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X-ray sources in regions of star formation. III - Naked T Tauri stars associated with the Taurus-Auriga complex
Ground-based and IRAS optical and IR spectroscopic and photometric observations are reported for 90 stars in or near 59 Einstein Observatory X-ray error circles in the Tau-Aur region. The data are presented in extensive tables and sample spectra and characterized in detail, with particular attention to 28 newly discovered 'naked' T Tau stars, which are shown to be normal stars with no significant IR or UV excess and ages of 1-40 Myr. These stars are found to outnumber normal T Tau stars by a factor of 10 in an area near the Tau-Aur dark clouds, and it is argued that their evolution toward the ZAMS is typical for low-mass stars. The implications of this finding for the time scales of circumstellar-disk dissipation and planet formation are discussed.
Complexes with Aquatic Organic Matter Suppress Hydrolysis and Precipitation of Fe(III)
Abstract Not Provided
Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O 2 activation by non-adiabatic oxidative addition to a single metal center]
A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp tBu,Me Cr V (O) 2 ] (Tp tBu,Me =hydrotris(3- tert -butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp tBu,Me Cr III (S 2 )]. The transformation of the putative peroxo intermediate [Tp tBu,Me Cr III (O 2 )] (S= 3 / 2 ) into [Tp tBu,Me Cr V (O) 2 ] (S= 1 / 2 ) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(Tp tBu,Me Cr) 2 (μ-O) 2 ] exists, mechanistic experiments suggest that O 2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.
Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis
The redox state and speciation of the metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known concerning environmental influences (e.g., coexisting ions) on the process. As such, in this study we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO 2 ) in the presence of dissolved Fe(II) using X-ray absorption spectroscopy, Mössbauer spectroscopy, and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). The As K-edge X-ray absorption near edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, whereas at higher Fe(II) concentrations (200–1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As–Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. Both As(III) and (V) adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO 2 were predominantly ferrihydrite-, goethite-, and ferric arsenate-like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) oxidation occurs as a two electron transfer with δ-MnO 2 and that the observed Mn(III) is due to conproportionation of surface-sorbed Mn(II) with Mn(IV) in the δ-MnO 2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO 2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of Fe(III)-(hydr)oxides plays a very important role in reducing As mobility.
Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry
Low-cost, non-empirical corrections to semi-local density functional theory are essential for accurately modeling transition-metal chemistry. Here, we demonstrate the judiciously modified density functional theory (jmDFT) approach with non-empirical U and J parameters obtained directly from frontier orbital energetics on a series of transition-metal complexes. We curate a set of nine representative Ti(III) and V(IV) d 1 transition-metal complexes and evaluate their flat-plane errors along the fractional spin and charge lines. We demonstrate that while jmDFT improves upon both DFT+U and semi-local DFT with the standard atomic orbital projectors (AOPs), it does so inefficiently. We rationalize these inefficiencies by quantifying hybridization in the relevant frontier orbitals. To overcome these limitations, we introduce a procedure for computing a molecular orbital projector (MOP) basis for use with jmDFT. We demonstrate this single set of d 1 MOPs to be suitable for nearly eliminating all energetic delocalization and static correlation errors. In all cases, MOP jmDFT outperforms AOP jmDFT, and it eliminates most flat-plane errors at non-empirical values. Unlike DFT+U or hybrid functionals, jmDFT nearly eliminates energetic delocalization and static correlation errors within a non-empirical framework.
Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt II →Ge IV Complex
Abstract Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [( o ‐(Ph 2 P)C 6 H 4 ) 2 Ge IV Cl 2 ]Pt II Cl 2 and [( o ‐(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [( o ‐(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl with quantum yields of 1.7 % and 3.2 % for the Ge IV –Pt II and Ge III –Pt III isomers, respectively. Conversion of the Ge IV –Pt II isomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the Ge III –Pt III isomer point to a ligand arene–Cl . charge‐transfer complex as an intermediate.
RNA and DNA Targeting by a Reconstituted Thermus thermophilus Type III-A CRISPR-Cas System
CRISPR-Cas (clustered regularly interspaced short palindromic repeats-CRISPR-associated) systems are RNA-guided adaptive immunity pathways used by bacteria and archaea to defend against phages and plasmids. Type III-A systems use a multi-subunit interference complex called Csm, containing Cas proteins and a CRISPR RNA (crRNA) to target cognate nucleic acids. The Csm complex is intriguing in that it mediates RNA-guided targeting of both RNA and transcriptionally active DNA, but the mechanism is not well understood. Here, we overexpressed the five components of the Thermus thermophilus (T. thermophilus) Type III-A Csm complex (TthCsm) with a defined crRNA sequence, and purified intact TthCsm complexes from E. coli cells. The complexes were thermophilic, targeting complementary ssRNA more efficiently at 65°C than at 37°C. Sequence-independent, endonucleolytic cleavage of single-stranded DNA (ssDNA) by TthCsm was triggered by recognition of a complementary ssRNA, and required a lack of complementarity between the first 8 nucleotides (50 tag) of the crRNA and the 30 flanking region of the ssRNA. Mutation of the histidine-aspartate (HD) nuclease domain of the TthCsm subunit, Cas10/Csm1, abolished DNA cleavage. Activation of DNA cleavage was dependent on RNA binding but not cleavage. This leads to a model in which binding of an ssRNA target to the Csm complex would stimulate cleavage of exposed ssDNA in the cell, such as could occur when the RNA polymerase unwinds double-stranded DNA (dsDNA) during transcription. Our findings establish an amenable, thermostable system for more in-depth investigation of the targeting mechanism using structural biology methods, such as cryoelectron microscopy and x-ray crystallography.
TRACER-Coastal Urban Boundary-Layer Interactions with Convection (TRACER-CUBIC) Field Campaign Report
To better understand the complicated web of processes governing convective cloud life cycle and aerosol-convection interactions, the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) user facility supported deployment of a variety of advanced atmospheric measurement systems to the greater Houston, Texas, area from 1 October 2021 to 30 September 2022 as part of the Tracking Aerosol Convection Interactions Experiment (TRACER). Houston was selected as a study area because isolated convection and a variety of aerosol conditions are common in this region. This one-year ARM Mobile Facility (AMF) deployment featured a four-month intensive operational period (IOP) during summer 2022 (1 June–30 September). The ARM instrumentation was deployed at three sites along an east-west transect from La Porte, Texas to an ancillary site in a less-polluted rural region southwest of downtown Houston (Figure 1). At the La Porte Site, which is located near the Houston ship channel in an area that experiences significant pollution, the first ARM Mobile Facility (AMF1) was deployed. During the IOP, the ARM tethered balloon system (TBS) operated at the ancillary site. The second-generation C-Band Scanning ARM Precipitation Radar (CSAPR) operated near Pearland, Texas, roughly halfway between the Laporte and ancillary sites. As part of the TRACER- Coastal Urban Boundary-Layer Interactions with Convection (CUBIC) project, three boundary-layer profiling systems) were deployed along a north-south transect spanning from the University of Houston Coastal Center to the Aldine site north of downtown Houston (also blue dot in Figure 1) during the TRACER IOP. These systems included the National Oceanic and Atmospheric Administration (NOAA) National Severe Storms Laboratory CLAMPS2 (C2), which was deployed at the UHCC, the University of Wisconsin SPARC, which was deployed at the ARM CSAPR site near Pearland (orange diamond in middle of map in Figure 1), and the University of Oklahoma CLAMPS1 (C1), which was deployed at Aldine. These three systems have been successfully operated in various field campaigns, providing data sets that collectively offer new insights into atmospheric-boundary-layer (ABL) processes, sea-breeze (SB) circulations, and convection initiation (CI). For the TRACER IOP window, these systems ran continuously between 1 June and 26 September, 2022. Due to commitments to NOAA projects, the Doppler lidar at the UHCC site was not available until 24 June 2022. The CLAMPS and SPARC profiling systems are self-contained platforms that have benefited from several years of development and deployment. Instruments and data processing were maintained remotely, which made the 4-month deployment for the TRACER-CUBIC IOP period possible. The same basic instrument configuration comprises each system: a scanning Doppler wind lidar for flow characterization and passive profiler(s) for characterizing planetary-boundary-layer (PBL) thermodynamic properties. Each platform includes a Halo Streamline Doppler wind lidar, an Atmospheric Emitted Radiance Interferometer (AERI), and a surface meteorology station. CLAMPS1 and CLAMPS2 each also include a microwave radiometer (MWR, Figure 1d). The TRACER-CUBIC hypotheses included (i) Interactions of SB and urban circulations and how they affect the PBL structure in the Houston environment, causing spatially (horizontally and vertically) and temporally highly variable flow patterns, (ii) heat, moisture, and aerosol transport and mixing depend on these flow dynamics, and (iii) an improved understanding of the flow patterns and PBL structure are critical for investigating the processes leading to CI. To test these hypotheses, the project aimed at (i) characterizing SB circulations and their impacts on the diurnal evolution of the structure of the ABL, (ii) studying the evolution of Houston’s complex urban boundary layer, and (iii) identifying effects of urban-induced circulations on pre-convective environments. TRACER-CUBIC observations generally provide good coverage during the summer IOP. Initial screening of the data indicates a good number of cases with bay-breeze (BB) and/or SB signatures, local CI, and interesting boundary-layer features such as strong nocturnal low-level jets (LLJs, Table 1). The numbers listed in rows 3-5 in this table will be further updated as part of ongoing in-depth analyses and systematic identification of local circulations and CI events. More detailed information about the data availability and quality for each instrument is provided in the “readme” files that were submitted to the ARM Data Center along with each archived data sets. These “readme” files also provide instrument descriptions, information about the data collection and processing procedures, data formats, and any additional information relevant for further data analysis.
Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt II →Ge IV Complex
Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph 2 P)C 6 H 4 ) 2 Ge IV Cl 2 ]Pt II Cl 2 and [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl with quantum yields of 1.7 % and 3.2 % for the Ge IV –Pt II and Ge III –Pt III isomers, respectively. Conversion of the Ge IV –Pt II isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Additionally, transient-absorption-spectroscopy studies carried out on the Ge III –Pt III isomer point to a ligand arene–Cl. charge-transfer complex as an intermediate.
Fe II Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-to-Ligand Charge-Transfer Excited-State Lifetime
In this paper, the iron carbene complex [Fe II (btz) 3 ](PF 6 ) 2 (where btz = 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)) has been synthesized, isolated, and characterized as a low-spin ferrous complex. It exhibits strong metal-to-ligand charge transfer (MLCT) absorption bands throughout the visible spectrum, and excitation of these bands gives rise to a 3 MLCT state with a 528 ps excited-state lifetime in CH 3 CN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported Fe II complex. The low potential of the [Fe(btz) 3 ] 3+ /[Fe(btz) 3 ] 2+ redox couple makes the 3 MLCT state of [Fe II (btz) 3 ] 2+ a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Finally, taken together with our recent results on the [Fe III (btz) 3 ] 3+ form of this complex, these results show that the Fe II and Fe III oxidation states of the same Fe(btz) 3 complex feature long-lived MLCT and LMCT states, respectively, demonstrating the versatility of iron N-heterocyclic carbene complexes as promising light-harvesters for a broad range of oxidizing and reducing conditions.
$\mathrm{ATR}$-$\mathrm{FTIR}$ spectroscopy as a probe for metal ion binding onto immobilized ligands
ATR-FTIR spectroscopy is shown to be useful in probing metal ion binding to ligands immobilized on polymer beads. Lu(III) is the metal ion, phosphinic and sulfonic acids are the immobilized ligands, and polystyrene beads crosslinked at low and high levels are the support. Analysis is based on ligand band positions and intensities before and after complexation as a function of time. ATR spectra of the phosphinic acid show two types of binding sites with different accessibilities: surface ligands that bind Lu(III) from solution and interior ligands that gain ions by diffusion from the surface. Initially bound Lu(III) ions are mobile within the solid phase and their movement is accompanied by the breaking of hydrogen bonds among the phosphinic acid ligands to form Lu(III) phosphinate complexes. Competition between hydrogen bonding and bond-making with Lu(III) contributes to slow sorption rates compared to results from the sulfonic acid ligand whose strong acidity and ionizability allows rapid Lu(III) sorption. Comparing ATR spectra of the phosphinic acid bound to lightly- and highly-crosslinked polystyrene shows how the extent of crosslinking affects the transport mechanism.
Algebraic ER=EPR and complexity transfer
We propose an algebraic definition of ER=EPR in the G N → 0 limit, which associates bulk spacetime connectivity/disconnectivity to the operator algebraic structure of a quantum gravity system. The new formulation not only includes information on the amount of entanglement, but also more importantly the structure of entanglement. We give an independent definition of a quantum wormhole as part of the proposal. This algebraic version of ER=EPR sheds light on a recent puzzle regarding spacetime disconnectivity in holographic systems with $\mathcal{O}$(1/G N ) entanglement. We discuss the emergence of quantum connectivity in the context of black hole evaporation and further argue that at the Page time, the black hole-radiation system undergoes a transition involving the transfer of an emergent type III 1 subalgebra of high complexity operators from the black hole to radiation. We argue this is a general phenomenon that occurs whenever there is an exchange of dominance between two competing quantum extremal surfaces.
Homolytic cleavage of both heme-bound hydrogen peroxide and hydrogen sulfide leads to the formation of sulfheme
Many heme-containing proteins with a histidine in the distal E7 (HisE7) position can form sulfheme in the presence of hydrogen sulfide (H 2 S) and a reactive oxygen species such as hydrogen peroxide. For reasons unknown, sulfheme derivatives are formed specifically on solvent-excluded heme pyrrole B. Sulfhemes severely decrease the oxygen-binding affinity in hemoglobin (Hb) and myoglobin (Mb). Here, use of hybrid quantum mechanical/molecular mechanical methods has permitted characterization of the entire process of sulfheme formation in the HisE7 mutant of hemoglobin I (HbI) from Lucina pectinata. This process includes a mechanism for H 2 S to enter the solvent-excluded active site through a hydrophobic channel to ultimately form a hydrogen bond with H 2 O 2 bound to Fe(III). Proton transfer from H 2 O 2 to His64 to form compound (Cpd) 0, followed by hydrogen transfer from H 2 S to the Fe(III) H 2 O 2 complex, results in homolytic cleavage of the O–O and S–H bonds to form a reactive thiyl radical (HS*), ferryl heme Cpd II, and a water molecule. Subsequently, the addition of HS to Cpd II, followed by three proton transfer reactions, results in the formation of a three-membered ring ferric sulfheme that avoids migration of the radical to the protein matrix, in contrast to that in other peroxidative reactions. The transformation of this three-membered episulfide ring structure to the five-membered thiochlorin ring structure occurs through a significant potential energy barrier, although both structures are nearly isoenergetic. Both three- and five-membered ring structures reveal longer N B –Fe(III) bonds compared with other pyrrole nitrogen–Fe(III) bonds, which would lead to decreased oxygen binding. Altogether, these results are in agreement with a wide range of experimental data and provide fertile ground for further investigations of sulfheme formation in other heme proteins and additional effects of H 2 S on cell signaling and reactivity.
Large booster launch complexes
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QUIJOTE scientific results – III. Microwave spectrum of intensity and polarization in the Taurus Molecular Cloud complex and L1527
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Characterizing Natural Attenuation of Cr(VI) in a Chromium Plume at Los Alamos National Laboratory - 18594
Characterization of natural attenuation of hexavalent (Cr(VI)) on aquifer sediments within the Cr plume at Los Alamos National Laboratory has been conducted to (1) refine conceptual and numerical models of chromium fate and transport, (2) evaluate the long-term stability of Cr(III)/Cr(VI) in the complex groundwater system along flow paths from the source to the regional aquifer, and (3) evaluate and develop options for successful remediation. The naturally high chromium abundance in aquifer sediments at Los Alamos pose an unique challenge for characterization of chromium reduction, making conventional approaches such as uptake tests and advanced spectroscopic measurements ineffective in identifying relatively small amounts of anthropogenic Cr(VI) in the sediments. To address this challenge and as complimentary to these conventional methods, sequential leaching tests were conducted on core hole sediments obtained from sonic drilled cores taken from both contaminated and non-contaminated horizons among two mineralogically distinct formations (Puye formation and Miocene Pumiceous Unit) within the Cr plume. A series of three and coherent sequential leaching steps were conducted: 1) an alkaline leach to determine the amount of Cr(VI) sorbed on the sediments. 2) a weak acid leach (using 0.01 M and 0.1 M HNO{sub 3}) to determine the amount of anthropogenic chromium (Cr(III) and Cr(VI)) on aquifer sediment surfaces, and 3) a strong acid leach (using 2 M HNO{sub 3}) to characterize the amount of releasable Cr(III) from aquifer minerals. Additionally we tested the efficiency and detection limit of sequential leaching on bentonite, which consists mainly of smectite, used in drill muds and laboratory-grade biotite spiked with known concentrations of Cr(VI). Smectite and biotite are two phases considered to be potentially important host minerals in aquifer sediments within the plume. Thus, by comparing contaminated and uncontaminated sediment leachate results of chromium and other major and trace elements, the signature and quantity of anthropogenic Cr(VI) can be derived. Our results from the weak acid leaching test indicate that the method detection limit for Cr 'uptake' was about 1 μg/g for biotite and about 0.5 μg/g for bentonite. Our results also indicate that all samples taken from known contaminated horizons in comparison to non-contaminated ones within the Puye formation showed no statistical difference in the amount of Cr leached indicative of its insignificant Cr(VI) attenuation capacity. The amount of excess Cr leached from the magnetic fraction of the contaminated Miocene Pumiceous samples was about 2 μg/g of sediment. Considering that the magnetic fraction was about 11% by mass of the bulk sample, the excess amount of Cr leached from the bulk material would be about 0.2 μg/g of sediment, suggesting the potential for some Cr(VI) attenuation capacity in the Miocene pumice unit. (authors)