SEARCH · Engineering Papers

Results for “coordinators”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,531 records · Page 85

All sources NASA NTRS DOE OSTI

DOE OSTI2015

Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal

Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel Cu{sup II}-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu{sub 2}[(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·3H{sub 2}O·DMF (1), and [Cu{sub 2}(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·7H{sub 2}O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible for the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays. - Graphical abstract: Cu-PDC-bpa 3-c herringbone arrays. - Highlights: • The most ideal herringbone array reported so far is a Cu-PDC-bpa SCF. • Conformational freedom of bpa results in 2D and 3D flexibility of the SCFs. • The flexibility of the SCFs is related to a phase transformation. • Dielectric measurements confirm the mobility of guest solvent molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{sup 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties. - Highlights: • Reaction variables affecting Mo(W)/S/Cu cluster-based CPs is firstly explored. • Replacing central metal atom had a pronounced effect on W/S/Cu cluster-based CPs. • Photocatalytic activities of Mo(W)/S/Cu cluster-based CPs are firstly investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Syntheses, structures and photoluminescent properties of Zn(Ⅱ)/Co(Ⅱ) coordination polymers based on flexible tetracarboxylate ligand of 5,5′-(butane-1,4-diyl)-bis(oxy)-di isophthalic acid

Three new mixed-ligand metal-organic frameworks based on 5,5′-(butane-1,4- diyl)-bis(oxy)-diisophthalic acid and transitional metal cations with the help of two ancillary bridging N-donor pyridyl and imidazole linkers, [Zn(L){sub 0.5}(4,4′-bpy)]·2(H{sub 2}O) (1), [M(L){sub 0.5}(bib)]·4(H{sub 2}O) (M = Zn (2), Co (3)), (4,4′-bpy=4,4′–bipyridine, bib=1,4-bis (1H-imidazol-1-yl)-butane), have been synthesized under solvothermal conditions. Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses (TGA). Compounds 1–3 display a 3D 3-fold interpenetrated frameworks linked by the L{sup 4−} ligands, ancillary N-donor linkers and the free water molecules in the crystal lattice. Topological analysis reveals that 1–3 are a (4,4)-connected bbf topology net with the (6{sup 4}·8{sup 2})(6{sup 6}) topology. The effects of the L{sup 4−} anions, the N-donor ligands, and the metal ions on the structures of the coordination polymers have been discussed. Furthermore, luminescence properties and thermogravimetric properties of these compounds were investigated. - Graphical abstract: Three new compounds of MOFs have been prepared and characterized. The luminescence properties and thermogravimetric properties of compounds were investigated. Display Omitted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Water linked 3D coordination polymers: Syntheses, structures and applications

Three new coordination polymers (CPs) based on Cd and Pb, [Cd(OBA)(μ-H{sub 2}O)(H{sub 2}O)]{sub n}1, [Pb(OBA)(μ-H{sub 2}O)]{sub n}2 [where OBA=4,4’-Oxybis(benzoate)] and [Pb(SDBA)(H{sub 2}O)]{sub n}.1/4DMF 3 (SDBA=4,4’-Sulfonyldibenzoate), have been synthesized and characterized. The single crystal structural studies reveal that CPs 1 and 2 have three dimensional structure. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. Compound 3 has a supramolecular 3D structure involving water molecule and hydrogen bonds. A structural transformation is observed when 3 was heated at 100 °C or kept in methanol, forming [Pb(SDBA)]{sub n}4. Compound 4 is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH{sub 4} at room temperature. Luminescence studies revealed that all CPs could be an effective sensor for nitroaromatic explosives. - Graphical abstract: Three new CPs based on Cd and Pb, have been synthesized and characterized. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. One of the CP is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol. Luminescence studies shown that all CPs could be an effective sensor for nitroaromatic explosives. - Highlights: • Three new CPs based on Cd and Pb, have been synthesized and characterized. • A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. • One of the CP is used as supporting matrix for palladium nanoparticles, PdNPs@4. • Luminescence studies shown that all CPs could be an effective sensor for nitroaromatic explosives.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas (Ln(H{sub 2}O){sub 6}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·xH{sub 2}O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], (Sm(H{sub 2}O){sub 5}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·10H{sub 2}O (5) and (Ln(H{sub 2}O){sub 5}(NO{sub 3})@Cy6Q[6])·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl{sub 2}. Single-crystal X-ray diffraction analyses revealed that compounds 1–8 all crystallize in monoclinic space group P2{sub 1}/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1–8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO){sub 3}, Tm(NO){sub 3}, Yb(NO){sub 3} under the same conditions resulted in the compounds 9–11 with formulas Cy6Q[6]·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations. - Graphical abstract: The reaction of cyclohexanocucurbit[6]uril with lanthanide ions (La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, Ho{sup 3+}, Tm{sup 3+} and Yb{sup 3+}) under hydrochloric acid in the presence of CdCl{sub 2} resulted in eleven compounds, which demonstrate interesting lanthanide contraction effect and provide a means of separating lanthanide ions. - Highlights: • Eleven compounds of the Ln{sup 3+} with the Cy6Q[6] were synthesized and described. • Compounds 1-8 demonstrate interesting lanthanide contraction effect. • In solid-state structures of compounds 9-11, no lanthanide ions were observed. • This study provides a means of separating lanthanides cations.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Design and construction of diverse structures of coordination polymers: Photocatalytic properties

The reaction of Cu(NO{sub 3}){sub 2}·3H{sub 2}O/Ni(NO{sub 3}){sub 2}·6H{sub 2}O with 4′-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2′:6′,4′′-terpyridine (H{sub 2}dbp) gave [Cu{sub 0.5}(Hdbp)]{sub n} (1) and [Ni(dbp)(H{sub 2}O)]{sub n} (2), while the reactions of Co(NO{sub 3}){sub 2}·6H{sub 2}O with H{sub 2}dbp in the presence of 4,4′-bipy and 2,2′-bpy generated [Co(dbp)(4,4′-bipy)]{sub n} (3) and ([Co(dbp)(2,2′-bipy)]{sub n}·H{sub 2}O) (4), respectively (4,4′-bipy=4.4′-pyridine and 2,2′-bipy=2,2′-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.6{sup 2}0.8{sup 3}){sub 2} topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4′-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1–4 for degradation of the methyl violet (MV) have been examined. - Graphical abstract: The photocatalytic activity and selectivity of complexes 1–4 prove that they may be good and stable photocatalysts for degradation of organic dyes.

36 MATERIALS SCIENCE↗

DOE OSTI2017

The assembly of two isomorphous coordination compounds based on 1,4-cyclohexanedicarboxylic acid and 2,4-diamino-6-phenyl-1,3,5-triazine

The compounds [Co(e,a-cis-1,4-chdc)(phdat)]{sub n} (1) and [Cd(e,a-cis-1,4-chdc)(phdat)]{sub n} (2) have been synthesized under hydrothermal method by using 1,4-cyclohexanedicarboxylic acid (1,4-H{sub 2}chdc), 2,4-diamino-6-phenyl-1,3,5-triazine (phdat) as well as CoCl{sub 2}·6H{sub 2}O, CdCl{sub 2}·2.5H{sub 2}O respectively and characterized by IR spectra, X-ray single-crystal diffraction, powder X-ray single-crystal diffraction (PXRD), elemental analyses and thermogravimetric analyses (TGA). The results show the compounds 1 and 2 are isomorphous and exhibit paddle-wheel dinuclear Co{sub 2}(CO{sub 2}){sub 4}/Cd{sub 2}(CO{sub 2}){sub 4} units, which are further connected to 1D chain structures by μ{sub 4}:η{sup 1}:η{sup 1}:η{sup 1}:η{sup 1} 1,4-chdc{sup 2–} ligands and extended into a 3D structures via different hydrogen bonding and π…π stacking interactions. Furthermore, compound 1 exhibits antiferromagnetic behavior and compound 2 displays luminescent behavior at solid state. - Graphical abstract: Two isomorphous coordination compounds 1–2 have been synthesized and characterized by XRD, IR spectra and TGA etc. Compound 1 and 2 display antiferromagnetic behavior and luminescent behavior respectively. - Highlights: • Two novel polymers based on 1,4-cyclohexanedicarboxylic acid have been synthesized. • Compounds 1 and 2 feather 1D chain structure built up from paddle-wheel SBUs. • The magnetism of 2 is investigated. • The electrochemical property and luminescent property of 1 are investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Binuclear and tetranuclear Mn(II) clusters in coordination polymers derived from semirigid tetracarboxylate and N‑donor ligands: syntheses, new topology structures and magnetism

Two topologically new Mn(II) coordination polymers, namely ([Mn{sub 2}(H{sub 4}ipca)(4,4′-bpy){sub 1.5}(CH{sub 3}CH{sub 2}OH){sub 0.5}(H{sub 2}O){sub 1.5}]·0.5CH{sub 3}CH{sub 2}OH·2.5H{sub 2}O){sub n} (1) and (Mn{sub 4}(H{sub 4}ipca){sub 2}(bze)(H{sub 2}O){sub 4}){sub n} (2) were prepared by the solvothermal reactions of Mn(II) acetate with 5-(2’,3’-dicarboxylphenoxy)isophthalic acid (H{sub 4}ipca) in the presence of different N-donor coligands (4,4′-bpy=4,4′-bipyridyl and bze=1, 4-bis(1-imidazoly)benzene). The single crystal X-ray diffractions reveal that two complexes display 3D metal-organic frameworks with binuclear and tetranuclear Mn(II) units, respectively. Complex 1 features a (3,4,6)-connected porous framework based on dinuclear Mn(II) unit with the (4.5{sup 2}){sub 2}(4{sup 2}.6{sup 8}.8{sup 3}.9{sup 2})(5{sup 2}.8.9{sup 2}.10) new topology, and complex 2 possesses a (3,8)-connected network based on tetranuclear Mn(II) unit with the (4{sup 2}.6){sub 2}(4{sup 4}.6{sup 14}.7{sup 7}.8{sup 2}.9) new topology. Magnetic analyses indicate that both two compounds show weak antiferromagnetic interactions within binuclear and tetranuclear Mn(II) units. - Graphical abstract: Two topologically new Mn(II) metal-organic frameworks with dinuclear and tetranuclear Mn(II) units respectively were assembled by using 5-(2′,3′-Dicarboxylphenoxy)isophthalic acid and N-donor ancillary coligands. Magnetic analysis revealed the existence of dominant antiferromagnetic interactions within the polynuclear Mn(II) units. - Highlights: • Mixed ligand strategy produces two topologically new MOFs with dinuclear and tetranuclear Mn(II) respectively. • Magnetic fitting gives weak antiferromagnetic interactions within the polynuclear Mn(II) units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Lead(II) coordination polymers based on rigid-flexible 3,5-bis-oxyacetate-benzoic acid: Structural transition driven by temperature control

Three Pb(II) complexes ([Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]·H{sub 2}O){sub n} (1), ([Pb{sub 4}(BOABA){sub 2}(µ{sub 4}-O)(H{sub 2}O){sub 2}]·H{sub 2}O){sub n} (2), and [Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]{sub n} (3) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid) were obtained under the same reaction systems with different temperatures. Complexes 1 and 2 are two dimensional (2D) networks based on Pb-BOABA chains and Pb{sub 4}(µ{sub 4}-O)(COO){sub 6} SBUs, respectively. Complex 3 presents an interesting three dimensional (3D) framework, was obtained by increasing the reaction temperature. Structural transition of the crystallization products is largely dependent on the reaction temperature. Moreover, the fluorescence properties of complexes 1–3 have been investigated. - Graphical abstract: Three Pb(II) coordination polymers were obtained under the same reaction systems with different temperatures. Both of complexes 1 and 2 are 2D network. 3 presents a 3D framework based on Pb–O–C rods SBUs. The 2D to 3D structures transition between three complexes was achieved successfully by temperature control. - Highlights: • Three Pb(II) complexes were obtained under the same reaction systems with different temperatures. • Structural transition of the crystallization products is largely dependent on the reaction temperature. • The luminescence properties studies reveal that three complexes exhibit yellow fluorescence emission behavior, which might be good candidates for obtaining photoluminescent materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N′-dimethylformamide

Five functional coordination polymers (formic-based CPs) namely: ([Cu{sub 2}(CHOO){sub 3}(bibp){sub 2}]·CHOO){sub n} (1), ([Co{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O)n (2), ([Ni{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O){sub n} (3) [Co(CHOO){sub 2}(bbibp)]{sub n} (4) and [Zn(CHOO){sub 2}(bbibp)]{sub n} (5) (bibp=4,4′-bis(imidazolyl)biphenyl, bbibp=4,4′-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N′-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1–3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C–H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni_3(TBIB)_2(BTC)_2(H_2O)_6]·5C_2H_5OH·9H_2O}{sub n} [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H{sub 3}BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe. - Graphical abstract: A number of nanoparticles including Au, Pd, Mn, Fe, Cu, Zn, Mg, Li as well as mixed NPs Fe/Cu, Zn/Mg have been synthesized at room temperature without use of any surfactant and reducing agent. Display Omitted - Highlights: • Different types of NPs have been synthesized in a 2D polymer at room temperature. • Surfactant and reducing agents have not been used for NPs synthesis. • Monodentate carboxylate groups of BTC linker act as anchoring sites for metal ions. • NPs were synthesized by acid formation and redox activity of the framework. • Fe NPs integrated framework shows paramagnetic properties at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Fe(III) and Cu(II) coordination polymers assembled from di/tris-phosphonic acid and auxiliary ligands: Structure, SOD-like activity and magnetic behavior

Hydrothermal reactions of (benzylazanediyl)bis(methylene)-diphosphonic acid (H{sub 4}L{sup 1}) or (benzene-1,3,5-triyltris(methylene))triphosphonic acid (H{sub 6}L{sup 2}) with Fe(III)/Cu(II) nitrate and 4, 4′-bipy or 2, 2′-bipy result in five new phosphonates, namely, [FeHL{sup 1}(H{sub 2}O)]{sub n} (1), {[Cu_2L"1(4, 4′-bipy)_0_._5(H_2O)]·0.25H_2O}{sub n} (2), [Cu{sub 2}H{sub 2}L{sup 2}(4, 4′-bipy)(H{sub 2}O){sub 2}]{sub n} (3), [CuH{sub 4}L{sup 2}(2, 2′-bipy)]{sub n} (4) and [Cu{sub 2}(H{sub 4}L{sup 2}){sub 2}(2, 2′-bipy){sub 2}(H{sub 2}O){sub 4}] (5), respectively. X-ray structural analysis indicates that 2 and 3 feature 3D framework structures with 3, 3, 3, 4-connected and 4, 5-connected topology; 1 and 4 display 1D chain structures, while 5 has a dimer structure. The di- or trisphosphonate ligands (H{sub 4}L{sup 1} and H{sub 6}L{sup 2}) in the five complexes adopt different coordination modes and auxiliary ligands (4, 4′-bipy and 2, 2′-bipy) control the dimensionality of the final complexes. The superoxide dismutase (SOD) activities of 2–5 were assessed by modified nitrobluetetrazolium (NBT) assay. The IC{sub 50} values required to yield 50% inhibition of the reduction of NBT are 1.84, 2.02, 6.95 and 1.70 μM for 2–5, respectively, demonstrating better SOD-like activity than most of the Cu-SOD mimic enzymes reported in literatures. Among them, 2 and 3 have good stability and reusability under the simulative physiological conditions. The dismutation of 4 and 5 toward superoxide anion radicals can be attributed to the synergistic effect of the decomposition products of 4 and 5 containing Cu(II) and [H{sub 4}L{sup 2}]{sup 2-} with or without 2, 2′-bipy or Cu(II) and 2, 2′-bipy, which were identified by liquid mass spectrometry (LC/MS). The magnetic properties of complexes 1–4 were also investigated, indicating the presence of magnetic exchange between metal ions. The results show that 1 and 3 exhibit antiferromagnetic interactions, while 2 and 4 show ferromagnetic interactions between metal centres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Nitrogen-coordinated single iron atom catalysts derived from metal organic frameworks for oxygen reduction reaction

Iron and nitrogen co-doped carbon (Fe-N-C) catalysts hold great promise to replace platinum group metal used for the oxygen reduction reaction (ORR) in low-temperature fuel cells. However, general synthesis routes require tedious acid washing and extensive heat treatment, usually resulting in uncontrollable morphologies and undesirable compounds. In this work, a zeolitic imidazolate framework (ZIF-8) was employed as a self-template for one-pot synthesis of a Fe-N-C catalyst consisting of uniformly dispersed Fe single atoms. Atomically dispersed Fe atoms were well distributed along the edges of the porous carbon matrix. Each of the Fe atoms was coordinated with four N atoms in the plane and two O atoms in the axial direction. The optimized Fe-N-C catalyst showed excellent ORR activities with half-wave potentials of 0.81 and 0.90 V in acidic and alkaline solutions, respectively. The results may be important for the optimization of single-atom-based catalysts for various reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

The IAEA coordinated research programme on HTGR uncertainty analysis: Phase I status and Ex. I-1 prismatic reference results

The quantification of uncertainties in design and safety analysis of reactors is today not only broadly accepted, but in many cases became the preferred way to replace traditional conservative analysis for safety and licensing analysis. The use of a more fundamental methodology is also consistent with the reliable high fidelity physics models and robust, efficient, and accurate codes available today. To facilitate uncertainty analysis applications a comprehensive approach and methodology must be developed and applied, in contrast to the historical approach where sensitivity analysis were performed and uncertainties then determined by a simplified statistical combination of a few important input parameters. New methodologies are currently under development in the OECD/NEA Light Water Reactor (LWR) Uncertainty Analysis in Best-Estimate Modelling (UAM) benchmark activity. High Temperature Gas-cooled Reactor (HTGR) designs require specific treatment of the double heterogeneous fuel design and large graphite quantities at high temperatures. The IAEA has therefore launched a Coordinated Research Project (CRP) on HTGR Uncertainty Analysis in Modelling (UAM) in 2013 to study uncertainty propagation specifically in the HTGR analysis chain. Two benchmark problems are defined, with the prismatic design represented by the General Atomics (GA) MHTGR-350 and a 250 MW modular pebble bed design similar to the Chinese HTR-PM. Work has started on the first phase and the current CRP status is reported in the paper. A comparison of the Serpent and SCALE/KENO-VI reference Monte Carlo results for Ex. I-1 of the MHTGR-350 design is also included. It was observed that the SCALE/KENO-VI Continuous Energy (CE) k ∞ values were 395 pcm (Ex. I-1a) to 803 pcm (Ex. I-1b) higher than the respective Serpent lattice calculations, and that within the set of the SCALE results, the KENO-VI 238 Multi-Group (MG) k ∞ values were up to 800 pcm lower than the KENO-VI CE values. The use of the latest ENDF-B-VII.1 cross section library in Serpent lead to ~180 pcm lower k ∞ values compared to the older ENDF-B-VII.0 dataset, caused by the modified graphite neutron capture cross section. Furthermore, the fourth beta release of SCALE 6.2 likewise produced lower CE k∞ values when compared to SCALE 6.1, and the improved performance of the new 252-group library available in SCALE 6.2 is especially noteworthy. A SCALE/TSUNAMI uncertainty analysis of the Hot Full Power variant for Ex. I-1a furthermore concluded that the 238 U(n,γ) (capture) and 235 U(View the MathML source) cross-section covariance matrices contributed the most to the total k ∞ uncertainty of 0.58%.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

Local search to improve coordinate-based task mapping

We present a local search strategy to improve the coordinate-based mapping of a parallel job’s tasks to the MPI ranks of its parallel allocation in order to reduce network congestion and the job’s communication time. The goal is to reduce the number of network hops between communicating pairs of ranks. Our target is applications with a nearest-neighbor stencil communication pattern running on mesh systems with non-contiguous processor allocation, such as Cray XE and XK Systems. Utilizing the miniGhost mini-app, which models the shock physics application CTH, we demonstrate that our strategy reduces application running time while also reducing the runtime variability. Furthermore, we further show that mapping quality can vary based on the selected allocation algorithm, even between allocation algorithms of similar apparent quality.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2023

Insights into substrate coordination and glycosyl transfer of poplar cellulose synthase-8

Cellulose is an abundant cell wall component of land plants. It is synthesized from UDP-activated glucose molecules by cellulose synthase, a membrane-integrated processive glycosyltransferase. Cellulose synthase couples the elongation of the cellulose polymer with its translocation across the plasma membrane. Here, we present substrate- and product-bound cryogenic electron microscopy structures of the homotrimeric cellulose synthase isoform-8 (CesA8) from hybrid aspen (poplar). UDP-glucose binds to a conserved catalytic pocket adjacent to the entrance to a transmembrane channel. The substrate’s glucosyl unit is coordinated by conserved residues of the glycosyltransferase domain and amphipathic interface helices. Site-directed mutagenesis of a conserved gating loop capping the active site reveals its critical function for catalytic activity. Molecular dynamics simulations reveal prolonged interactions of the gating loop with the substrate molecule, particularly across its central conserved region. These transient interactions likely facilitate the proper positioning of the substrate molecule for glycosyl transfer and cellulose translocation.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Improving the performance of first- and last-mile mobility services through transit coordination, real-time demand prediction, advanced reservations, and trip prioritization

Socio-demographic trends and recent economic development patterns have resulted in travel behavior changes that call for more flexible and accessible public transit options. Because flexible transit services vary in scope, size, and service type, new data-informed methods are useful to optimize services based on the specific needs of local communities and riders. In this study, real-world demand and vehicle trajectory data were used to evaluate and optimize system performance for an existing first-mile–last-mile (FMLM) service in Robinson Township, PA. A general FMLM model for arbitrary demand and service supply was then developed to quantify system performance—both travel time costs and day-to-day reliability—for various operational polices considering spatio-temporal demand variation and transportation network dynamics. Heuristics were used for optimal real-time vehicle routing in sizable real-world networks accommodating various service types and scopes. In this case study, total user costs were reduced by 18.6% when rides were coordinated with mainline fixed-route transit. Predictive routing strategies were shown to marginally improve system performance under sparse and variable spatio-temporal demand. The case study also highlights potentially large travel time and user reliability improvements—reductions of 51% and 53.8%, respectively—when trip requests were made in advance of their desired pickup time. Finally, we show that travel time reliability can be improved for time-inflexible trips with trip prioritization without increasing total user costs. These results were stable to changes in demand density.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2026

Integrating three plan evaluation approaches for coordinated heat resilience in cities across the Arizona urban corridor

Increasing heat poses a growing threat to cities worldwide due to both climate change and the urban heat island effect. While heat planning and governance are still emergent, research suggests that silos and conflicts within cities' networks of plans often impede heat resilience. Integrated heat resilience planning, therefore, requires a systematic and comprehensive analysis of the silos and conflicts relevant to heat resilience within networks of plans. This study is the first to combine three complementary plan evaluation methods to assess how cities' networks of plans address heat resilience. We applied 1) plan cross-referencing, 2) Plan Quality Evaluation for Heat Resilience, and 3) Plan Integration for Resilience Scorecard™ (PIRS™) for Heat to 19 plans from seven Arizona cities. We find similarities and differences in how these cities' networks of plans address heat hazards. The plans have consistently high-quality participation and coordination principles but lack details on vulnerability and climate change uncertainty, suggesting a need to move beyond immediate heat risks. We also identify opportunities to diversify policy mechanisms, spatially target high heat risk areas, and enhance the connection between planning efforts. These results validate that plan elements are interlinked and the importance of integrative plan development processes to improve heat resilience.

Extreme heat↗