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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.

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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Impact of f-element complexation on the radiolytic robustness of separations ligands

Impact of f-element complexation on the radiolytic robustness of separations ligands Gregory P. Horne, Makayla R. Baxter, Corey D. Pilgrim, Travis S. Grimes, Center for Radiation Chemistry Research, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID, 83415, USA Cristian Celis Barros, Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA. E-mail: ccelisbarros@fsu.edu Andrew R. Cook, Department of Chemistry, Brookhaven National Laboratory, Upton, New York, 11973, USA Stephen P. Mezyk, Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Boulevard, Long Beach, California, 90840-9507, USA The effects of ionizing radiation are ubiquitous throughout all aspects of a nuclear fuel cycle. However, the complexity and intensity of these effects are greatest during the management of used nuclear fuel, owing to the presence of a wide spectrum of radionuclides from neutron capture and fission processes. With regards to used nuclear fuel (UNF) reprocessing, radiation-induced processes typically promote the destruction of active compounds (e.g., complexants and additives) with the concomitant formation of potentially detrimental degradation products and corresponding changes in physical and chemical properties, which ultimately impact the effectiveness and longevity of a given reprocessing system. Concerning UNF complexants, radiation chemistry studies have historically focused on their radiation robustness in the absence of the metal ions they were designed to selectively complex. This knowledge gap is worrisome as previous studies on aqueous phase complexants have demonstrated significant changes in radiolytic behavior upon metal ion complexation.1-4 More recently, the rate of reaction of the n-dodecane radical cation—believed to be the major organic phase radiation-induced transient species responsible for complexant radiolysis in n-dodecane based solvent systems—with hexa-n-octylnitrilo-triacetamide (HONTA) was shown to increase by an order-of-magnitude upon complexation of europium or americium.5 These findings have significant implications on the projected longevity of complexants in UNF reprocessing solvent systems. Consequently, a thorough understanding of metal ion complexation effects on the radiolytic integrity of UNF complexants is essential to evaluate their potential for process application. Presented here are two recent studies from the Idaho National Laboratory Center for Radiation Chemistry Research group that demonstrate the various impacts of f-element complexation (uranium, americium, and lanthanides) on the radiolytic integrity (gamma and electron pulse) of tributyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), N,N-di-2-ethylhexylisobutryamide (DEHiBA), and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) under UNF reprocessing conditions. References 1) Bhattacharyya and Kundu, Int. J. Radiat. Phys. Chem., 1971, 3, 1. 2) Kundu and Matuura, Int. J. Radiat. Phys. Chem., 1975, 7, 565. 3) Ilan and Czapski, Biochimica et Biophysica Acta, 1977, 498, 386. 4) Buettner, Doherty, and Patterson, Fed. Euro. Biochem. Soc., 1983, 158 (1), 143. 5) Toigawa, Peterman, Meeker, Grimes, Zalupski, Mezyk, Cook, Yamashita, Kumagai, Matsumura, Horne, PCCP, 2021, 23, 1343.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2013

Concentration-dependent oligomerization of cross-linked complexes between ferredoxin and ferredoxin–NADP{sup +} reductase

Highlights: •Cross-linked complexes of ferredoxin (Fd) and Fd–NADP{sup +} reductase form oligomers. •In the crystal structures, Fd- and FNR moieties swap across the molecules. •The complexes exhibit concentration-dependent oligomerization at sub-milimolar order. -- Abstract: Ferredoxin–NADP{sup +} reductase (FNR) forms a 1:1 complex with ferredoxin (Fd), and catalyzes the electron transfer between Fd and NADP{sup +}. In our previous study, we prepared a series of site-specifically cross-linked complexes of Fd and FNR, which showed diverse electron transfer properties. Here, we show that X-ray crystal structures of the two different Fd–FNR cross-linked complexes form oligomers by swapping Fd and FNR moieties across the molecules; one complex is a dimer from, and the other is a successive multimeric form. In order to verify whether these oligomeric structures are formed only in crystal, we investigated the possibility of the oligomerization of these complexes in solution. The mean values of the particle size of these cross-linked complexes were shown to increase with the rise of protein concentration at sub-milimolar order, whereas the size of dissociable wild-type Fd:FNR complex was unchanged as analyzed by dynamic light scattering measurement. The oligomerization products were detected by SDS–PAGE after chemical cross-linking of these complexes at the sub-milimolar concentrations. The extent and concentration-dependent profile of the oligomerizaion were differentiated between the two cross-linked complexes. These results show that these Fd–FNR cross-linked complexes exhibit concentration-dependent oligomerization, possibly through swapping of Fd and FNR moieties also in solution. These findings lead to the possibility that some native multi-domain proteins may present similar phenomenon in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Cobalt(II) complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine: Structures, photoluminescent and photocatalytic properties

Six new Co{sup II} complexes [Co(L{sup 1}){sub 4}(OH){sub 2}] (1), {[Co(L"1)(H_2O)_4]·2ClO_4}{sub ∞} (2), {[Co(L"1)(H_2O)_4]·SiF_6}{sub ∞} (3), {[Co(L"1)_3]·2ClO_4}{sub ∞} (4), [Co(L{sup 2})Cl{sub 2}]{sub ∞} (5) and {[Co(L"2)_2]·SiF_6}{sub ∞} (6) [L{sup 1}=3,6-bis(N-imidazolyl) pyridazine, L{sup 2}=3,6-bis (N-benzimidazolyl) pyridazine] have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 has a mononuclear structure, while complexes 2 and 3 have 1-D chain structures. Considering the Co{sup II} centers were linked by the L{sup 1} ligands, the 3-D framework of complex 4 can be rationalized to be a {4^12.6^3} 6-c topological net with the stoichiometry uninodal net. 5 reveals a coordination 1-D zigzag chain structure consisting of a neutral chain [Co(L{sup 2})Cl{sub 2}]{sub n} with the Co{sup II} centers. Complex 6 has a rhombohedral grid with a (4, 4) topology. The TGA property, fluorescent property and photocatalytic activity of complexes 1–6 have been investigated and discussed. - Graphical abstract: Six Co{sup II} complexes of bis(N-imidazolyl/benzimidazolyl)pyridazine were synthesized and structurally characterized. The fluorescence properties and photocatalytic activity for dye degradation under UV light of all complexes have been investigated and discussed. Display Omitted - Highlights: • Six new Co{sup II} complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine. • Structural analysis of all complexes. • Fluorescent property of all complexes. • Photocatalytic activity for dye degradation under UV light of all complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ultrastructure of Critical-Gel-like Polyzwitterion–Polyoxometalate Complex Coacervates: Effects of Temperature, Salt Concentration, and Shear

The structure of unconventional complex coacervates, such as polymer-nonpolymer complex coacervates, remains less investigated than that of the conventional coacervates formed between oppositely charged polyelectrolytes with symmetric charge species. Yet, their microscopic structural organization is important to further elucidate the mechanism of liquid-liquid-phase separation processes upon complexation. In this work, we characterize the microstructural organization of complex coacervates formed between inorganic polyoxometalate (POM) and polyzwitterion by small-angle X-ray scattering (SAXS) with in situ temperature and shear control. Furthermore, despite the apparent transparent and homogeneous morphology of dense coacervates as observed by optical microscopy, our previous results (Macromolecules 2018, 51, 22, 9405-9411) suggest that dense polyzwitterion-POM coacervates exhibit critical-gel-like networks containing both complex-poor region (mesh pore) and complex-rich region (connective network). SAXS results as reported in this work support that the complex-rich region is actually in the form of loosely packed POM aggregates linked by polyzwitterion, designated as complex particles. The structure of aggregating complex particles is further examined against varied composition and salt concentrations, temperature, and shear, thanks to the high X-ray scattering contrast of POMs from that of other components in the coacervates. The complex particles in the dense coacervates appear to grow with more tightly packed POM aggregates with increasing POM-to-polyzwitterion concentration ratio, in contrast to more loosely packed POM aggregates with decreasing salt concentration. Conversely, increasing temperature could result in smaller complex particles containing more loosely packed POM aggregates, consistent with temperature-dependent viscoelasticity of dense coacervates. Furthermore, such POM-based hybrid dense coacervates exhibit intriguing strain-hardening behavior, resulting from shear-enhanced POM packing inside the complex particles. Distinct from the shear-thinning behavior of most conventional crosslinked polymeric networks, the strain-hardening property combined with thermal- and salt-responsive characteristics of polyzwitterion-POM coacervates could broaden the applications of hybrid organic-inorganic macroion coacervates as smart functional materials working under extreme environmental conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Positional effects of hydroxy groups on catalytic activity of proton-responsive half-sandwich Cp*Iridium(III) complexes

Proton-responsive half-sandwich Cp*Ir(III) complexes possessing a bipyridine ligand with two hydroxy groups at the 3,3'-, 4,4'-, 5,5'- or 6,6'-positions (3DHBP, 4DHBP, 5DHBP, or 6DHBP) were systematically investigated. UV-vis titration data provided average pK a values of the hydroxy groups on the ligands. Both hydroxy groups were found to deprotonate in the pH 4.6–5.6 range for the 4–6DHBP complexes. One of the hydroxy groups of the 3DHBP complex exhibited the low pK a value of < 0.4 because the deprotonation is facilitated by the strong intramolecular hydrogen bond formed between the generated oxyanion and the remaining hydroxy group, which in turn leads to an elevated pK a value of ~13.6 for the second deprotonation step. The crystal structures of the 4– and 6DHBP complexes obtained from basic aqueous solutions revealed their deprotonated forms. The intramolecular hydrogen bond in the 3DHBP complex was also observed in the crystal structures. The catalytic activities of these complexes in aqueous phase reactions, at appropriate pH, for hydrogenation of carbon dioxide (pH 8.5), dehydrogenation of formic acid (pH 1.8), transfer hydrogenation reactions using formic acid/formate as a hydrogen source (pH 7.2 and 2.6) were investigated to compare the positional effects of the hydroxy groups. The 4– and 6DHBP complexes exhibited remarkably enhanced catalytic activities under basic conditions because of the resonance effect of the strong electrondonating oxyanions, whereas the 5DHBP complex exhibited negligible activity despite the presence of electron-donating groups. The 3DHBP complex exhibited relatively high catalytic activity at low pH owing to the one strong electron-donating oxyanion group stabilized by the intramolecular hydrogen bond. DFT calculations were employed to study the mechanism of CO₂ hydrogenation by the 4DHBP and 6DHBP complexes, and comparison of the activation free energies of the H₂ heterolysis and CO₂ insertion steps indicated that H₂ heterolysis is the rate-determining step for both complexes. The presence of a pendent base in the 6DHBP complex was found to facilitate the rate-determining step, and renders 6DHBP a more effective catalyst for formate production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Chemical bonding in actinyl( V / VI ) dipyriamethyrin complexes for the actinide series from americium to californium: a computational investigation

The separation of minor actinides in their dioxocation (i.e., actinyl) form in high-valence oxidation states requires efficient ligands for their complexation. Here, in this work, we evaluate the complexation properties of actinyls including americyl, curyl, berkelyl, and californyl in their pentavalent and hexavalent oxidation states with the dipyriamethyrin ligand (L) using density functional theory calculations. The calculated bond parameters show shorter An&#x2550O yl bonds with covalent character and longer An–N bonds with ionic character. The bonding between the actinyl cation and the ligand anion shows a flow of charges from the ligand to actinyl in all [An V/VI O 2 –L] 1–/0 complexes. However, across the series, backdonation of charges from the metal to the ligand becomes prominent and stabilizes the complexes. The thermodynamic parameters in the gas phase and solution suggest that the complex formation reaction is spontaneous for [Cf V/VI O 2 –L] 1–/0 complexes and spontaneous at elevated temperatures (>298.15 K) for all other complexes. Spin–orbit corrections have a quantitative impact while the overall trend remains the same. Energy decomposition analysis (EDA) reveals that the interaction between actinyl and the ligand is mainly due to electrostatic contributions that decrease from Am to Cf along with an increase in orbital contributions due to the backdonation of charges from the actinyl metal center to the ligand that greatly stabilizes the Cf complex. The repulsive Pauli energy contribution is observed to increase in the case of [An V O 2 –L] 1– complexes from Am to Cf while a decrease is observed among [An VI O 2 –L] 0 complexes, showing minimum repulsion in [Cf VI O 2 –L] 0 complex formation. Overall, the hexavalent actinyl complexes show greater stability (increasing from Am to Cf) than their pentavalent counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ', N '-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙ + from 10–40 °C, giving the activation energy (E a = 17.43 ± 1.64 kJ mol –1 ) and pre-exponential factor (A = (2.36 ± 0.05) × 10 13 M –1 s –1 ). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙ + , relative to the non-complexed ligand: k([Ln III (TODGA) 3 (NO 3 ) 3 ] + RH˙ + ) = (8.99 ± 0.93) × 10 10 , (2.88 ± 0.40) × 10 10 , and (1.53 ± 0.34) × 10 10 M –1 s –1 , for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations—based on a model [Ln III (TOGDA)] 3+ complex system—indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [Ln III (TEGDA) 3 (NO 3 ) 3 ], toward electrophilic attack is for the coordinated nitrate (NO 3 – ) counter anions. Furthermore, it is possible that radical reactions with the complexed NO 3 – counter anions dominate the differences in rates seen for the [Ln III (TODGA) 3 (NO 3 ) 3 ] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Cryo-EM structures of light-harvesting 2 complexes from Rhodopseudomonas palustris reveal the molecular origin of absorption tuning

The genomes of some purple photosynthetic bacteria contain a multigene puc family encoding a series of α- and β-polypeptides that together form a heterogeneous antenna of light-harvesting 2 (LH2) complexes. To unravel this complexity, we generated four sets of puc deletion mutants in Rhodopseudomonas palustris , each encoding a single type of pucBA gene pair and enabling the purification of complexes designated as PucA-LH2, PucB-LH2, PucD-LH2, and PucE-LH2. The structures of all four purified LH2 complexes were determined by cryogenic electron microscopy (cryo-EM) at resolutions ranging from 2.7 to 3.6 Å. Uniquely, each of these complexes contains a hitherto unknown polypeptide, γ, that forms an extended undulating ribbon that lies in the plane of the membrane and that encloses six of the nine LH2 αβ-subunits. The γ-subunit, which is located near to the cytoplasmic side of the complex, breaks the C9 symmetry of the LH2 complex and binds six extra bacteriochlorophylls (BChls) that enhance the 800-nm absorption of each complex. The structures show that all four complexes have two complete rings of BChls, conferring absorption bands centered at 800 and 850 nm on the PucA-LH2, PucB-LH2, and PucE-LH2 complexes, but, unusually, the PucD-LH2 antenna has only a single strong near-infared (NIR) absorption peak at 803 nm. Comparison of the cryo-EM structures of these LH2 complexes reveals altered patterns of hydrogen bonds between LH2 αβ-side chains and the bacteriochlorin rings, further emphasizing the major role that H bonds play in spectral tuning of bacterial antenna complexes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

SU-E-T-353: Decoding the Beam Complexity in Intensity-Modulated Radiation Therapy Plans

Purpose: Modern IMRT relies on computers to generate treatment plans of varied complexity. A highly complex treatment plan may use a large number of small and irregular beam apertures in order to achieve high dose conformity. However, excessive beam complexity can increase dosimetric uncertainty, prolong treatment time, and increase susceptibility to target or organ motion. In this study we sought to develop metrics to assess the complexity of IMRT beams and plans. Methods: Based the information of leaf positions and MU for each beam segment, we calculated the following beam complexity metrics: aperture area, shape irregularity, and beam modulation. Then these beam complexity metrics were averaged to obtain the corresponding plan complexity metrics, using the beam MUs as weighting factors. We evaluated and compared the beam and plan complexity scores for 65 IMRT plans from 3 sites (prostate, head and neck, and spine). We also studied how the plan complexity scores were affected by adjusting inverse planning parameters. Results: For prostate IMRT, the lateral beams had large MUs and smaller shape irregularity, while the anterior or posterior beams had larger modulation values. On average, the prostate IMRT plans had the smallest shape irregularity and beam modulation; the HN IMRT plans had the largest aperture area, shape irregularity, and beam modulation; and the spine stereotactic IMRT plans often had small aperture area, which may be associated with relatively large discrepancies between calculated and measures doses. The plan complexity increased as the number of optimization iterations and the number of beam segments increased and as the minimum segment area decreased. Conclusion: Complexity of IMRT beams and plans were quantified in terms of aperture area, shape irregularity and beam modulation. The complexity metrics varied among IMRT plans for different disease sites and were affected when the planning parameters were adjusted.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2011

Stephen Jay Kline on systems, or physics, complex systems, and the gap between.

At the end of his life, Stephen Jay Kline, longtime professor of mechanical engineering at Stanford University, completed a book on how to address complex systems. The title of the book is 'Conceptual Foundations of Multi-Disciplinary Thinking' (1995), but the topic of the book is systems. Kline first establishes certain limits that are characteristic of our conscious minds. Kline then establishes a complexity measure for systems and uses that complexity measure to develop a hierarchy of systems. Kline then argues that our minds, due to their characteristic limitations, are unable to model the complex systems in that hierarchy. Computers are of no help to us here. Our attempts at modeling these complex systems are based on the way we successfully model some simple systems, in particular, 'inert, naturally-occurring' objects and processes, such as what is the focus of physics. But complex systems overwhelm such attempts. As a result, the best we can do in working with these complex systems is to use a heuristic, what Kline calls the 'Guideline for Complex Systems.' Kline documents the problems that have developed due to 'oversimple' system models and from the inappropriate application of a system model from one domain to another. One prominent such problem is the Procrustean attempt to make the disciplines that deal with complex systems be 'physics-like.' Physics deals with simple systems, not complex ones, using Kline's complexity measure. The models that physics has developed are inappropriate for complex systems. Kline documents a number of the wasteful and dangerous fallacies of this type.

42 ENGINEERING↗
NASA NTRS1999

Environmental Conditions and Threatened and Endangered Species Populations near the Titain, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1995-1998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for greater than 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally- listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitant resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycteria americana) and several state-listed species of special concern including the Snowy Egret (Egretta thula thula), Reddish Egret (Egretta rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egretta tricolor ruficolis), and Little Blue Heron (Egretta caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch complexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗
DOE OSTI2021

The Stellar decomposition: A compact representation for simplicial complexes and beyond

Here, we introduce the Stellar decomposition, a model for efficient topological data structures over a broad range of simplicial and cell complexes. A Stellar decomposition of a complex is a collection of regions indexing the complex’s vertices and cells such that each region has sufficient information to locally reconstruct the star of its vertices, i.e., the cells incident in the region’s vertices. Stellar decompositions are general in that they can compactly represent and efficiently traverse arbitrary complexes with a manifold or non-manifold domain. They are scalable to complexes in high dimension and of large size, and they enable users to easily construct tailored application-dependent data structures using a fraction of the memory required by a corresponding global topological data structure on the complex. As a concrete realization of this model for spatially embedded complexes, we introduce the Stellar tree, which combines a nested spatial tree with a simple tuning parameter to control the number of vertices in a region. Stellar trees exploit the complex’s spatial locality by reordering vertex and cell indices according to the spatial decomposition and by compressing sequential ranges of indices. Stellar trees are competitive with state-of-the-art topological data structures for manifold simplicial complexes and offer significant improvements for cell complexes and non-manifold simplicial complexes. We conclude with a high-level description of several mesh processing and analysis applications that utilize Stellar trees to process large datasets.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Quantification of Coexisting Inner- and Outer-Sphere Complexation of Sulfate on Hematite Surfaces

Sulfate adsorption on hematite surfaces controls sulfate mobility and environmental behavior but whether sulfate forms both inner- and outer-sphere complexes and the type of the inner-sphere complexes remain contentious. With ionic strength tests and S K-edge X-ray absorption near-edge structure spectroscopy, we show that sulfate forms both outer- and inner-sphere complexes on hematite surfaces. Both S K-edge extended X-ray absorption fine structure spectroscopy and the differential pair distribution function analyses determine the S–Fe interatomic distance (~3.24 Å) of the inner-sphere complex, suggesting bidentate-binuclear complexation. A multivariate curve resolution (MCR) analysis of the attenuated total reflection–Fourier-transform infrared spectra of adsorption envelope samples shows that increasing ionic strength does not affect the inner-sphere but decreases the outer-sphere complex adsorption loading, consistent with the ionic strength effect. The extended triple layer model directly and successfully models the MCR-derived inner- and outer-sphere surface loadings at various ionic strengths, indicating weaker sulfate inner-sphere complexation on hematite than on ferrihydrite surfaces. Results also show that sample drying, lower pH, and higher ionic strength all favor sulfate inner-sphere complexation, but the hematite particle size does not affect the relative proportions of the two types of complexes. Sulfate adsorption kinetics show increasing ratio of exchanged OH– to adsorbed sulfate with time, attributed to inner- and outer-sphere complexation dominating at different adsorption stages and to the changes of the relative abundance of surface OH – and H 2 O groups with time. This work clarifies sulfate adsorption mechanisms on hematite and has implications for understanding sulfate availability, behavior and fate in the environment. Our work suggests that the simple macroscopic ionic strength test correlates well with directly measured outer-sphere complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Synthesis, crystal growth, structural and physicochemical studies of novel binary organic complex: 4-chloroaniline-3-hydroxy-4-methoxybenzaldehyde

The solid-state reaction, which is solvent free and green synthesis, has been adopted to explore the novel compound. The phase diagram of 4-chloroaniline (CA) and 3-hydroxy-4-methoxybenzaldehyde (HMB) system shows the formation of a novel 1:1 molecular complex, and two eutectics on either sides of complex. Thermochemical studies of complex and eutectics have been carried out for various properties such as heat of fusion, entropy of fusion, Jackson's parameters, interfacial energy and excess thermodynamic functions. The formation of molecular complex was also studied by IR, NMR, elemental analysis and UV-Vis absorption spectra. The single crystal of molecular complex was grown and its XRD study confirms the formation of complex and identifies the crystal structure and atomic packing of crystal of complex. Transmission spectra of grown crystal of the complex show 70% transmittance efficiency with cut off wavelength 412 nm. The band gap and refractive index of the crystal of complex have also been studied. - Graphical abstarct: Exploiting phase diagram study and solvent free synthesis a novel compound was synthesized and its single crystal growth, atomic packing, energy band gap and refractive index were studied. Highlights: Black-Right-Pointing-Pointer Novel organic complex was synthesized using Green or solvent free synthesis. Black-Right-Pointing-Pointer Phase diagram study provided the information to identify the worthy composition of novel complex. Black-Right-Pointing-Pointer The single crystal of the sufficient size was grown from the ethanol solution. Black-Right-Pointing-Pointer Crystal analysis suggested that the covalent bond is formed between the two parent compounds. Black-Right-Pointing-Pointer The transmittance of the crystal was found to be 70% and it was transparent from 412 to 850 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Complexation of Light Trivalent Lanthanides with N-(2-Hydroxyethyl)ethylenediamine-N,N',N'-triacetic Acid in Aqueous Solutions: Thermodynamic Analysis and Coordination Modes

N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA, denoted as H 3 L) is a strong chelating ligand that is widely used in separation of f-elements as relevant to the nuclear fuel cycle. There is much to be known about the structure and composition of the coordination sphere of the complexes of HEDTA with lanthanides. The complexation of HEDTA with light lanthanides (La 3+ , Nd 3+ and Eu 3+ ) was investigated thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were performed to acquire the complexation constants (25-70°C) and enthalpies (25°C), respectively, at I = 1.0mol·L -1 NaClO 4 . Coordination modes of the complexes were analyzed by luminescence spectroscopy and nuclear magnetic resonance spectroscopy. The results indicate that there are two successive Ln 3+ /HEDTA complexes, LnL(aq) and Ln 2 (H -1 L) 2 2- (Ln 3+ referred to La 3+ , Nd 3+ and Eu 3+ ; H -1 L 4- referred to the deprotonation of the hydroxyl group) during the titration. The hydroxyl group of HEDTA is coordinated in Ln 3+ /HEDTA complex. The dinuclear Ln 2 (H -1 L) 2 2- complex is present as a carboxyl-bridged centrosymmetric dimer, and two carboxyl groups in bridging positions are coordinated to two adjacent Ln 3+ cations. Complexation of the NdL(aq) is exothermic, while formation of the hydrolytic complex Nd 2 (H -1 L) 2 2- is endothermic. Both NdL aq and Nd 2 (H -1 L) 2 2- complexes are driven by entropic force. These data will help to predict the behavior of lanthanides in the separation process where HEDTA is used as the aqueous complexant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Influence of Hydrophobicity on Polyelectrolyte Complexation

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) with methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. Furthermore, the rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synthesis of thin film containing 4-amino-1,2,4-triazole iron(II) complexes

The Iron(II) complex with 4-amino-1,2,4 triazole (NH{sub 2}-trz) ligand has potential applications as smart material since the compounds show a distinct color change from lilac at low temperature to colorless at high temperature. The lilac color of the complex represent the diamagnetic low spin state while the colorless correspond to the paramagnetic high spin state of iron(II). The transition between the two states could be tuned by changing the anionic group. Generally, the complex was synthesized directly from aqueous solution of iron(II) salt with considerable amounts of NH{sub 2}-trz solution produced solid powder compound. For application as an electronic molecular device, the complex should be obtained as a thin film. The transparent [Fe(NH{sub 2}trz){sub 3}]-Nafion film has been successfully obtained, however, no anion variation can be produced since the nafion is an anionic resin. In this work, the [Fe(NH{sub 2}trz){sub 3}]-complexes with several anions have been synthesized inside nata de coco membrane that commonly used as a medium for deposition metal nano-particles. After drying the membrane containing the complex became a thin film. At room temperature, the film containing iron(II) complexes of sulphate and nitrate salts show lilac color, similar to that of the original complexes in the powder form. On heating, the color of the complex film changed to colorless and this color change was observed reversibly. In contrast, the films containing perchlorate and tetrafluoroborate iron(II) complexes are colorless at room temperature and changed to lilac on cooling. The significant color changing of the iron(II)complexes in the nata de coco film can be used for demonstration thermo chromic effect of smart materials with relatively small amount of the compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2011

The C-F...F-C short contacts in the metal complexes of fluoro-phenyl-acrylic acids

Four new complexes of fluoro-phenyl-acrylic acids (E)-3-(3-fluoro-phenyl)-acrylic acid (L1) [Mn{sub 3}(L1){sub 6}(L2){sub 2}].H{sub 2}O.CH{sub 3}CN (1), [Zn{sub 2}(L1){sub 4}(L3)]{sub n} (2), [Mn(L1){sub 2}(H{sub 2}O){sub 2}]{sub n} (3) and [Co(L1){sub 2}(H{sub 2}O){sub 2}]{sub n} (4) (L2=1,10-phenanthroline, L3=4,4'-bipy) have been synthesized based on the molecular design and research of halogen-halogen interactions (especially fluoro-fluoro contact). The structure analyses reveal that complex 1 is a trinuclear complex, which is blocked by L2. Complex 2 is a 1D chain bridged through L3. Complexes 3 and 4 exhibit 2D grid like metal-organic framework structures through carboxylato bridge ligand. Variable-temperature magnetic measurements showed an antiferromagnetic interaction between Mn(II) ions and between Co(II) ions in complexes 3 and 4, respectively. A short C-F...F-C contact with a distance of 2.953 A was found between the trinuclear coordination compound 1. -- Graphical Abstract: The short distance between F...F (2.953 A) was found in the complex of [Mn{sub 3}(L1){sub 6}(L2){sub 2}].H{sub 2}O.CH{sub 3}CN (L1=(E)-3-(3-fluoro-phenyl)-acrylic acid, L2=1,-10-phenanthroline). Display Omitted Research highlights: > Four new complexes of fluoro-phenyl-acrylic acids (E)-3-(3-fluoro-phenyl)-acrylic acid (L1) [Mn{sub 3}(L1){sub 6}(L2){sub 2}].H{sub 2}O.CH{sub 3}CN (1), [Zn{sub 2}(L1){sub 4}(L3)]{sub n} (2), [Mn(L1){sub 2}(H{sub 2}O){sub 2}]{sub n} (3) and [Co(L1){sub 2}(H{sub 2}O){sub 2}]{sub n} (4) (L2=1,10-phenanthroline, L3=4,4'-bipy) have been synthesized based on the molecular design and research of halogen-halogen interactions (especially fluoro-fluoro contact). > A short C-F...F-C contact with a distance of 2.953 A was found between the trinuclear coordination compound 1. > Variable-temperature magnetic measurements showed an antiferromagnetic interaction between Mn(II) ions and between Co(II) ions in complexes 3 and 4, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗