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VTc is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. V3+ is bonded in a body-centered cubic geometry to eight equivalent Tc3- atoms. All V–Tc bond lengths are 2.62 Å. Tc3- is bonded in a body-centered cubic geometry to eight equivalent V3+ atoms.
Correction for ‘Computational approaches for XANES, VtC-XES, and RIXS using linear-response time-dependent density functional theory based methods’ by Daniel R. Nascimento et al. , Phys. Chem. Chem. Phys. , 2022, 24 , 14680–14691, https://doi.org/10.1039/D2CP01132H.
Time-dependent density functional theory provides a sufficiently accurate framework to study X-ray spectroscopies.
The outline for the presentation is: Programmatic considerations; End use of data; Holdup measurements used to support safeguards; Quality assurance program components; Technical and administrative challenges; and, Summary.
This viewgraph presentation gives a detailed description of the video teleconference equipment upgrade, salvo updates, and a service/change request status.
Venoconstrictive thigh cuffs (VTC) are a mechanical countermeasure capable of attenuating the spaceflight induced headward fluid shift, and thus may be a viable spaceflight associated neuro-ocular syndrome (SANS) countermeasure. Crewmembers can use VTC to mitigate the headward fluid shift to aid in adapting to spaceflight. However, data are needed to determine if VTC affect ocular structures. PURPOSE The purpose of this study is to determine the efficacy of long duration use of VTC application to mitigate the spaceflight-induced headward fluid shift. We hypothesize that a VTC countermeasure will temporarily reverse the headward fluid shift and attenuate spaceflight-induced changes of internal jugular vein (IJV) cross-sectional area, IJV pressure, stroke volume, cardiac output, intraocular pressure (IOP), and optic nerve head and retinal morphology. METHODS This study will evaluate the effectiveness of VTC countermeasure application on the headward fluid shift, as well as cardiovascular and ocular variables. VTC during spaceflight will be worn for an extended duration (up to 6 hours) with data collected at three time points (30 minutes, 3 hours, and 6 hours) to characterize the temporal profile of key fluid shift outcome measures of the vascular fluid shift, IOP, and ocular structure changes. Ten astronauts will be recruited to participate and will be studied before and during approximately 180-day International Space Station (ISS) spaceflight missions. Baseline data collection will occur approximately 90-days before launch (Figure). Preflight, each leg of the crewmember will be measured to determine the VTC cuff size and a cuff fit check session will occur prior to the preflight baseline ground imaging to verify the appropriate fit measured via a surface contact pressure. Prior to donning the VTC, baseline measures without VTC will be collected seated, supine, and supine followed by data collection with the VTC. The baseline data collection will include ultrasound (IJV area and pressure, stroke volume and cardiac output), brachial blood pressure and heart rate, optical coherence tomography (OCT) imaging (total retinal thickness and choroid thickness), and IOP. An inflight cuff fit check session, same as the preflight fit check, will occur prior to VTC use on ISS. The inflight VTC experiment will be conducted early (FD45) and late (R-45) to determine if mission duration affects VTC fit and the efficacy of fluid redistribution. A system usability scale comfort questionnaire will be included in each VTC session to capture feedback from crewmembers regarding the comfort and usability of the VTC. SCIENTIFIC & MISSION IMPACT Results will narrow knowledge gaps described in the Human Research Roadmap to mitigate the headward fluid shift during spaceflight and help NASA to 1) determine the efficacy of extended use VTC application to mitigate the spaceflight-induced headward fluid shift and 2) further the understanding of the use of VTC on vascular fluid shifts, IOP, and ocular structure during spaceflight. Supported by NASA Human Research Program Directed Research. Figure. Detailed Testing Schedule. Baseline data collection at L-90 will be performed in a randomized order of position.
X-ray emission spectroscopy (XES) of transition metal compounds is a powerful tool for investigating the spin and oxidation state of the metal centers. Valence-to-core (vtc) XES is of special interest, as it contains information on the ligand nature, hybridization, and protonation. To date, most vtc-XES studies have been performed with high-brightness sources, such as synchrotrons, due to the weak fluorescence lines from vtc transitions. Here, we present a systematic study of the vtc-XES for different titanium compounds in a laboratory setting using an X-ray tube source and energy dispersive microcalorimeter sensors. With a full-width at half-maximum energy resolution of approximately 4 eV at the Ti Kβ lines, we measure the XES features of different titanium compounds and compare our results for the vtc line shapes and energies to previously published and newly acquired synchrotron data as well as to new theoretical calculations. Finally, we report simulations of the feasibility of performing time-resolved vtc-XES studies with a laser-based plasma source in a laboratory setting. Our results show that microcalorimeter sensors can already perform high-quality measurements of vtc-XES features in a laboratory setting under static conditions and that dynamic measurements will be possible in the future after reasonable technological developments.
Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal is the decisive interaction in the C–H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal–alkane interactions during transition-metal mediated C–H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO) 2 ), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C–H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C–H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO) 2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C–H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.
Experimental detection of the Pt 5d densities of states in the valence band is conducted on a series of Pt-Ni alloys by high energy resolution valence-to-core X-ray emission spectroscopy (VTC-XES) at the Pt L 3 -edge. VTC-XES measurements reveal that the Pt d-band centroid shifts away from the Fermi level upon dilution, accompanied by concentration-dependent Pt d-band width. The competition between the strain effect and ligand effect is observed experimentally for the first time. It is found that the d-band widths in Pt 3 Ni and PtNi are broader than that of Pt metal due to compressive strain which overcompensates the effect of dilution, while it is narrower in PtNi 3 where the ligand effect dominates. VTC-XES is demonstrated to be a powerful tool to study the Pt d-band contribution to the valence band of Pt-based bimetallic. The implication for the enhanced activity of Pt-Ni catalysts in oxygen reduction reaction is discussed.
In this work, we report valence-to-core (VTC) X-ray emission spectroscopy (XES) measurements and theoretical calculations of the electrochemical sequence ε-VOPO 4 , ε-LiVOPO 4 , ε-Li 2 VOPO 4 and the reference oxides V 2 O 3 , VO 2 , and V 2 O 5 . In our analysis of these results, we establish a framework for interrogating chemical bonding that is generally applicable to a wide range of systems, including complex, extended inorganic compounds. While this latter regime has garnered less focused application than, e.g. , metalloenzymes in many excellent catalysis studies, we show that the technique provides high utility in materials-focused energy storage research. Here, sensitivities to the local atomic structure and hybridization schemes are discussed in detail. Similarly, the effect of lithiation on oxidation, delocalization, and shifts in ligand valence energy levels are all readily apparent in the analyzed results. Finally, the TDDFT projections clearly reveal the directional dependencies of the valence band at each of the vanadium sites. Our results demonstrate laboratory-based X-ray spectroscopy instrumentation is a viable route for attaining well-resolved VTC-XES features for inorganic compounds of 3d transition metals, even for samples of limited quantity or suffering from sensitivity to the atmosphere. The experimental results are in good agreement with results produced by real-space Green's function and time-dependent density functional theory (TDDFT) methods, respectively. Hence, we propose that VTC-XES, when equipped with appropriate theoretical support, can be a valuable complement to X-ray absorption pre-edge features for more detailed characterization of a compound's electronic structure. We expect similar analyses will find application in a broad range of materials chemistry research and provide both fundamental and applied insights.
Here we report a comprehensive computational study of unsupervised machine learning for extraction of chemically relevant information in X-ray absorption near edge structure (XANES) and in valence-to-core X-ray emission spectra (VtC-XES) for classification of a broad ensemble of sulphorganic molecules. By progressively decreasing the constraining assumptions of the unsupervised machine learning algorithm, moving from principal component analysis (PCA) to a variational autoencoder (VAE) to t-distributed stochastic neighbour embedding (t-SNE), we find improved sensitivity to steadily more refined chemical information. Surprisingly, when embedding the ensemble of spectra in merely two dimensions, t-SNE distinguishes not just oxidation state and general sulphur bonding environment but also the aromaticity of the bonding radical group with 87% accuracy as well as identifying even finer details in electronic structure within aromatic or aliphatic sub-classes. We find that the chemical information in XANES and VtC-XES is very similar in character and content, although they unexpectedly have different sensitivity within a given molecular class. We also discuss likely benefits from further effort with unsupervised machine learning and from the interplay between supervised and unsupervised machine learning for X-ray spectroscopies. Our overall results, i.e., the ability to reliably classify without user bias and to discover unexpected chemical signatures for XANES and VtC-XES, likely generalize to other systems as well as to other one-dimensional chemical spectroscopies.
Astronauts experience a chronic headward fluid shift in weightlessness as evidenced by increased cardiac output, decreased leg volume, a redistribution of venous fluid, and venous congestion in the upper body. Alterations in cerebrospinal fluid hydrodynamics and changes in cerebral venous pressure secondary to the headward fluid shift may contribute to ocular changes associated with spaceflight-associated neuro-ocular syndrome (SANS). Veno-constrictive thigh cuffs (VTC; Braslets) provided to Soyuz crewmembers alleviate symptoms of the headward fluid shift during the first week of spaceflight and have been documented to reduce internal jugular vein (IJV) distension during weightlessness. Application of VTCs designed collaboratively by NASA Johnson Space Center Cardiovascular and Vision Laboratory (CVL) and Clemson Textile Laboratory at Clemson University to improve fit and comfort was documented to mitigate changes in choroid thickness, intraocular pressure, and IJV area during posture-induced headward fluid shifts. VTC are demonstrated to reduce headward fluid shifts in both ground-based and spaceflight studies, and thus, may be a countermeasure against development of SANS. In addition, VTC are a simple mechanical countermeasure currently at a high technical readiness level (TRL) and are compact and lightweight, making them compatible with the spaceflight operations environment
As the second most common transition metal in the human body, Zinc is of great interest in research but has few viable routes for its direct structural study in biological systems. Herein, Zn valence-to-core X-ray emission spectroscopy (VtC XES) and Zn K-edge X-ray absorption spectroscopy (XAS) are presented as a means to understand the local structure of zinc in biological systems through the application of these methods to a series of biologically relevant model complexes. Taken together, the Zn K-edge XAS and VtC XES provide a means to establish the ligand identity, local geometry, and metal-ligand bond lengths. Experimental results were supported by strongly correlated density-functional-theory-based calculations, which, coupled with the complementarity of the two spectroscopic approaches, further enables future applications to protein systems to be examined in a predictive fashion. In this regard, test calculations were performed to showcase the sensitivity of these techniques to realistic biological applications.
Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped “His-brace” configuration including the N-terminal histidine and its amine group as ligands. Here, this study explicitly investigates the electronic structure of the d 10 Cu(I) active site in a LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H 2 O 2 O–O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H 2 O 2 .
For ships at sea. satellites provide the only option for high data rate (HDR), long haul communications. Furthermore the demand for HDR satellite communications (SATCOM) for military and commercial ships. and other offshore platforms is increasing. Presently the bulk of this maritime HDR SATCOM connectivity is provided via C-band and X-band. However, the shipboard antenna sizes required to achieve a data rate of, say T 1 (1.544 Mbps) with present C-/X-band SATCOM systems range from seven to ten feet in diameter. This limits the classes of ships to which HDR services can be provided to those which are large enough to accommodate the massive antennas. With its high powered K/Ka-band spot beams, the National Aeronautics and Space Administration's (NASA) Advanced Communications Technology Satellite (ACTS) was able to provide T I and higher rate services to ships at sea using much smaller shipboard antennas. This paper discusses three shipboard HDR SATCOM demonstrations that were conducted with ACTS between 1996 and 1998. The first demonstration involved a 2 Mbps link provided to the seismic survey ship MN Geco Diamond equipped with a 16-inch wide, 4.5-inch tall, mechanically steered slotted waveguide array antenna developed by the Jet Propulsion Laboratory. In this February 1996 demonstration ACTS allowed supercomputers ashore to process Geco Diamond's voluminous oceanographic seismic data in near real time. This capability allowed the ship to adjust its search parameters on a daily basis based on feedback from the processed data, thereby greatly increasing survey efficiency. The second demonstration was conducted on the US Navy cruiser USS Princeton (CG 59) with the same antenna used on Geco Diamond. Princeton conducted a six-month (January-July 1997) Western Hemisphere solo deployment during which time T1 connectivity via ACTS provided the ship with a range of valuable tools for operational, administrative and quality-of-life tasks. In one instance, video teleconferencing (VTC) via ACTS allowed the ship to provide life-saving emergency medical aid, assisted by specialists ashore. to a fellow mariner - the Master of a Greek cargo ship. The third demonstration set what is believed to be the all-time SATCOM data rate record to a ship at sea, 45 Mbps in October 1998. This Lake Michigan (Chicago area) demonstration employed one of ACTS' fixed beams and involved the smallest of the three vessels, the 45-foot Bayliner M/V Entropy equipped with a modified commercial-off-the-shelf one-meter antenna. A variety of multi-media services were provided to Entropy through a stressing range of sea states. These three demonstrations provided a preview of the capabilities that could be provided to future mariners on a more routine basis when K/Ka-band SATCOM systems are widely deployed.
A large-scale, distributed, high-speed data acquisition system (HSDAS) is currently being installed at the Space Power Facility (SPF) at NASA Glenn Research Center s Plum Brook Station in Sandusky, OH. This installation is being done as part of a facility construction project to add Vibro-acoustic Test Capabilities (VTC) to the current thermal-vacuum testing capability of SPF in support of the Orion Project s requirement for Space Environments Testing (SET). The HSDAS architecture is a modular design, which utilizes fully-remotely managed components, enables the system to support multiple test locations with a wide-range of measurement types and a very large system channel count. The architecture of the system is presented along with details on system scalability and measurement verification. In addition, the ability of the system to automate many of its processes such as measurement verification and measurement system analysis is also discussed.
Spaceflight-associated neuro-ocular syndrome (SANS) is a human spaceflight risk recognized by NASA. Elevated intracranial pressure (ICP) has been implicated as a root cause of many SANS signs and symptoms, yet there is no reliable noninvasive means of monitoring ICP. We have developed a noninvasive method of monitoring ICP change that exploits ear canal acoustic and otoacoustic emission (OAE) measurements. Changed ICP alters pressure in the inner ear, leading to changes in the tension and position of middle ear (ME) components; tension of these components determines the phase of the stimulus in the ear canal and the OAE response sound transmission back through the ME. The OAE method has been validated in several studies, including our own experiments as part of the NASA Fluid Shifts study. Systematic OAE phase changes demonstrating increased ME tension (an ICP indicator) are observed as posture is changed from seated to supine to head-down tilt (HDT). This effect can be substantially mitigated by lower body negative pressure (LBNP). The OAE technique has also been used on International Space Station (ISS) crewmembers, providing evidence that ICP in microgravity is similar to that seen on the ground in the supine position. The OAE method is also a rapid and noninvasive means of assessing the effectiveness of SANS countermeasures. Here we report results from two studies which used OAEs. In the most recent study (Venous Congestion Countermeasures - VCCM), three promising countermeasures [LBNP, an impedance threshold device (ITD), and veno-occlusive thigh cuffs (VTC)] were applied individually and in combination. In our previous ITD-only study, ITD was investigated for its ability to reduce ICP and cephalic venous congestion in supine and various HDT postures. Internal jugular vein (IJV) ultrasound showed a clear decongestive effect at all postures, however OAE data showed that ITD only caused a phase decrease (tension decrease) in HDT postures. In supine, ITD appeared to INCREASE tension. This paradox leads us to hypothesize that the OAE method is not accurately representing ICP changes with countermeasures (CM), which can alter ME tension through other means, such as ME pressure (MEP) changes. More generally, the exact mechanism for observed OAE response and stimulus phase shifts are not clearly understood, specifically with regard to the effects of MEP. The VCCM study examined the effects of externally-applied MEP on OAE recordings to document the relationship between these parameters. Analysis of these data provide new insights to these OAE mechanisms, in addition to results on CM effectiveness.
Significance Transition metals are of crucial importance for primary productivity; their scarcity limits crop yield in agriculture and carbon sequestration on a global scale. Copper (Cu), iron (Fe), and manganese (Mn) are among the most important trace elements that enable the redox chemistry in oxygenic photosynthesis. The single-celled, eukaryotic green alga Chlamydomonas reinhardtii is a choice experimental system for studying trace metal homeostasis in the context of phototrophy, offering all the advantages of a classical microbial system with a well-characterized photosystem and trace metal metabolism machinery of relevance to plants. This project identifies and differentiates different trace metal storage sites in Chlamydomonas and uncovers the dynamics of trace metal storage and mobilization in situations of fluctuating resources.