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At least 271 records · Page 15

Citrate-based sol-gel synthesis of blue- and green-emitting BaLa{sub 2}WO{sub 7}:Tm{sup 3+} or Er{sup 3+} phosphors and their luminescence properties

Highlights: • The BLWO:Tm{sup 3+} or Er{sup 3+} phosphors were prepared by a citrate-based sol-gel method. • The BLWO:Tm{sup 3+} or Er{sup 3+} phosphors exhibited blue and green emissions under UV or NUV excitations. • The blue- and green-emitting BLWO:Tm{sup 3+} or Er{sup 3+} phosphors exhibited good thermal properties. - Abstract: BaLa{sub 2}WO{sub 7}:Tm{sup 3+} or Er{sup 3+} (BLWO:Tm{sup 3+} or Er{sup 3+}) single doped phosphors were prepared by a citrate-based sol-gel method. The crystalline properties of the prepared blue- and green-emitting phosphor materials were analyzed by X-ray diffraction (XRD) after annealing at 1350 °C. The XRD patterns of the both phosphors revealed monoclinic structure with a space group of P21/b. The morphological properties and elemental mappings of the BLWO:0.02Tm{sup 3+} and BLWO:0.01Er{sup 3+} phosphors were measured by field-emission scanning electron microscope images and energy dispersive X-ray spectrum, respectively. The photoluminescence (PL) spectra of BLWO:Tm{sup 3+} phosphors showed characteristic emission peaks of Tm{sup 3+} ions from the visible blue to near-infrared regions with the dominant emission at 799 nm ({sup 3}H{sub 4} → {sup 3}H{sub 6}) under ultraviolet (UV) and near-UV excitation wavelengths. Similarly, Er{sup 3+} ions activated BLWO phosphors exhibited intense green emissions at 548 nm ({sup 4}S{sub 3/2} → {sup 4}I{sub 15/2}) under the characteristic excitation wavelength of 381 nm. Furthermore, the temperature-dependent PL emission spectra and the luminescence decay curves were measured for the optimized BLWO:0.02Tm{sup 3+} and BLWO:0.01Er{sup 3+} phosphors. The chromaticity coordinates for the optimized blue- and green-emitting phosphors were calculated.

36 MATERIALS SCIENCE↗

Magnetocaloric Effect in La{sub 0.67}Ba{sub 0.33}Mn{sub 0.95}Ni{sub 0.05}O{sub 3} Manganite Near Room Temperature

We report the structural, magnetic, and magnetocaloric properties of La{sub 0.67}Ba{sub 0.33}Mn{sub 0.95}Ni{sub 0.05}O{sub 3} (LBMNO) manganite, synthesized by sol-gel method. X-ray diffraction (XRD) analysis using Rietveld refinement showed that this sample crystallizes in the rhombohedral structure with R 3-bar c space group. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analysis were used to confirm the structure formation of the LBMNO material. The temperature dependent magnetization data revealed a transition from ferromagnetic (FM) to paramagnetic (PM) phase at T{sub C}= 308 K. Using Arrott plots, it was found that the transition is of a second order. From the measured magnetization data as a function of magnetic applied field, the magnetic entropy change (−ΔS{sub M}) and the relative cooling power RCP have been determined. In the vicinity of T{sub C} (−ΔS{sub M}) reached a maximum value of 2.15 J kg{sup − 1} K{sup − 1} and a large RCP value of about 299 J kg{sup − 1} under 5 T{sup − 1}. This magnetocaloric effect has been analyzed by considering the Landau theory of magnetic phase transition. Consequently, our sample can be considered a promising material in room-temperature magnetic refrigeration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Observation of Room-Temperature Range Magnetocaloric Effect in PrSr{sub 1−x}Pb{sub x}Mn{sub 2}O{sub 6} (0.4 ≤ x ≤ 0.6) Double-Perovskite Manganite System

The Pr(Sr{sub 1−x}Pb{sub x})Mn{sub 2}O{sub 6} (0.4 ≤ x ≤ 0.6) double-perovskite manganite samples have been produced by using a sol-gel method. The Rietveld refinement method has been used to analyse the structural properties, and the results show that all samples are crystallized in monoclinic structure with P21/n space group without any impurity phase. The temperature dependence of magnetization measurement shows that samples exhibit paramagnetic to ferromagnetic phase transition by decreasing temperature. The values of the T{sub C} are determined as 286, 280 and 278 K for x= 0.4, 0.5 and 0.6 in Pr(Sr{sub 1−x}Pb{sub x})Mn{sub 2}O{sub 6} samples, respectively. Isothermal applied magnetic field-dependent magnetization curves are used to determine both order of magnetic phase transition and magnetic entropy change (ΔS{sub M}) value. −ΔS{sub M} values are found as 3.68, 3.15 and 2.85 J kg{sup − 1} K{sup − 1} for PSPM-4, PSPM-5 and PSPM-6 samples, respectively. Additionally, magnetic phase transition of the samples is identified as second-order magnetic phase transition that indicates accompanying small thermal and magnetic hysteresis to the samples during the phase transition. Relative cooling power (RCP) values are determined as 282, 233 and 268 J kg{sup − 1} for PSPM-4, PSPM-5 and PSPM-6 samples, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Elucidating structural order and disorder phenomena in mullite-type Al{sub 4}B{sub 2}O{sub 9} by automated electron diffraction tomography

The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, structural and electrical characterizations of DySr{sub 5}Ni{sub 2.4}Cu{sub 0.6}O{sub 12-{delta}}

A new compound DySr{sub 5}Ni{sub 2.4}Cu{sub 0.6}O{sub 12-{delta}} has been prepared by sol gel method and annealed at 1473 K in 1 atm of Ar gas flow. The X-ray diffraction (XRD) is used for phase identification. The sample shows to adopt the K{sub 2}NiF{sub 4}-type structure based on tolerance factor calculation. XRD analysis using the Rietveld method was carried out and it was found that DySr{sub 5}Ni{sub 2.4}Cu{sub 0.6}O{sub 12-{delta}} (Dy{sub 0.33}Sr{sub 1.67}Ni{sub 0.8}Cu{sub 0.2}O{sub 4-{delta}}') compound crystallizes in tetragonal symmetry with space group I4/mmm (Z=2). The lattice parameters are found to be at room temperature a=3.7696(5) A and c=12.3747(2) A. The final reliability indices were: R{sub B}=5.219% and {chi}{sup 2}=3.47. Four probe electrical resistivity measurements were performed versus temperature in the range 294-579 K. A semiconducting behaviour over the whole range of temperature, with a conductivity maximum of 0.4 S cm{sup -1} is observed at 510 K. - Graphical abstract: DySr{sub 5}Ni{sub 2.4}Cu{sub 0.6}O{sub 12-{delta}} exhibits a semi-conducting behaviour over the whole temperature range 294-579 K with a conductivity maximum of 0.4 S cm{sup -1} at 510 K. Highlights: > We described our attempts to synthesize the pure compound DySr{sub 5}Ni{sub 2.4}Cu{sub 0.6}O{sub 12-{delta}}. > Product was characterized by XRD and electrical resistivity measurements. > Iodometric titration was used for the analysis of the oxygen nonstoichiometry. > Calculated tolerance factor was included in the tetragonal symmetry stability range. > Compound exhibits a semi-conducting behaviour over the whole temperature range 294-579 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and electrical properties of the sol-gel prepared Sr{sub 1-x}Er{sub x}SnO{sub 3-{delta}} compounds

Erbium-substituted strontium stannates, with Er content 0{<=}x{<=}0.09, have been prepared by sol-gel method. The solubility limit of Er was found to be about 3%. The influence of temperature and the duration of the calcination, on the confirmation of single phase of Er doped SrSnO{sub 3} were investigated by using X-ray powder diffraction. The distribution of Er{sup 3+} in the crystal structure has been studied. Rietveld refinement of the data revealed that the crystal structure of the representative compound (Sr{sub 0.97}Er{sub 0.03}SnO{sub 3-{delta}}) is orthorhombic perovskite (space group Pbnm). The cell dimensions are: a=5.7152(1) A, b=5.7092(1) A and c=8.0710(2) A. The IR spectroscopy measurements of the samples with x{<=}0.03 were done in a wavelength range 400-2000 cm{sup -1} and confirmed the observed tilting in the SnO{sub 6} octahedra. The transport properties in the system Sr{sub 1-x}Er{sub x}SnO{sub 3-{delta}}, x{<=}0.03, were investigated at high temperature. The Sr{sub 0.97}Er{sub 0.03}SnO{sub 3-{delta}} compound exhibits semiconductive behaviour and the electrical transport mechanism agrees with the non-adiabatic small polaron hopping model between nominal states Sn{sup 4+}/Sn{sup 2+} in the temperature ranges 350-525 and 525-693 K separately. - Graphical abstract: The Sr{sub 0.97}Er{sub 0.03}SnO{sub 3-{delta}} compound exhibits semiconductive behaviour and the electrical transport mechanism agrees with the non-adiabatic small polaron hopping model between nominal states Sn{sup 4+}/Sn{sup 2+}. Highlights: Black-Right-Pointing-Pointer Er showed a maximum solubility of 3 mol% in SrSnO{sub 3} perovskite at 1173 K. Black-Right-Pointing-Pointer SnO{sub 6} octahedra in Sr{sub 1-x}Er{sub x}SnO{sub 3-{delta}} are tilted. Black-Right-Pointing-Pointer The expansion of the cell parameters ascribed to the apparition of Sn{sup 2+} ions. Black-Right-Pointing-Pointer Transport mechanism in Sr{sub 0.97}Er{sub 0.03}SnO{sub 3-{delta}} agrees with the non-adiabatic small polaron hopping model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural investigation and luminescence of nanocrystalline lanthanide doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3}

Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanostructured multiferroics (nanoparticles or nanorods) were prepared by a sol-gel route. X-Ray powder diffraction results evidence that the sodium and mixed sodium-potassium niobates show orthorhombic (Pmc2{sub 1} space group), and monoclinic structure (Pm space group), respectively, confirmed by the Raman spectra. The local structure around the trivalent lanthanides was investigated with Extended X-ray Absorption Fine Structure spectroscopy at the Ln-K edge and luminescence spectroscopy. The Ln{sup 3+} ions enter the structure by substituting the alkali metals, with a 12-fold oxygen coordination, and inducing a large amount of static disorder. The visible emission bands of the Eu{sup 3+} ions indicate that multiple sites exist for the lanthanide ions, in agreement with the EXAFS results showing the largest amount of static disorder in these samples. A possible indication of clustering of oxygen vacancies around the Ln{sub Na} Double-Prime defect is obtained by VBS calculations. - Graphical Abstract: Ln{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods can be prepared by a simple sol-gel procedure. The synergy of X-ray diffraction, EXAFS and luminescence spectroscopy gives important information on the Ln{sup 3+} local environment. Highlights: Black-Right-Pointing-Pointer Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods are prepared by sol-gel. Black-Right-Pointing-Pointer EXAFS indicates that the Ln{sup 3+} ions substitutes the Na{sup +} and K{sup +} ions, inducing a large amount of static disorder. Black-Right-Pointing-Pointer The visible emission bands of the Eu{sup 3+} ions confirm that multiple sites exist for the lanthanide ions.

36 MATERIALS SCIENCE↗

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt II →Ge IV Complex

Abstract Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [( o ‐(Ph 2 P)C 6 H 4 ) 2 Ge IV Cl 2 ]Pt II Cl 2 and [( o ‐(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [( o ‐(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl with quantum yields of 1.7 % and 3.2 % for the Ge IV –Pt II and Ge III –Pt III isomers, respectively. Conversion of the Ge IV –Pt II isomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the Ge III –Pt III isomer point to a ligand arene–Cl . charge‐transfer complex as an intermediate.

Karimi, Mohammadjavad↗

An energy model of droplet impingement on an inclined wall under isothermal and non-isothermal environments

The observation of spray-wall interaction is of great importance to understand the dynamics that occur during fuel impingement onto the chamber wall or piston surfaces in internal combustion engines. It is found that the maximum spreading length of an impinged droplet can provide a quantitative estimation of heat transfer and energy transformation for spray-wall interaction. Furthermore, it influences the air-fuel mixing and hydrocarbon and particle emissions at combusting conditions. In this paper, an analytical model of different droplet-wall impingement conditions is developed in terms of βm (dimensionless maximum spreading length, the ratio of maximum spreading length to initial droplet diameter) to understand the detailed impinging dynamic process. These conditions are grouped as: a single diesel droplet impinging on the wall with different inclined angles (α); cold wall - heated droplet and heated wall - cold droplet impingement when inclined angle of the wall is 0°, respectively. The analytical model is built up based on the energy conservation that considers kinetic energy, gravitation energy, and surface energy before impingement, as well as viscous dissipation, gravitation energy, adhesion energy, deformation energy, and heat energy after impingement. The experimental work of diesel droplet impinging on an inclined wall is performed at a certain range of the Weber number (We of 33 to 420) with various inclined angles (α of 0° to 45°), while for inclined angle is 0°, droplet and wall temperature are varied from 25°C to 150°C to study the effects of the inclined angle and temperature on the temporal evolution of the post-impingement characteristics (i.e. droplet spreading length, dynamic contact angle). The analytical model is validated and evaluated at the aforementioned experimental operating points. The validated model can be employed to predict maximum spreading length of the droplet impinged on the wall. It is further utilized to determine the transition from capillary regime to kinetic regime, then to viscous regime at different inclined angle of the wall.

42 ENGINEERING↗

Studies of the factors effecting the preparation of heterogeneous platinum-based catalyst on silica supports

Pt nanoparticles with an average size of {approx}3 nm were successfully immobilized on the surface of SiO{sub 2} functionalized with -NH{sub 2} and -SH groups through chemical reduction process using polyvinylpyrrolidone as a stabilizer and different reducing agents. The effects of molecular weight of polyvinylpyrrolidone, molar ratio of reducing agent to Pt salt, type of reducing agent on the size and degree of agglomeration of Pt nanoparticles on the SiO{sub 2} surface were investigated. The X-ray diffraction and transmission electron micrograph analyses were performed to identify the product phase, size and morphology of immobilized Pt onto SiO{sub 2}. UV-vis analysis was also conducted to identify the degree of reduction of Pt ions. The Pt-SiO{sub 2} nanocomposite prepared from both NH{sub 2}- and SH-functionalized SiO{sub 2} exhibited similar behavior. The number of immobilized Pt nanoparticles and their average size was increased with polyvinylpyrrolidone concentration while the number of immobilized Pt was decreased with its molecular weight.

36 MATERIALS SCIENCE↗

Peroxide-Selective Reduction of O 2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La–Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93–99% O22-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2( O 2 2- )(18C6) 2 (EG)2][OTf]4; 18C6 = 18-crown-6, EG = ethylene glycol, - OTf = - O 3 SCF 3 ; 2-Pr) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal–ligand binding events preceding electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ancestral genome reconstruction identifies the evolutionary basis for trait acquisition in polyphosphate accumulating bacteria

The evolution of complex traits is hypothesized to occur incrementally. Identifying the transitions that lead to extant complex traits may provide a better understanding of the genetic nature of the observed phenotype. A keystone functional group in wastewater treatment processes are polyphosphate accumulating organisms (PAOs), however the evolution of the PAO phenotype has yet to be explicitly investigated and the specific metabolic traits that discriminate non-PAO from PAO are currently unknown. Here we perform the first comprehensive investigation on the evolution of the PAO phenotype using the model uncultured organism Candidatus Accumulibacter phosphatis (Accumulibacter) through ancestral genome reconstruction, identification of horizontal gene transfer, and a kinetic/stoichiometric characterization of Accumulibacter Clade IIA. The analysis of Accumulibacter’s last common ancestor identified 135 laterally derived genes, including genes involved in glycogen, polyhydroxyalkanoate, pyruvate and NADH/NADPH metabolisms, as well as inorganic ion transport and regulatory mechanisms. In contrast, pathways such as the TCA cycle and polyphosphate metabolism displayed minimal horizontal gene transfer. We show that the transition from non-PAO to PAO coincided with horizontal gene transfer within Accumulibacter’s core metabolism; likely alleviating key kinetic and stoichiometric bottlenecks, such as anaerobically linking glycogen degradation to polyhydroxyalkanoate synthesis. These results demonstrate the utility of investigating the derived genome of a lineage to identify key transitions leading to an extant complex phenotype.

59 BASIC BIOLOGICAL SCIENCES↗

Visualizing molecular juggling within a B[subscript 12]-dependent methyltransferase complex

Derivatives of vitamin B{sub 12} are used in methyl group transfer in biological processes as diverse as methionine synthesis in humans and CO{sub 2} fixation in acetogenic bacteria. This seemingly straightforward reaction requires large, multimodular enzyme complexes that adopt multiple conformations to alternately activate, protect and perform catalysis on the reactive B{sub 12} cofactor. Crystal structures determined thus far have provided structural information for only fragments of these complexes, inspiring speculation about the overall protein assembly and conformational movements inherent to activity. Here we present X-ray crystal structures of a complete 220 kDa complex that contains all enzymes responsible for B{sub 12}-dependent methyl transfer, namely the corrinoid iron-sulphur protein and its methyltransferase from the model acetogen Moorella thermoacetica. These structures provide the first three-dimensional depiction of all protein modules required for the activation, protection and catalytic steps of B{sub 12}-dependent methyl transfer. In addition, the structures capture B{sub 12} at multiple locations between its 'resting' and catalytic positions, allowing visualization of the dramatic protein rearrangements that enable methyl transfer and identification of the trajectory for B{sub 12} movement within the large enzyme scaffold. The structures are also presented alongside in crystallo spectroscopic data, which confirm enzymatic activity within crystals and demonstrate the largest known conformational movements of proteins in a crystalline state. Taken together, this work provides a model for the molecular juggling that accompanies turnover and helps explain why such an elaborate protein framework is required for such a simple, yet biologically essential reaction.

59 BASIC BIOLOGICAL SCIENCES↗

Probing the active fraction of soil microbiomes using BONCAT-FACS

The ability to link soil microbial diversity to soil processes requires technologies that differentiate active microbes from extracellular DNA and dormant cells. Here, we use BONCAT (bioorthogonal non-canonical amino acid tagging) to measure translationally active cells in soils. We compare the active population of two soil depths from Oak Ridge (Tennessee, USA) and find that a maximum of 25-70% of the extractable cells are active. Analysis of 16S rRNA sequences from BONCAT-positive cells recovered by fluorescence-activated cell sorting (FACS) reveals that the phylogenetic composition of the active fraction is distinct from the total population of extractable cells. Some members of the community are found to be active at both depths independently of their abundance rank, suggesting that the incubation conditions favor the activity of similar organisms. We conclude that BONCAT-FACS is effective for interrogating the active fraction of soil microbiomes in situ and provides a new approach for uncovering the links between soil processes and specific microbial groups.

59 BASIC BIOLOGICAL SCIENCES↗

Adoption of a token-based authentication model for the CMS Submission Infrastructure

The CMS Submission Infrastructure (SI) is the main computing resource provisioning system for CMS workloads. A number of HTCondor pools are employed to manage this infrastructure, which aggregates geographically distributed resources from the WLCG and other providers. Historically, the model of authentication among the diverse components of this infrastructure has relied on the Grid Security Infrastructure (GSI), based on identities and X509 certificates. In contrast, commonly used modern authentication standards are based on capabilities and tokens. The WLCG has identified this trend and aims at a transparent replacement of GSI for all its workload management, data transfer and storage access operations, to be completed during the current LHC Run 3. As part of this effort, and within the context of CMS computing, the Submission Infrastructure group is in the process of phasing out the GSI part of its authentication layers, in favor of IDTokens and Scitokens. The use of tokens is already well integrated into the HTCondor Software Suite, which has allowed us to fully migrate the authentication between internal components of SI. Additionally, recent versions of the HTCondor-CE support tokens as well, enabling CMS resource requests to Grid sites employing this CE technology to be granted by means of token exchange. After a rollout campaign to sites, successfully completed by the third quarter of 2022, the totality of HTCondor CEs in use by CMS are already receiving Scitoken-based pilot jobs. On the ARC CE side, a parallel campaign was launched to foster the adoption of the REST interface at CMS sites (required to enable token-based job submission via HTCondor-G), which is nearing completion as well. In this contribution, the newly adopted authentication model will be described. We will then report on the migration status and final steps towards complete GSI phase out in the CMS SI.

Pérez-Calero Yzquierdo, Antonio↗

Stochastic Euler-Poincaré reduction

We prove a Euler-Poincaré reduction theorem for stochastic processes taking values on a Lie group, which is a generalization of the reduction argument for the deterministic case [J. E. Marsden and T. S. Ratiu, Introduction to Mechanics and Symmetry: A Basic Exposition of Classical Mechanical Systems, Texts in Applied Mathematics (Springer, 2003)]. We also show examples of its application to SO(3) and to the group of diffeomorphisms, which includes the Navier-Stokes equation on a bounded domain and the Camassa-Holm equation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Atomistic mechanisms governing structural stability change of zinc antimony thermoelectrics

The structural stability of thermoelectric materials is a subject of growing importance for their energy harvesting applications. Here, we study the microscopic mechanisms governing the structural stability change of zinc antimony at its working temperature, using molecular dynamics combined with experimental measurements of the electrical and thermal conductivity. Our results show that the temperature-dependence of the thermal and electrical transport coefficients is strongly correlated with a structural transition. This is found to be associated with a relaxation process, in which a group of Zn atoms migrates between interstitial sites. This atom migration gradually leads to a stabilizing structural transition of the entire crystal framework, and then results in a more stable crystal structure of β–Zn{sub 4}Sb{sub 3} at high temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Computational design of a homotrimeric metalloprotein with a trisbipyridyl core

Significance This article reports the computational design of a threefold symmetric, self-assembling protein homotrimer containing a highly stable noncanonical amino acid-mediated metal complex within the protein interface. To achieve this result, recently developed protein–protein interface design methods were extended to include a metal-chelating noncanonical amino acid containing a bipyridine functional group in the design process. Bipyridine metal complexes can give rise to photochemical properties that would be impossible to achieve with naturally occurring amino acids alone, suggesting that the methods reported here could be used to generate novel photoactive proteins.

59 BASIC BIOLOGICAL SCIENCES↗