP was predicted to affect its stability onto the mitochondrial membrane rather than its subcellular localization.

60 APPLIED LIFE SCIENCES↗

A strategy based on thermal flexibility to design triosephosphate isomerase proteins with increased or decreased kinetic stability

Kinetic stability of proteins determines their susceptibility to irreversibly unfold in a time-dependent process, and therefore its half-life. A residue displacement analysis of temperature-induced unfolding molecular dynamics simulations was recently employed to define the thermal flexibility of proteins. This property was found to be correlated with the activation energy barrier (E{sub act}) separating the native from the transition state in the denaturation process. The E{sub act} was determined from the application of a two-state irreversible model to temperature unfolding experiments using differential scanning calorimetry (DSC). The contribution of each residue to the thermal flexibility of proteins is used here to propose multiple mutations in triosephosphate isomerase (TIM) from Trypanosoma brucei (TbTIM) and Trypanosoma cruzi (TcTIM), two parasites closely related by evolution. These two enzymes, taken as model systems, have practically identical structure but large differences in their kinetic stability. We constructed two functional TIM variants with more than twice and less than half the activation energy of their respective wild-type reference structures. The results show that the proposed strategy is able to identify the crucial residues for the kinetic stability in these enzymes. As it occurs with other protein properties reflecting their complex behavior, kinetic stability appears to be the consequence of an extensive network of inter-residue interactions, acting in a concerted manner. The proposed strategy to design variants can be used with other proteins, to increase or decrease their functional half-life.

60 APPLIED LIFE SCIENCES↗

Comparative study of three yttrium organometallic compounds for the stabilization of the cubic phase in YSZ deposited by PE-CVD

In this work, the efficiencies of three organometallic yttrium precursors used to produce YSZ coatings by plasma-enhanced chemical vapor deposition were studied. Yttrium (III) acetylacetonate, Y (acac) 3 , yttrium (III) hexafluoroacetylacetonate, Y (acacF 6 ) 3 , and yttrium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), Y (tmhd) 3 , were used to stabilize the cubic phase in zirconia deposited at temperatures from 500 to 800 °C. Our results showed that at temperatures between 500 and 600 °C, Y (tmhd) 3 appeared to be the most efficient dopant as it introduced the highest concentration of yttria (1–2.7 mol%) with only 6.4–5.6 at.% carbon. However, at 700 and 800 °C, Y (acac) 3 introduced twice as much yttria (8–15 mol%) as Y (tmhd) 3 with almost the same amount of carbon (5.4–3 at.%). Conversely, Y (acacF6)3 was the least efficient as it maintained a low concentration of yttria of around 0.7–1.8 mol% with 3.6–8.2 at.% carbon for all the deposition temperatures. Among these precursors, only Y (acac) 3 surpassed 8 mol% yttria and achieved a fully stabilized cubic phase at 800 °C, with the remaining samples stabilizing only the tetragonal phase. The tetragonal phase was stabilized due to the formation of crystallites of around 10 nm. The observed difference in the efficiency of the three precursors was correlated to important differences in their decomposition behavior as observed by mass spectrometry and thermogravimetry/differential scanning calorimetry.

36 MATERIALS SCIENCE↗