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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Recovery of Chromium(III) from Tannery Wastewater by Nanoparticles and Whiskers of Chitosan

Chitosan, its nanoparticles and whiskers present an excellent capacity to complex chromium ions. However, this phenomenon is influenced by different parameters. In our search, we determined the appropriate range of pH to form chitosan–Cr(III), nanoparticles Cr(III) and whiskers–Cr(III) complex. We studied also the influence of chromium concentration and nature of chitosan-based materials on complexation process. Our main aim is approximate the optimal conditions to remove chromium(III) from tanning bath, recuperated from tannery wastewater of Marrakech in Morocco. However, the results of adsorption kinetic in tannery wastewater revealed that chitosan, its nanoparticles, whiskers and biocomposites are good sorbent of chromium as well, even if the adsorbed quantity is less compared to chromium solution. Although, according to ICP-OES analysis in this real effluent, nanoparticles are the best complexing ligand, after 24 h of contact nanoparticles can remove 70% of chromium from this tannery wastewater.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Crystal structure of di-μ-hydroxido-κ 4 O : O -bis[bis(acetylacetonato-κ 2 O , O ')cobalt(III)]

The dinuclear title complex, [Co 2 (C 5 H 7 O 2 ) 4 (μ-OH) 2 ] or [Co(acac) 2 (μ-OH)] 2 , where acac is acetylacetonate, is centrosymmetric with half of the molecule per asymmetric unit. The molecular structure is a dimer of octahedrally coordinated Co III atoms with four O atoms from two chelating acac ligands and two O atoms from bridging hydroxide ligands. The crystal packing features weak C—H...O interactions between neighboring molecules, leading to the formation of chains normal to the ac plane. The hydroxide H atoms are not involved in hydrogen bonding because of the bulky acac ligands. This is the first crystal structure reported of a dimeric transition metal bis-acac complex with OH - as the bridging group.

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

Stable abnormal N-heterocyclic carbenes and their applications

Although N-heterocyclic carbenes (NHCs) have been known as ligands for organometallic complexes since the 1960s, these carbenes did not attract considerable attention until Arduengo et al. reported the isolation of a metal-free imidazol-2-ylidene in 1991. In 2001 Crabtree et al. reported a few complexes featuring an NHC isomer, namely an imidazol-5-ylidene, also termed abnormal NHC (aNHCs). In 2009, it was shown that providing to protect the C-2 position of an imidazolium salt, the deprotonation occurred at the C-5 position, affording imidazol-5-ylidenes that could be isolated. Over the last ten years, stable aNHCs have been used for designing a range of catalysts employing Pd(II), Cu(I), Ni(II), Fe(0), Zn(II), Ag(I), and Au(I/III) metal based precursors. These catalysts were utilized for different organic transformations such as the Suzuki–Miyaura cross-coupling reaction, C–H bond activation, dehydrogenative coupling, Huisgen 1,3-dipolar cycloaddition (click reaction), hydroheteroarylation, hydrosilylation reaction and migratory insertion of carbenes. Main-group metal complexes were also synthesized, including K(I), Al(III), Zn(II), Sn(II), Ge(II), and Si(II/IV). Among them, K(I), Al(III), and Zn(II) complexes were used for the polymerization of caprolactone and rac-lactide at room temperature. In addition, based on the superior nucleophilicity of aNHCs, relative to that of their nNHCs isomers, they were used for small molecules activation, such as carbon dioxide (CO 2 ), nitrous oxide (N 2 O), tetrahydrofuran (THF), tetrahydrothiophene and 9-borabicyclo[3.3.1]nonane (9BBN). aNHCs have also been shown to be efficient metal-free catalysts for ring opening polymerization of different cyclic esters at room temperature; they are among the most active metal-free catalysts for ε-caprolactone polymerization. Recently, aNHCs successfully accomplished the metal-free catalytic formylation of amides using CO 2 and the catalytic reduction of carbon dioxide, including atmospheric CO 2 , into methanol, under ambient conditions. Although other transition metal complexes featuring aNHCs as ligand have been prepared and used in catalysis, this review article summarize the results obtained with the isolated aNHCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Discovery of FoTO1 and Taxol genes enables biosynthesis of baccatin III

Abstract Plants make complex and potent therapeutic molecules 1,2 , but sourcing these molecules from natural producers or through chemical synthesis is difficult, which limits their use in the clinic. A prominent example is the anti-cancer therapeutic paclitaxel (sold under the brand name Taxol), which is derived from yew trees (Taxusspecies) 3 . Identifying the full paclitaxel biosynthetic pathway would enable heterologous production of the drug, but this has yet to be achieved despite half a century of research 4 . WithinTaxus’ large, enzyme-rich genome 5 , we suspected that the paclitaxel pathway would be difficult to resolve using conventional RNA-sequencing and co-expression analyses. Here, to improve the resolution of transcriptional analysis for pathway identification, we developed a strategy we term multiplexed perturbation × single nuclei (mpXsn) to transcriptionally profile cell states spanning tissues, cell types, developmental stages and elicitation conditions. Our data show that paclitaxel biosynthetic genes segregate into distinct expression modules that suggest consecutive subpathways. These modules resolved seven new genes, allowing a de novo 17-gene biosynthesis and isolation of baccatin III, the industrial precursor to Taxol, inNicotiana benthamianaleaves, at levels comparable with the natural abundance inTaxusneedles. Notably, we found that a nuclear transport factor 2 (NTF2)-like protein, FoTO1, is crucial for promoting the formation of the desired product during the first oxidation, resolving a long-standing bottleneck in paclitaxel pathway reconstitution. Together with a new β-phenylalanine-CoA ligase, the eight genes discovered here enable the de novo biosynthesis of 3’-N-debenzoyl-2’-deoxypaclitaxel. More broadly, we establish a generalizable approach to efficiently scale the power of co-expression analysis to match the complexity of large, uncharacterized genomes, facilitating the discovery of high-value gene sets.

Science & Technology - Other Topics↗
DOE OSTI2023

Isolation of a californium(II) crown–ether complex

The actinides, from californium to nobelium (Z = 98–102), are known to have an accessible +2 oxidation state. Understanding the origin of this chemical behaviour requires characterizing Cf II materials, but investigations are hampered by the fact that they have remained dificult to isolate. This partly arises from the intrinsic challenges of manipulating this unstable element, as well as a lack of suitable reductants that do not reduce Cf III to Cf°. Here we show that a Cf II crown–ether complex, Cf(18-crown-6)I 2 , can be prepared using an Al/Hg amalgam as a reductant. Spectroscopic evidence shows that Cf III can be quantitatively reduced to Cf II , and rapid radiolytic re-oxidation in solution yields co-crystallized mixtures of Cf II and Cf III complexes without the Al/Hg amalgam. Furthermore, quantum-chemical calculations show that the Cf– ligand interactions are highly ionic and that 5f/6d mixing is absent, resulting in weak 5f→5f transitions and an absorption spectrum dominated by 5f→6d transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

H-treatment impact on conductive-filament formation and stability in Ta{sub 2}O{sub 5}-based resistive-switching memory cells

In this article, we evidence the lower formation energy and improved stability of the conductive filament (CF) formed in TiN\Ta{sub 2}O{sub 5}\Ta resistive-switching memory cells treated in NH{sub 3} atmosphere at 400 °C. This annealing treatment results in (i) lower forming voltage, (ii) lower CF resistance, and (iii) longer retention lifetime of the oxygen-vacancy (V{sub o}) chain constituting the CF. Atomistic insights into these processes are provided by ab initio calculations performed for hydrogen (H) species incorporated in non-stoichiometric Ta{sub 2}O{sub 5} supercells: (i) V{sub o} formation energy is reduced by the presence of H, (ii) V{sub o}-chain CF conductivity is increased by V{sub o} + OH complex formation, and (iii) V{sub o}-chain retention is strengthened by the stable V{sub o} + OH complex. As a result, efficient CF formation and excellent state stability are obtained after 15 days at 250 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Direct Determination of Absolute Absorption Cross Sections at the L-Edge of Dilute Mn Complexes in Solution Using a Transmission Flatjet

The 3d transition metals play a pivotal role in many charge transfer processes in catalysis and biology. X-ray absorption spectroscopy at the L-edge of metal sites probes metal 2p–3d excitations, providing key access to their valence electronic structure, which is crucial for understanding these processes. In this paper, we report L-edge absorption spectra of Mn II (acac) 2 and Mn III (acac) 3 complexes in solution, utilizing a liquid flatjet for X-ray absorption spectroscopy in transmission mode. With this, we derive absolute absorption cross-sections for the L-edge transitions with peak magnitudes as large as 12 and 9 Mb for Mn II (acac) 2 and Mn III (acac) 3 , respectively. We provide insight into the electronic structure with ab initio restricted active space calculations of these L-edge transitions, reproducing the experimental spectra with excellent agreement in terms of shapes, relative energies, and relative intensities for the two complexes. Crystal field multiplet theory is used to assign spectral features in terms of the electronic structure. Comparison to charge transfer multiplet calculations reveals the importance of charge transfer in the core-excited final states. Finally, on the basis of our experimental observations, we extrapolate the feasibility of 3d transition metal L-edge absorption spectroscopy using the liquid flatjet approach in probing highly dilute biological solution samples and possible extensions to table-top soft X-ray sources.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Sequestration of cerium(III) bromide into mesoporous silica

In this study, a variety of surface-functionalized mesoporous silica monoliths were reacted with a cerium(III) bromide molecular complex and a successful scaffold for luminescent materials is demonstrated. The variation in structure of the materials is shown through infrared spectroscopy, and the luminescent properties illustrate the varying coordination environment of cerium(III) bromide.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Amplified spontaneous emission from europium-based molecular complexes coupled to photonic crystal cavities

Rare-earth ion-based materials bear many remarkable optical properties that render them highly appealing for lighting and quantum-related applications. However, their small oscillator strength and weak emission often pose limitations. Here, in this work, we synthesize and couple Eu(III)-based molecular complexes to nanobeam photonic crystals supporting air modes. A reasonable spatial overlap between the molecular complexes and cavity modes leads to an average spontaneous emission coupling efficiency of 0.19. Our pump power-dependent photoluminescence measurements evidence amplified spontaneous emission from the molecular complexes with an amplification threshold as low as 4.4 W/cm 2 , likely benefiting from the efficient coupling. These findings suggest that integrating rare-earth ion-based molecular complexes with photonic structures could be a viable approach for regulating their emission characteristics for particular applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The roles of 4f- and 5f-orbitals in bonding: A magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

The electronic structures of 4f 3 /5f 3 Cp" 3 M and Cp" 3 M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. As a result, while interaction with the isocyanide π*-orbitals lowers the energies of the 5f xz 2 and 5f yz 2- orbitals, spin–orbit coupling greatly reduces the population of 5f xz 2 and 5f yz 2 in the ground state.

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

Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source

High-valent iron-oxo complexes are key intermediates in C–H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding (TAML)Fe III –OH 2 complex. Cyclic voltammetry (CV) and spectroelectrochemical studies are used to elucidate the relevant (TAML)Fe redox processes and determine the predominant (TAML)Fe species present in solution during bulk electrolysis. Evidence for iron( IV ) and iron( V ) species is presented, and these species are used in the electrochemical oxygenation of benzylic C–H bonds and dehydrogenation of alcohols to ketones.

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

Csx3 is a cyclic oligonucleotide phosphodiesterase associated with type III CRISPR–Cas that degrades the second messenger cA 4

Cas10 is the signature gene for type III CRISPR–Cas surveillance complexes. Unlike type I and type II systems, type III systems do not require a protospacer adjacent motif and target nascent RNA associated with transcriptionally active DNA. Further, target RNA recognition activates the cyclase domain of Cas10, resulting in the synthesis of cyclic oligoadenylate second messengers. These second messengers are recognized by ancillary Cas proteins harboring CRISPR-associated Rossmann fold (CARF) domains and regulate the activities of these proteins in response to invading nucleic acid. Csx3 is a distant member of the CARF domain superfamily previously characterized as a Mn 2+ -dependent deadenylation exoribonuclease. However, its specific role in CRISPR–Cas defense remains to be determined. Here we show that Csx3 is strongly associated with type III systems and that Csx3 binds cyclic tetra-adenylate (cA 4 ) second messenger with high affinity. Further, Csx3 harbors cyclic oligonucleotide phosphodiesterase activity that quickly degrades this cA 4 signal. In addition, structural analysis identifies core elements that define the CARF domain fold, and the mechanistic basis for ring nuclease activity is discussed. Overall, the work suggests that Csx3 functions within CRISPR–Cas as a counterbalance to Cas10 to regulate the duration and amplitude of the cA 4 signal, providing an off ramp from the programmed cell death pathway in cells that successfully cure viral infection.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A conserved epitope III on hepatitis C virus E2 protein has alternate conformations facilitating cell binding or virus neutralization

Epitope III, a highly conserved amino acid motif of 524 APTYSW 529 on the hepatitis C virus (HCV) E2 glycoprotein, resides in the critical loop that binds to the host receptor CD81, thus making it one of the most important antibody targets for blocking HCV infections. Here, we have determined the X-ray crystal structure of epitope III at a 2.0-Å resolution when it was captured by a site-specific neutralizing antibody, monoclonal antibody 1H8 (mAb1H8). The snapshot of this complex revealed that epitope III has a relatively rigid structure when confined in the binding grooves of mAb1H8, which confers the residue specificity at both ends of the epitope. Such a high shape complementarity is reminiscent of the “lock and key” mode of action, which is reinforced by the incompatibility of an antibody binding with an epitope bearing specific mutations. By subtly positioning the side chains on the three residues of Tyr 527 , Ser 528 , and Trp 529 while preserving the spatial rigidity of the rest, epitope III in this cocrystal complex adopts a unique conformation that is different from previously described E2 structures. With further analyses of molecular docking and phage display–based peptide interactions, we recognized that it is the arrangements of two separate sets of residues within epitope III that create these discrete conformations for the epitope to interact selectively with either mAb1H8 or CD81. These observations thus raise the possibility that local epitope III conformational dynamics, in conjunction with sequence variations, may act as a regulatory mechanism to coordinate “mAb1H8-like” antibody-mediated immune defenses with CD81-initiated HCV infections.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

[Ni III (OMe)]-mediated reductive activation of CO 2 affording a Ni(κ 1 -OCO) complex

Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C 1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO 2 , i.e. insertion of CO 2 producing bicarbonate/acetate/formate, cleavage of CO 2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO 2 affording CO/HCOOH/CH 3 OH/CH 4 /C 2 H 4 /oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO 2 by the [Ni III (OMe)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] – complex, yielding the [Ni III (κ 1 -OCO˙ – )(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] – complex. The formation of this unusual Ni III (κ 1 -OCO ˙– ) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [Ni III (SPh)], [Ni II (CO)], and [Ni II (N 2 H 4 )] toward CO 2 , in contrast, demonstrates that the ionic [Ni III (OMe)] core attracts the binding of weak σ-donor CO 2 and triggers the subsequent reduction of CO 2 by the nucleophilic [OMe] – in the immediate vicinity. This metal–ligand cooperative activation of CO 2 may open a novel pathway promoting the subsequent incorporation of CO 2 in the buildup of functionalized products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Isolation of Ce( IV ) centered polyoxoalkoxide sandwich-type complexes allows comparison of metal–oxygen bond covalency

The new Ce III centered sandwich-type complex (TBA) 3 [Ce{W 4 O 13 (OMe) 4 MoNO} 2 ] is reported. The redox properties of this molecule, and its all-molybdenum analogue, (TBA) 3 [Ce{Mo 5 O 13 (OMe) 4 NO} 2 ], were investigated using cyclic voltammetry. The data reveals the presence of reversible Ce IV /Ce III redox couples at modest potentials. One electron oxidation of the complexes provides facile access to the corresponding Ce IV derivatives, which were fully characterized. 17 O NMR spectroscopy reveals that the chemical shifts of the oxygen nuclei directly bound to Ce IV are much higher than the corresponding signals in isostructural, diamagnetic, Zr IV , Hf IV , or Th IV centered complexes. Density functional theory (DFT) calculations indicate that the increase in chemical shift correlates with an increase in the covalency of the M IV –O bonds, illustrating that 17 O NMR spectroscopy is a powerful experimental tool for interrogating the nature of metal oxygen bonding in diamagnetic complexes.

Shiels, Dominic [Univ. of Rochester, NY (United St↗
DOE OSTI2017

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2 L 4 F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp – ); 2, L = diphenyl formamidinate (dpf – )) were prepared from the solid-state melt reactions (SSMRs) between (NH 4 ) 2 [Re 2 F 8 ]·2H 2 O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2 (hpp) 4 F 2 ]PF 6 (3) was prepared from the one-electron oxidation of Re 2 (hpp) 4 F 2 with [Cp 2 Fe]PF 6 . Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2 (hpp) 4 F 2 (1) is more easily oxidized than its chloro and bromo analogues.

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

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz), 5-amino-tetrazole (5-NH 2 -HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl 3 ⋅ 7H 2 O, [C 2 mim] 3 [CeCl 6 ] ([C 2 mim] + =1-ethyl-2-methylimidazolium), and Ce(NO 3 ) 3 ⋅ 6H 2 O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH 2 -1,2,4-Triaz is structure directing via η 2 μ 2 κ 2 bridging, with the formation of the dinuclear complexes [Ce 2 Cl 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (H 2 O) 8 ]Cl 4 ⋅ 4H 2 O, [Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 (Cl) 6 ], and [4-NH 2 -1,2,4-HTriaz][Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 2 (μ 2 -NO 3 )(NO 3 ) 6 (H 2 O) 2 ]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ] ⋅ 7H 2 O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M 6 X 8 core, and the first reported Ce(III) hexanuclear complex of this type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗