Influence of iron redox cycling on organo-mineral associations in Arctic tundra soil
Abstract not provided
Herndon, Elizabeth↗
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A proof-of-concept application of water-soluble ytterbium( iii ) molecular probes in in vivo NIR-II whole body bioimaging
Lanthanide complexes are firstly applied for in vivo NIR-II high resolution whole body bioimaging.
Ning, Yingying↗
How Many Trip Requests Could We Support? An Activity-Travel Based Vehicle Scheduling Approach
In a world of ever-changing travel behavior and ever-increasing modal options, is vital to have integrated models that could capture the interactions between supply and demand layers of travel. Addressing this need, we propose three different versions of network representation and mathematical models for the activity-based vehicle routing problem to connect activity-travel graphs of passengers (demand layer) to spatio-temporal networks of vehicles (supply layer). Versions I and II are arc-based, while version III is path-based. In version I, we introduce the concept of activity-travel graphs for passengers. For vehicles, we construct space–time networks and add a new dimension, called “under-service state”, to track the execution status of trip requests at any location and time. In version II, we reduce the complexity of the network structure by eliminating the state dimension and some other modifications in the structure of the passengers’ and vehicles’ network. Although both versions can capture various behavioral constraints of the activity-based vehicle routing problem (e.g., mandatory and optimal activities, duration of activities, chain of activities, preferred starting and ending times of activities), due to the high level of complexity of the network structure, both versions can only solve small-sized problems. To tackle the computational complexity, we propose a path-based network representation in version III, and to make a balance between the disutility of passengers and vehicles, we present a tolled user equilibrium problem. Mathematical models are coded in C and GAMS and implemented on real-world Phoenix regional transportation network with more than 39 million trip requests, which demonstrate the effectiveness of the proposed solution for the original and restricted master problems.
33 ADVANCED PROPULSION SYSTEMS↗
Radio and visible-light observations of a coronal arcade transient
Simultaneous visible-light and radio observations of a coronal transient that occurred on April 9, 1980 are discussed. Visible-light observations of the transient and the associated erupting prominence were available from the Coronagraph/Polarimeter carried aboard SMM, the P78-1 coronagraph, and from the Haleakala Observatory. Radio observations of the related type III-II-IV bursts were available from the Clark Lake and Culgoora Observatories. The transient was extremely complex; it is suggested that an entire coronal arcade rather than just a single loop participated in the event. Type III burst sources observed at the beginning of the event were located along a nearby streamer, which was not disrupted, but was displaced by the outmoving loops. The type II burst showed large tangential motion, but, unlike such sources usually do, it had no related herringbone structure. A moving type IV burst source can be associated with the most dense feature of the white-light transient.
Gergely, T. E.↗
The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions
Not Available
Tomaszewski, Elizabeth J.↗
A cancer-associated polymorphism in ESCRT-III disrupts the abscission checkpoint and promotes genome instability
Cytokinetic abscission facilitates the irreversible separation of daughter cells. This process requires the endosomal-sorting complexes required for transport (ESCRT) machinery and is tightly regulated by charged multivesicular body protein 4C (CHMP4C), an ESCRT-III subunit that engages the abscission checkpoint (NoCut) in response to mitotic problems such as persisting chromatin bridges within the midbody. Importantly, a human polymorphism in CHMP4C (rs35094336, CHMP4C T232 ) increases cancer susceptibility. Here, we explain the structural and functional basis for this cancer association: The CHMP4C T232 allele unwinds the C-terminal helix of CHMP4C, impairs binding to the early-acting ESCRT factor ALIX, and disrupts the abscission checkpoint. Cells expressing CHMP4C T232 exhibit increased levels of DNA damage and are sensitized to several conditions that increase chromosome missegregation, including DNA replication stress, inhibition of the mitotic checkpoint, and loss of p53. Our data demonstrate the biological importance of the abscission checkpoint and suggest that dysregulation of abscission by CHMP4C T232 may synergize with oncogene-induced mitotic stress to promote genomic instability and tumorigenesis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cycling of oxyanion-forming trace elements in groundwaters from a freshwater deltaic marsh
For this study, pore waters and surface waters were collected from a freshwater system in southeastern Louisiana to investigate the geochemical cycling of oxyanion-forming trace elements (i.e., Mo, W, As, V). A small bayou (Bayou Fortier) receives input from a connecting lake (Lac des Allemands) and groundwater input at the head approximately 5 km directly south of the Mississippi River. Marsh groundwaters exchange with bayou surface water but are otherwise relatively isolated from outside hydrologic forcings, such as tides, storms, and effects from local navigation canals. Rather, redox processes in the marsh groundwaters appear to drive changes in trace element concentrations. Elevated dissolved S(-II) concentrations in marsh groundwaters suggest greater reducing conditions in the late fall and winter as compared to the spring and late summer. The data suggest that reducing conditions in marsh groundwaters initiate the dissolution of Fe(III)/Mn(IV) oxide/hydroxide minerals, which releases adsorbed and/or co-precipitated trace elements into solution. Once in solution, the fate of these elements is determined by complexation with aqueous species and precipitation with iron sulfide minerals. The trace elements remain soluble in the presence of Fe(III)- and SO 4 2 - - reducing conditions, suggesting that either kinetic limitations or complexation with aqueous ligands obfuscates the correlation between V and Mo sequestration in sediments with reducing or euxinic conditions.
54 ENVIRONMENTAL SCIENCES↗
Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA – ); Synthesis and Structure of M IV TTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III (TTA) 4 – (M III = Ce, Nd, Sm, Yb)
Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide
Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2{sub 1} helical chains. While the Nd(III) ions are bridged through μ{sub 2}-HIDC{sup 2−} and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2{sub 1} helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2{sub 1} helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Metal–Organic-Framework-Supported and -Isolated Ceria Clusters with Mixed Oxidation States
The formation of oxygen vacancies via reversible transitions between Ce(IV) and Ce(III) plays a crucial role in the propensity of cerium oxide to act as a supporting promoter in oxidative heterogeneous catalysis. An open challenge is, however, preparation of high-porosity, supported arrays of isolated ceria(IV, III) clusters with high porosity. In this article, we report two examples of oxy-Ce(IV, III) clusters supported and spatially isolated on an oxy-zirconium MOF, NU-1000. The clusters are introduced using either of two Ce complexes (precursors): Ce IV (tmhd) 4 (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate) or Ce III (iPrCp) 3 (iPrCp = tris(isopropyl-cyclopenta-dienyl), via SIM (solvothermal installation in MOFs). The prepared materials are named Ce-l-SIM-NU-1000 and Ce-n-SIM-NU-1000, respectively. X-ray photoelectron spectroscopy characterization shows that the ratio of Ce(III) to Ce(IV) oxidation states can be modulated. Difference envelope density analyses of X-ray scattering show that Ce x O y H z clusters in Ce-n-SIM-NU-1000 are located between pairs of Zr6 nodes, whereas in Ce-l-SIM-NU-1000, they are sited on MOF linkers throughout the micropores of NU-1000. Cluster size differences were further evaluated by pair function distribution (PDF) analyses of total X-ray scattering reveal that the node sited clusters contain of only a few cerium ions, whereas the linker-sited clusters each contain ~90 cerium ions. The observed size appears to be defined by the size of NU-1000s triangular pores, that is, cluster formation appears to be pore templated. The Ce-SIM functionalized materials are catalytically active for hydrolysis of DMNP (dimethyl 4-nitrophenyl phosphate), a nerve-agent simulant. Conversion of a small fraction of the Ce(IV) ions in which the presence of small fractions of the cerium(IV) ions in Ce-l-SIM-NU-1000 to cerium(III) significantly enhances catalytic activity-perhaps by labilizing aqua ligands and facilitating simulant binding to the clusters Lewis-basic metal ions. While not explored here, the larger clusters, when partially reduced, are, we believe, candidate catalysts for O 2 activation and subsequent selective oxidation of organic substrates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Applying Anodic Stripping Voltammetry to Complex Wastewater Streams for Rapid Metal Detection (Final Report)
The overall objective of this project is the development of a lab-on-a-chip (LOC) electrochemical sensor capable of accurately measuring heavy metal (lead (Pb), cadmium (Cd), and arsenic (As)) concentrations in complex aqueous streams such as wastewater. The specific goals include: i) identify how heavy metal speciate and transform during the different stages of the wastewater treatment train, and explore pre-treatment methods that will de-complex heavy metals, making them available to ASV, ii) develop appropriate electrodes for ASV using organic/inorganic nanomaterials, and iii) integrate pre-treatment steps and specialized electrodes into an LOC sensor device capable of autonomously determining heavy metal concentrations in complex wastewater streams.
99 GENERAL AND MISCELLANEOUS↗
DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid
We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Impact of organic acids on extraction of rare earth elements: Mechanisms and optimization
Organic acids are increasingly recognized as an environmentally friendly and efficient selective leaching agent of critical minerals. However, their impact on subsequent extraction processes remains unclear. This study investigates the extraction behavior of rare earth elements (REEs), representative of critical minerals, in the presence of various organic acids, including citric acid, maleic acid, malonic acid, DL-malic acid, L(+)-tartaric acid, and L-ascorbic acid. The results show that organic acids slightly reduce the extraction of REEs but greatly increase the extraction of aluminum (Al³⁺), making it harder to separate REEs from other elements. To avoid this, it is best to keep organic acid concentrations as low as possible in practical applications. However, by optimizing extraction conditions, these negative effects can be minimized. Specifically, adjusting the contact time between solutions allows for efficient REE extraction while limiting unwanted aluminum extraction. Among the acids tested, malonic acid and L(+)-tartaric acid were found to be the most effective for selectively extracting REEs. Mechanistically, organic acids are likely to form complexes with REEs and D2EHPA during extraction, except for Y (III), offering practical guidelines for optimizing REE recovery. Beyond extraction, this study also highlights a way to recover organic acids by precipitating REEs from stripping solutions using oxalic acid, which adds both environmental and economic benefits. Furthermore, these findings provide useful insights for optimizing REE recovery and offer a reference for extracting other critical minerals from solutions containing organic acids.
D2EHPA↗
Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear Co IV –Dinitrate Complex
High-valent Fe IV =O intermediates with a terminal metal–oxo moiety are key oxidants in many enzymatic and synthetic C–H bond oxidation reactions. While generating stable metal–oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo–metal species of late transition metals have been recently described as strong oxidants that activate C–H bonds. In this work, we obtained an unprecedented mononuclear Co IV –dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt d z2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp 3 C–H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2–6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C–H bonds has yet to be observed for Co IV –O and Co III =O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species that is both structurally characterized by X-ray crystallography and capable of activating strong C–H bonds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Hydration of ferric chloride and nitrate in aqueous solutions: water-mediated ion pairing revealed by Raman spectroscopy
Iron is the most abundant transition metal in the earth's crust and is important for the proper functioning of many technological and natural processes. Despite the importance, a complete microscopic understanding of the hydration of ferric ions and water mediated ion pairing has not been realized. Hydrated Fe(III) is difficult to study due to the process of complexation to the anion and hydrolysis of the hydrating water molecules leading to a heterogeneous solution with diverse speciation. Here, ferric chloride and nitrate aqueous solutions are studied using polarized Raman spectroscopy as a function of concentration and referenced to their respective sodium salt or mineral acid. Perturbed water spectra (PWS) were generated using multivariate curve resolution-alternating least squares (MCR-ALS) to show the residual spectral response uniquely attributable to the hydration of ferric speciation. The hydrogen bonding network associated with the hydrating water molecules in ferric chloride solutions are found to be more similar to hydrochloric acid solutions, whereas in ferric nitrate solutions, the network behaves more similar to sodium nitrate, despite increased acidity. Thus, in the FeNO 3 and FeCl 3 solutions, ion pairing and coordination, respectively, are significantly influencing the hydration spectra signature. These results further reveal concentration dependent changes to the hydrogen bonding network, hydrating water symmetry, and changes to the relative abundance of solvent shared ion pairs that are governed primarily by the ferric salt identity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The underappreciated influence of ancillary halide on metal–ligand proton tautomerism
Ligand protonated Ir I bisphosphine carbonyl complexes isolated as halide salts equilibrate with their neutral Ir III –H congeners in solution. The equilibrium constant and energy barrier to interconversion are dependent on the identity of the halide.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A directed-overflow and damage-control N -glycosidase in riboflavin biosynthesis
Plants and bacteria synthesize the essential human micronutrient riboflavin (vitamin B2) via the same multistep pathway. The early intermediates of this pathway are notoriously reactive, and may be overproduced in vivo because riboflavin biosynthesis enzymes lack feedback controls. Here we demonstrate disposal of riboflavin intermediates by COG3236 (DUF1768), a protein of previously unknown function that is fused to two different riboflavin pathway enzymes in plants and bacteria (RIBR and RibA, respectively). We present cheminformatic, biochemical, genetic, and genomic evidence to show that: (i) plant and bacterial COG3236 proteins cleave the N-glycosidic bond of the first two intermediates of riboflavin biosynthesis, yielding relatively innocuous products; (ii) certain COG3236 proteins are in a multienzyme riboflavin biosynthesis complex that gives them privileged access to riboflavin intermediates; and (iii) COG3236 action in Arabidopsis thaliana and Escherichia coli helps maintain flavin levels. We find COG3236 proteins thus illustrate two emerging principles in chemical biology: directed overflow metabolism, in which excess flux is diverted out of a pathway, and the pre-emption of damage from reactive metabolites.
59 BASIC BIOLOGICAL SCIENCES↗
High pressure-induced distortion in face-centered cubic phase of thallium
The complex and unusual high-pressure phase transition of III-A (i.e. Al, Ga, and In) metals have been investigated in the last several decades because of their interesting periodic table position between the elements having metallic and covalent bonding. Here, our present first principles-based electronic structure calculations and experimental investigation have revealed the unusual distortion in face-centered cubic (f.c.c.) phase of the heavy element thallium (Tl) induced by the high pressure. We have predicted body-centered tetragonal (b.c.t) phase at 83 GPa using an evolutionary algorithm coupled with ab initio calculations, and this prediction has been confirmed with a slightly distorted parameter (2–√ × a-c)/c lowered by 1% using an angle-dispersive X-ray diffraction technique. The density functional theory (DFT)-based calculations suggest that s–p mixing states and the valence-core overlapping of 6s and 5d states play the most important roles for the phase transitions along the pathway h.c.p→f.c.c.→b.c.t.
36 MATERIALS SCIENCE↗