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Surface Dynamics of Selective Hydration of Rutile TiO 2 : A Kinetic Monte Carlo Approach

The utility of atomic layer deposition (ALD) continues to expand beyond conformal thin-film fabrication to include area- or site-selective ALD. We previously identified a strategy for site-selective ALD (SS-ALD) via the evaluation of thermodynamically preferred hydration of rutile TiO 2 surfaces, as deduced from electronic structure calculations. Here, we report a novel kinetic Monte Carlo (KMC) model that allows for the investigation of surface dynamics and kinetics that improves our understanding of and intuition for the selective hydration strategy. Here we demonstrate the validity of the strategy with respect to step-edge defects for the lowest energy (110) facet as well as report results for the other common facets which agree with experimental STM observations. The results here indicate that the selective hydration strategy is feasible both thermodynamically (evaluated in our previous publication) and kinetically (from the KMC model). Because diffusion has a slower rate than others, we find that any proximity effects between terrace and defect sites are unlikely to affect the selective hydration strategy for rutile TiO 2 . The KMC model further provides relevant timescales for achieving selectivity experimentally and establishes the kinetic viability of the selective hydration approach to SS-ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Operando XAS and DFT Uncover Structure-Performance Relationships in Re/TiO 2 for Selective CO 2 Hydrogenation to Methanol

The conversion of CO 2 into value-added chemicals, such as methanol, offers a promising pathway toward a renewable energy future. However, a precise kinetic control and a highly selective catalyst are necessary to overcome the thermodynamic preference for CO 2 hydrogenation to methane. Rhenium-based catalysts, particularly Re/TiO 2 , demonstrate high activity and selectivity for methanol under high-pressure conditions. For example, at 100 bar and 200 °C, a methanol selectivity of 97−99% was obtained. Catalysts with 1 wt % Re and 5 wt % Re/ TiO 2 were used to study the effect of cluster sizes. At 250 °C, the 1 wt % catalyst achieves 97% selectivity at 23% conversion, whereas 5 wt % Re/TiO 2 achieves 74% selectivity at 40% conversion, corresponding to a drop in space-time yield from 65 to 16 g CH 3 OH ·g Re −1 ·h −1 , respectively. X-ray absorption spectroscopy provided insights into the structure of the active sites, while density functional theory calculations revealed the effects of cluster size on the energy barriers for H 2 activation, CH 3 OH dissociation, and CH 3 OH desorption, all of which directly influence conversion and selectivity. These results underscore the importance of balancing cluster size for optimal catalyst performance and provide insights into the design of efficient and selective catalysts for renewable methanol production.

XAS

Controlling solvation in conducting redox polymers for selective electrochemical separation of nitrate from wastewater

Selective capture of nitrate from wastewater is crucial for ensuring safe drinking water and promoting resource circularity. This study investigated alkylated polyaniline redox polymers as highly-selective electrosorbents to address this challenge. By controlling polymer solvation properties through synthetic functionalization, poly(N-methylaniline) (PNMA) achieves a nitrate uptake of up to 1.38 mmol g −1 -polymer and a separation factor of 7 over chloride. Poly(N-butylaniline) (PNBA) further enhances selectivity, achieving a separation factor beyond 14 due to increased hydrophobicity. The mechanisms underlying this selectivity are investigated using ab initio molecular dynamics (AIMD) and in-situ electrochemical quartz crystal microbalance (EQCM) studies, which reveal that hydrophobicity reduces chloride binding. A technoeconomic analysis indicates that methylation on PANI reduces nitrate removal costs by 50% compared to non-functionalized PANI, due to enhanced selectivity and uptake, and decreased energy consumption. PNMA electrodes demonstrate practical nitrate selectivity over 20 versus chloride in real wastewater, while avoiding sulfate binding. This study highlights the potential of controlling solvation at electroactive polymers to enhance nitrate selectivity, offering a promising design path for redox-mediated electrochemical separations.

chemical engineering

A family portrait of lanmodulin selectivity for enhanced rare-earth separations

Proteins offer a molecular design space to create bespoke ligands for the separation of critical metals like rare earth elements (REs). However, data-intensive approaches to tune metalloprotein selectivity are constrained by the low-throughput nature of existing characterization methods. Here we invented an assay called ‘SpyTag-Catcher Immobilization of Lanmodulin for Assaying Metal-Binding Selectivity’ (SpyCI-LAMBS) to measure metalloprotein selectivity en masse. This 96-format workflow was used to study the selectivity of 621 lanmodulin (LanM) orthologs for 15 REs, revealing eight distinct selectivity profiles based on sequence-to-function analyses. We discovered >200 LanMs with stronger selectivity against low-value LaIII relative to the prototypical LanM. This includes a LanM that can perform a challenging one-stage separation of PrIII from LaIII with up to >99.9 mol% purity and 83% yield. SpyCI-LAMBS is a powerful tool that can rapidly collect high-fidelity selectivity data to inform metal ion separations and machine-learning-assisted metalloprotein design.

59 BASIC BIOLOGICAL SCIENCES

Diacylglycerol enantiomer selectivity of diacylglycerol acyltransferases highlights metabolic specialization in triacylglycerol synthesis across the tree of life

Triacylglycerols are the major energy storage lipids in plants, animals, and microorganisms, and are predominantly produced by acyl-CoA:diacylglycerol (DAG) acyltransferases (DGATs). Two enantiomers of the DAG substrate, sn -1,2 and sn -2,3, can be produced by different biological mechanisms; however, little is known about which species produce each enantiomer, the selectivity of DGAT isoforms for either enantiomer, or whether DGAT enantiomer selectivity varies across organisms. Here, DAG enantiomer selectivity of DGAT1 and DGAT2 was measured from eight seed plants, two mammals, one oleaginous yeast, and one photosynthetic microalga using enantiomer-specific in vitro DGAT assays. Across most plants, DGAT1 favored sn -1,2-DAG, whereas DGAT2 preferentially utilized sn -2,3-DAG. However, there were several exceptions. Mammalian DGAT1, DGAT2, and microbial DGAT1s efficiently used both DAG enantiomers, while microbial DGAT2s had unique selectivity. The selectivity of several DGATs for combined acyl-CoA and DAG enantiomer molecular species were also evaluated for biotechnical applications. Therefore, DGAT DAG enantiomer selectivity is common yet strongly dependent on lineage and isoform and likely shaped in part by species-specific metabolic context of triacylglycerol synthesis, turnover, and remodeling. This work expands our understanding of DGAT function and establishes a foundation for leveraging enantiomer-selective acyltransferases in metabolic engineering of tailored lipid products.

Arabidopsis thaliana

Improving galaxy cluster selection with the outskirt stellar mass of galaxies

The number density and redshift evolution of optically selected galaxy clusters offer an independent measurement of the amplitude of matter fluctuations, 𝑆 8 . However, recent results have shown that clusters chosen by the redMaPPer algorithm show richness-dependent biases that affect the weak lensing signals and number densities of clusters, increasing uncertainty in the cluster mass calibration and reducing their constraining power. Here, in this work, we evaluate an alternative cluster proxy, outskirt stellar mass, 𝑀 out , defined as the total stellar mass within a [50, 100] kpc envelope centered on a massive galaxy. This proxy exhibits scatter comparable to redMaPPer richness, 𝜆, but is less likely to be subject to projection effects. We compare the Dark Energy Survey Year 3 redMaPPer cluster catalog with a 𝑀 out selected cluster sample from the Hyper-Suprime Camera survey. We use weak lensing measurements to quantify and compare the scatter of 𝑀 out and 𝜆 with halo mass. Our results show 𝑀 out has a scatter consistent with 𝜆, with a similar halo mass dependence, and that both proxies contain unique information about the underlying halo mass. We find 𝜆-selected samples introduce features into the measured Δ⁢Σ signal that are not well fit by a log-normal scatter only model, absent in 𝑀 out selected samples. Our findings suggest that 𝑀 out offers an alternative for cluster selection with more easily calibrated selection biases, at least at the generally lower richnesses probed here. Combining both proxies may yield a mass proxy with a lower scatter and more tractable selection biases, enabling the use of lower mass clusters in cosmology. Finally, we find the scatter and slope in the 𝜆 −𝑀 out scaling relation to be 0.49 ±0.02 and 0.38 ±0.09.

79 ASTRONOMY AND ASTROPHYSICS

A systematic decision-making methodology to formalize the selection of degree of realism in screening analysis of probabilistic risk assessment

In the nuclear power domain, Probabilistic Risk Assessment (PRA) is used to inform decision-making for Nuclear Power Plants (NPPs). Recently, there has been an increase in the utilization of modeling and simulation (M&S) to support the estimation of PRA inputs. Risk analysts should carefully select the PRA items that require M&S and their degree of realism (DoR) with consideration of the required resources. To support this selection, this article formulates a systematic decision-making approach for the DoR selection. The DoR selection is made based on two predictive decision-making attributes: the predicted differences in safety risk estimate (ΔSaRi) and the cost of analysis (ΔCAN). This research also develops and quantifies causal models to estimate ΔSaRi and ΔCAN. The causal model-based prediction of ΔSaRi and ΔCAN helps reduce the trial-and-error nature of the DoR selection in the PRA screening analysis and provides insights for DoR selection and the gradual refinements of PRA realism. This approach is demonstrated for a case study on fire PRA of NPPs, where an adequate DoR is selected from two fire models: an engineering correlation and a zone model.

Alkhatib, Sari [Department of Nuclear, Plasma, and

Optical and radio properties of X-ray selected BL Lacertae objects

The eight BL Lac objects from the HEAO 1 A-2 all-sky survey and from the Einstein medium-sensitivity survey (MSS) form a flux-limited complete X-ray selected sample. The optical and radio properties of the MSS BL Lac objects are presented and compared with those of the HEAO 1 A-2 sample and with those of radio-selected BL Lac objects. The X-ray selected BL Lac objects possess smaller polarized fractions and less violent optical variability than radio-selected BL Lac objects. These properties are consistent with the substantial starlight fraction seen in the optical spectra of a majority of these objects. This starlight allows a determination of definite redshifts for two of four MSS BL Lac objects and a probable redshift for a third. These redshifts are 0.2, 0.3, and 0.6. Despite the differences in characteristics between the X-ray selected and radio-selected samples, it is concluded that these eight objects possess most of the basic qualities of BL Lac objects and should be considered members of that class. Moreover, as a class, these X-ray selected objects have the largest ratio of X-ray to optical flux of any active galactic nuclei yet discovered.

Stocke, J. T.

Role of orientation reference selection in motion sickness

The overall objective of this proposal is to understand the relationship between human orientation control and motion sickness susceptibility. Three areas related to orientation control will be investigated. These three areas are (1) reflexes associated with the control of eye movements and posture, (2) the perception of body rotation and position with respect to gravity, and (3) the strategies used to resolve sensory conflict situations which arise when different sensory systems provide orientation cues which are not consistent with one another or with previous experience. Of particular interest is the possibility that a subject may be able to ignore an inaccurate sensory modality in favor of one or more other sensory modalities which do provide accurate orientation reference information. We refer to this process as sensory selection. This proposal will attempt to quantify subjects' sensory selection abilities and determine if this ability confers some immunity to the development of motion sickness symptoms. Measurements of reflexes, motion perception, sensory selection abilities, and motion sickness susceptibility will concentrate on pitch and roll motions since these seem most relevant to the space motion sickness problem. Vestibulo-ocular (VOR) and oculomotor reflexes will be measured using a unique two-axis rotation device developed in our laboratory over the last seven years. Posture control reflexes will be measured using a movable posture platform capable of independently altering proprioceptive and visual orientation cues. Motion perception will be quantified using closed loop feedback technique developed by Zacharias and Young (Exp Brain Res, 1981). This technique requires a subject to null out motions induced by the experimenter while being exposed to various confounding sensory orientation cues. A subject's sensory selection abilities will be measured by the magnitude and timing of his reactions to changes in sensory environments. Motion sickness susceptibility will be measured by the time required to induce characteristic changes in the pattern of electrogastrogram recordings while exposed to various sensory environments during posture and motion perception tests. The results of this work are relevant to NASA's interest in understanding the etiology of space motion sickness. If any of the reflex, perceptual, or sensory selection abilities of subjects are found to correlate with motion sickness susceptibility, this work may be an important step in suggesting a method of predicting motion sickness susceptibility. If sensory selection can provide a means to avoid sensory conflict, then further work may lead to training programs which could enhance a subject's sensory selection ability and therefore minimize motion sickness susceptibility.

Peterka, Robert J.

Forty Years of Psychological and Psychiatric Selection of NASA Astronauts

The purpose of this presentation is to chronicle the history and development of the psychological selection process for NASA astronauts. For over 40 years, astronaut applicants have undergone rigorous medical testing to qualify for candidacy. Psychological selection has an equally long history, dating back to 1958, when psychological requirements were established for astronauts during the Mercury program. However, for many years, psychological selection consisted of psychiatric screening for psychopathology. As we approach the day in which the first ISS crew will live and work in space for months at a time, it becomes clear that both the psychological criteria and the selection system to detect said criteria have changed. This presentation discusses the events that led to the current, dual-phase selection system that is used to select individuals into the astronaut corps. Future directions for psychological selection will also be addressed.

Holland, Albert W.

Selection and Assessment of Predictions of the Mars Pathfinder Landing Site

The successful landing of the Mars Pathfinder spacecraft on Mars allows the review of the process of selecting the landing site and assessing predictions made for the site based on Viking and Earth-based data. Selection of the landing site for Mars Pathfinder was a two-phase process. The first phase took place from October 1993 to June 1994 and involved: initial identification of engineering constraints, definition of environmental conditions at the site for spacecraft design, and evaluation of the scientific potential of different landing sites. This phase culminated with the first "Mars Pathfinder Landing Site Workshop", held at the Lunar and Planetary Institute in Houston, Texas on April 18-19, 1994, in which suggested approaches and landing sites were solicited from the entire scientific community. A preliminary site was selected by the project for design purposes in June 1994. The second phase took place from July 1994 to March 1996 and involved: developing criteria for evaluating site safety using images and remote sensing data, testing of the spacecraft and landing subsystems (with design improvements) to establish quantitative engineering constraints on landing site characteristics, evaluating all potential landing sites on Mars, and certification of the site by the project. This phase included a second open workshop, "Mars Pathfinder Landing Site Workshop II: Characteristics of the Ares Vallis Region and Field Trips in the Channeled Scabland, Washington" held in Spokane and Moses Lake September 24-30, 1995 and formal acceptance of the site by NASA Headquarters. Engineering constraints on Pathfinder landing sites were developed from the initial design of the spacecraft and the entry, descent and landing scenario. The site must be within 5 degrees of the subsolar latitude at the time of landing (15N for maximum solar power and flexible communications with Earth. It also must be below 0 km elevation to enable enough time for the parachute to bring the lander to the proper terminal velocity for landing. The entire landing ellipse, which is 70 km by 200 km due to navigational, ephemeris and atmospheric uncertainties, must be free of steep slopes, scarps and obvious hazards in Viking orbiter images, have acceptable radar reflectivity, moderate rock abundances and have little or no dust. Scientific considerations of the Mars Pathfinder payload and mission indicate that analyses of "grab bag" samples at the mouths of outflow channels can offer a first order assessment of a variety of rock types on Mars. Highland sites offer the advantage of in situ analysis of ancient rocks on Mars that record crustal differentiation and the nature of the early environment. Dark gray sites offer the potential of analyzing unweathered and unoxidized materials. Following a general assessment of the safety of different sites, a preliminary selection of a "grab bag" site was made. This site, Ares Vallis, is near the mouth of an outflow channel that may contain ancient Noachian terrain, Hesperian ridged plains, and reworked channel materials. All potential landing sites on Mars that met basic safety criteria were analyzed in detail. Sites (100 by 200 km target ellipses) were considered safe if they were below 0 km elevation, were free of obvious hazards (high relief surface features) in high-resolution (< 50 m/pixel) Viking orbiter images and had acceptable reflectivity and roughness at radar wavelengths, high thermal inertia, moderate rock abundance, low red to violet ratio, and low albedo. Only 4 sites on Mars met all the above criteria, which included 1995 opposition 3.5 cm delay-Doppler radar data. Complete data were evaluated for 7 sites and the Viking landing sites for comparison for all the above criteria as well as crater abundance, hill and mesa abundance, slopes over meter to kilometer scales, low altitude winds (from global circulation models and slopes), the size-frequency distribution of large rocks, as well as rover trafficability and science potential. Discussion of potential hazards at Ares Vallis using a variety of data sets (including radar) at a second open workshop, indicated this site cannot be shown to be any more hazardous than the Viking landing sites. Field trips to the Channeled Scabland and the Ephrata Fan, analogs for Ares Vallis and the landing site, respectively, provided valuable insight into possible geologic processes and potential surface characteristics. Three sites met all the data requirements and safety criteria for landing Pathfinder. Ares Vallis was selected by the project because it appeared acceptably safe (although it appeared to have greater rock abundances than other sites, its elevation was likely the best known) and offered the prospect of analyzing a variety of rock types expected to be deposited by catastrophic floods, which would enable addressing first-order scientific questions such as differentiation of the crust, the development of weathering products, and the nature of the early martian environment and its subsequent evolution. The selection was reviewed by an external board at a number of meetings and accepted, and the site was approved by NASA Headquarters. Data gathered by the Pathfinder lander' and rover provides the opportunity to test the predictions made for the site in the selection process based on remote observations from Earth, orbit, and the surface. The discussion below is taken from Golombek et al. to which the reader is referred for a more complete discussion and a complete list of references, which are omitted here for brevity. Many characteristics of the landing site are consistent with its being shaped and deposited by the Ares and Tiu catastrophic floods. The rocky surface is consistent a depositional plain comprising semi-rounded pebbles, cobbles and tabular boulders (some of which appear imbricated and/or inclined in the direction of flow) that appear similar to depositional plains in terrestrial catastrophic floods. The Twin Peaks appear to be streamlined hills in lander images, which is consistent with interpretations of larger hills in Viking orbiter images of the region that suggest the lander is on the flank of a broad, gentle ridge trending northeast from Twin Peaks. This ridge, which is the rise to the north of the lander, is aligned in the downstream direction from the Ares and Tiu Valles floods, and may be a debris tail deposited in the wake of the Twin Peaks. Channels visible throughout the scene may be a result of late stage drainage. As predicted by delay-Doppler radar measurements and tracking results, the average elevation of the center of the site was about the same as Viking Lander I relative to the 6.1 mbar geoid. The Doppler tracking and two-way ranging estimate for the elevation of the spacecraft is only 45 in lower than the Viking I Lander and within 100 in of that expected, which is within the uncertainties of the measurements. After landing, surface pressures and winds (5-10 m/s) were found to be similar to expectations based on Viking data, although temperatures were about 10 K warmer. The temperature profile below 50 km was also roughly 20 K warmer. As a result, predicted densities were 5% higher near the surface and up to 40% lower at 50 km but within the entry, descent and landing design margins. The populations of craters and small hills and the slopes of the hills measured in high-resolution (38 m/pixel) Viking orbiter images and the radar derived slopes of the landing site are all consistent with observations of these properties in the lander images. A rocky surface was expected from Viking Infra-Red Thermal Mapper (IRTM) observations and comparisons with the Viking landing sites. The observed cumulative fraction of area covered by rocks with diameters greater than 3 cm and heights greater than 0.5 in (potentially hazardous to landing) at Ares is similar to that predicted by IRTM observations and models of Viking lander and Earth analog rock size-frequency distributions. The IRTM prediction postulated an effective thermal inertia of 30 (10(exp -3) cgs units - cal/cubic cm/s(exp 0.5)/K) for the rock population, but we obtain a slightly different effective thermal inertia for the actual rock population. The validity of interpretations of radar echoes prior to landing are supported by a simple radar echo model, an estimate of the reflectivity of the soil from its bulk density, and the fraction of area covered by rocks. In the calculations, the soil produces the quasi-specular echo and the rocks produce the diffuse echo. The derived quasispecular cross section is comparable to the cross-sections and reflectivities reported for 3.5-cm wavelength observations. The model yields a diffuse echo that is modestly larger than the polarized diffuse echo reported for 3.5-cm wavelength observations. At 12.5-cm wavelength, similar rock populations at Ares and the Viking I site were expected because the diffuse echoes are comparable, but the large normal reflectivities suggests that bulk densities of the soils at depth are greater than those at the surface. We also obtain a fine-component inertia near 8.4 which agrees with the fine-component inertia of 8.7 (in 10(exp -3) cgs units) estimated from thermal observations from orbit by the IRTM; for this estimate, we used a bulk thermal inertia of 10.4 for the landing site, an effective thermal inertia near 40 (10(exp -3) cgs units) for the rock population, and a graphical representation of Kieffer's model. Color and albedo data for Ares suggested surfaces of materials at Ares Vallis would be relatively dust free or unweathered prior to landing compared with the materials at the Viking landing sites. This suggestion is supported by the abundance of relatively dark-gray rocks at Ares and their relative rarity at the Viking landing sites, where rocks are commonly coated with bright red dust. Finally, the 40 km long Ephrata Fan of the Channeled Scabland in Washington state, which was deposited where c

Golombek, M. P.

Development of a modulator to measure water vapor selectively in a gaseous mixture

Selective thermal modulation (STM) is a technique which produces a concentration-dependent pulse by selectively modulating a sample in a gas stream. Several types of modulation techniques, both chemical and physical, using adsorption, decomposition, and catalytic and mechanical methods have been developed for use with multiplex gas chromatography. Two of these applications involve selective modulation of the components present in the sample gas stream. The selective modulation of the concentration of specific sample molecules or classes of molecules provides additional analytical selectivity which can lead to selective detection. For some specific applications, the column may even be eliminated. Chemical modulation by absorption of a substance from the sample stream by a stationary phase will also produce a change in the signal intensity. Removal of a substance from the sample stream results in a signal containing a vacancy peak. In the work reported here, a selective thermal modulation technique has been developed as a method for determination of water vapor for possible use in Mars' atmosphere.

NASA Center ARC

XMM-Newton Observations of the DLS Shear-Selected Cluster Survey

The goal of this project continues to be to test the selection effects in cluster surveys by investigating the X-ray properties of the first shear-selected sample of galaxy clusters, the Deep Lens Survey (DLS). Because lensing signal is only sensitive to mass (albeit with projection effects), lensing signal can be used to select a sample that is independent of its X-ray properties. If a lensing-selected sample has very different X-ray properties from an X-ray selected sample, it would have important consequences for evolutionary studies based on existing cluster samples was aimed at refining the lensing-selected sample as part of this continuing study The grant supported a KPNO run to obtain data on another region of the sky to extend the cluster sample, and also the purchase of a disk array for archiving the optical mosaic data (Two terabytes worth) from which the lensing maps are derived As a result of the grant, we have extended the lensing cluster sample to another 4-square degree patch of the sky, adding another three clusters to our sample to be observed While the sample of X-ray observed clusters is too small to derive a firm conclusion yet, our preliminary finding is that the X-ray properties of the observed sample do not differ from those of X-ray selected surveys A paper discussing the first results has been published, and a second paper on the mass differences is still in preparation (with J Hughes as first author)

DellAntonio, Ian

Identifying or measuring selected substances or toxins in a subject using resonant raman signals

Methods and systems of the present invention identify the presence of and/or the concentration of a selected analyte in a subject by: (a) illuminating a selected region of the eye of a subject with an optical excitation beam, wherein the excitation beam wavelength is selected to generate a resonant Raman spectrum of the selected analyte with a signal strength that is at least 100 times greater than Raman spectrums generated by non-resonant wavelengths and/or relative to signals of normal constituents present in the selected region of the eye; (b) detecting a resonant Raman spectrum corresponding to the selected illuminated region of the eye; and (c) identifying the presence, absence and/or the concentration of the selected analyte in the subject based on said detecting step. The apparatus may also be configured to be able to obtain biometric data of the eye to identify (confirm the identity of) the subject.

Lambert, James L.

In Vitro Selection of Antibodies Targeting Yersinia pestis Membrane Lipids Using Nanodisc-Based Antigen Presentation

Proteins are the most common targets for antibody discovery and vaccine development, but their sequence variability can limit the breadth of resulting antigens. Lipids represent an alternative class of antigens due to their structural conservation and roles in host–pathogen interactions. Here, we describe the development and optimization of an in vitro antibody selection workflow using lipid-containing nanodiscs as antigen presentation platforms to enable phage and yeast display selections under conditions adapted for these non-protein targets. Lipopolysaccharide (LPS) nanodiscs were first used as a model system to evaluate selection strategies, including competitive and subtractive approaches to reduce non-specific binders, yielding peptide and single-chain variable fragment (scFv) binders that were affinity matured to improve binding signals. The same approach was subsequently used to select scFv antibodies that recognize lipid nanodiscs prepared from Yersinia pestis membrane lipid extracts. These antibodies show binding to lipid nanodiscs derived from Y. pestis, with evidence of selectivity relative to control nanodiscs. Overall, this work establishes a workflow for antibody selection against lipid-containing nanodisc antigens and highlights practical considerations associated with these targets. The approach may be useful for generating affinity reagents to membrane-associated lipids, although further characterization is required to define antigen specificity and functional activity.

59 BASIC BIOLOGICAL SCIENCES

Selectivity mechanisms of ion intercalation in Prussian blue analogs

Prussian blue analogs (PBAs) are a family of materials with facile, reversible, and selective ion transport capability for various ions via electrochemical intercalation, owing to their vacancy structure. The large tunable compositional space of PBAs allows for manipulation of intercalation behavior and selectivity by controlling structural vacancy level through choice of transition metal centers and modifications to the synthesis process. However, a lack of understanding of the mechanisms of ion selectivity hinders the material’s design process. Here, for this work, we investigated the origins of ion selectivity using a model PBA, copper hexacyanoferrate, and focused on eight technologically and biologically prominent ions, for which we determined a sequence of selectivity: Rb + > K + > Na + > Ba 2+ > Sr 2+ ≈ Ca 2+ > Mg 2+ > Li + . We provide electrochemical, structural, and redox evidence of strong correlation between the ion identity, the dominant charge-compensating redox, and preferred occupancy site. Specifically, using synchrotron anomalous X-ray diffraction (AXRD), we reveal that monovalent ions exhibit significant association with the corner sites of the unit cell and iron redox, whereas divalent ions display affinity toward the center site with higher ratios of copper redox. Informed by selectivity results, we applied CuHCFe to Li purification and achieved 99.9% purity. Our findings demonstrate an approach to elucidating ion intercalation behavior in order to distinguish and manipulate material properties to optimize separation performance.

Prussian blue analog

3D Printing of Functional Hydrogel Devices for Screenings of Membrane Permeability and Selectivity

Developing a fundamental understanding of the effects of varying ligand chemistries on mass transport rates is key to designing membranes with solute-specific selectivity. While permeation cells offer a robust method to characterize membrane performance, they are limited to assessing a single membrane chemistry or salt solution per test. As a result, investigating the effects of varying ligand chemistries on membrane performance can be a tedious process, involving both the preparation of multiple samples and numerous, time-consuming permeation tests. This study uses digital light processing (DLP) 3D printing to fabricate a millifluidic flow-based permeation device made from a hydrogel active ester network that can be easily functionalized with ion-selective ligands. Without the need for bonding or assembly steps, ligands can be introduced and tested in the permeation device by simply injecting a small volume of a ligand solution. Various salt concentrations and molecular species can be cycled through a single device by switching the solution feeding into the salt reservoir, thereby reducing the number of samples needed for permeability and selectivity screenings. This research sets the groundwork for formulation development and postprocessing methods to 3D-print functional millifluidic devices capable of assessing solute selectivity in membranes and polymer adsorbents for aqueous separations. In this work, comparable salt permeability trends were observed with both 3D-printed devices and traditional assays. Devices were functionalized with an imidazole ligand to investigate salt permeability and selectivity of monovalent and divalent salts. Measurements showed increasing permeability for monovalent salts (NaCl) relative to divalent salts (MgCl 2 , CuCl 2 ) in functionalized membranes, with higher monovalent/divalent selectivity at increasing imidazole grafting densities. Here, the methods and findings described here represent a step toward developing higher-throughput methods with 3D-printed devices for screening the effects of ligand chemistry on mass transport rates in membrane materials.

36 MATERIALS SCIENCE

Enhanced Selectivity for C 2 H 4 Production from C 2 H 6 on Partially Chlorinated IrO 2 (110) Surfaces

Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. Here, in this study, we investigated the oxidation of C 2 H 6 on Cl-modified IrO 2 (110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO 2 (110) surface enhances the selectivity for C 2 H 6 conversion to C 2 H 4 during TPRS by suppressing extensive oxidation to CO x products, while also either enhancing C 2 H 4 production or altering it to a lesser extent, depending on the initial C 2 H 6 coverage. The C 2 H 4 selectivity increased with increasing C 2 H 6 and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C 2 H 6 oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C 2 H 4 and CO x product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C 2 H 6 conversion to C 2 H 4 occurs on Cl-IrO 2 (110) by the hydrogenation of C 2 H 3 * species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C 2 H 3 * to escape blocked configurations and dehydrogenate, and that this process can limit the C 2 H 4 selectivity on Cl-IrO 2 (110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO 2 (110) enhances the selectivity for C 2 H 4 production from C 2 H 6 and provides insights into the reaction mechanism that can guide strategies to further improve the C 2 H 4 selectivity.

IrO2