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At least 577 records · Page 32

Effects of Molecular Size on Resolution in Charge Detection Mass Spectrometry

Instrumental resolution of Fourier transform-charge detection mass spectrometry instruments with electrostatic ion trap detection of individual ions depends on the precision with which ion energy is determined. Energy can be selected using ion optic filters or from harmonic amplitude ratios (HARs) that provide Fellgett’s advantage and eliminate the necessity of ion transmission loss to improve resolution. Unlike the ion energy-filtering method, the resolution of the HAR method increases with charge (improved S/N) and thus with mass. An analysis of the HAR method with current instrumentation indicates that higher resolution can be obtained with the HAR method than the best resolution demonstrated for instruments with energy-selective optics for ions in the low MDa range and above. However, this gain is typically unrealized because the resolution obtainable with molecular systems in this mass range is limited by sample heterogeneity. Here, this phenomenon is illustrated with both tobacco mosaic virus (0.6–2.7 MDa) and AAV9 (3.7–4.7 MDa) samples where mass spectral resolution is limited by the sample, including salt adducts, and not by instrument resolution. Nevertheless, the ratio of full to empty AAV9 capsids and the included genome mass can be accurately obtained in a few minutes from 1× PBS buffer solution and an elution buffer containing 300+ mM nonvolatile content despite extensive adduction and lower resolution. Empty and full capsids adduct similarly indicating that salts encrust the complexes during late stages of droplet evaporation and that mass shifts can be calibrated in order to obtain accurate analyte masses even from highly salty solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Demonstration of Capture, Cooling, Tagging, and Spectroscopic Characterization of UV Photoproduct Ions in a Cryogenic Ion Trap: Application to 266 nm Photofragment Ions from Rhodamine 6G

We demonstrate a method to determine the structures of the primary photodissociation products from a cryogenically cooled parent ion. In this approach, a target ion is cooled by a pulse of buffer gas and tagged in a 20 K Paul trap. The cold ion is then photodissociated by pulsed (~5 ns) UV laser excitation, and the ionic products are trapped, cooled, and tagged by introduction of a second buffer gas pulse in the same trap. The tagged fragments are then ejected into a triple focusing, UV/vis/IR time-of-flight photofragmentation mass spectrometer which yields vibrational and electronic spectra of the mass-selected photofragments. Furthermore, these methods are demonstrated by application to the 266 nm photodissociation of the Rhodamine 6G cation to yield the R575 fragment ion based on loss of ethene as well as to a weaker secondary fragment arising from loss of m/z 43.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Selective Electrolytic Reduction of CO 2 to Ethylene

We investigate the reduction of CO 2 to ethylene across buffered anolyte pH values 4 to 14 using a copper–phosphorus (Cu–P) electrocatalyst in a zero-gap membrane electrode assembly. Electrochemical CO 2 reduction using alkaline electrolytes typically shows limited carbon efficiencies and single-pass efficiencies, while acidic conditions typically favor the hydrogen evolution reaction. Results from this work show that weakly phosphate-buffered acidic anolytes (pH 6) maximize ethylene production with a 73% FE at 300 mA cm –2 and 51% FE at 500 mA cm –2 , including a 51% single-pass CO 2 conversion efficiency for over 400 h of continuous operation. We propose a mechanism based on pH-dependent CO coverage that controls the selectivity at the *HCCOH intermediate. Low CO coverage at pH 6 favors hydroxide elimination to *CCH, yielding ethylene (98% of C 2 products), while high coverage at pH 14 promotes hydrogenation to ethanol (44% of C 2 ). The HER mechanism transitions from H 2 O-mediated at pH 14 to phosphate-mediated (H 2 PO 4 – /HPO 4 2– ) at weakly acidic pH, minimizing HER competition at pH 6. This mechanistic understanding enables controlled C 2 product selectivity through manipulation of the CO coverage and local proton activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling the Magneto-Optical Response in Ultrathin Films of EuO 1– x via Interface Engineering with Ferroelectric BaTi 2 O 5

Utilizing pulsed laser deposition, a film of EuO 1–x was deposited onto a Si(001) substrate with MgO buffer and compared to the same heterostructure with an additional BaTi 2 O 5 thin film on top of the EuO 1–x surface. X-ray diffraction (XRD) indicates the films crystallize into a preferred EuO(111) orientation; it also reveals the clear presence of EuSi 2 , which suggests Si or Eu diffuses across the MgO buffer layer. EuO 1–x films exhibit a ferromagnetic (FM) signature and temperature-dependent exchange bias, indicated by MOKE measurements, suggesting the presence of a magnetic order well above the EuO Curie temperature with possible origins in charge carrier density near the interface. In comparison, an antiferromagnetic character persists well above the EuO Curie temperature of 69 K and the enhanced Curie temperature of 150 K for BaTi 2 O 5 films grown on the EuO 1–x films. Furthermore, the antiferromagnetic behavior is not seen in thicker EuO 1–x thin films when integrated with other ferroelectric (FE) phases of the BaO–TiO 2 system, suggesting an origin in the perturbed charge population at the BaTi 2 O 5 /EuO 1–x interface.

36 MATERIALS SCIENCE↗

Optimizing Catalysis by Combining Molecular Scaling Relationships: Iron Porphyrin-Catalyzed Electrochemical Oxygen Reduction as a Case Study

Here, the present work demonstrates the generality of molecular scaling relationships toward achieving faster catalysis at lower overpotentials. In iron porphyrin-catalyzed oxygen reduction, independent tuning of the catalyst E 1/2 and buffer pK a resulted in improvement of both the maximum turnover frequency (TOF max ) and the effective overpotential (η eff ). Interestingly, the most optimal system is achieved with the most reducing catalyst and a weak buffered acid—a perhaps counterintuitive conclusion. More generally, this study illustrates a path to optimization of catalytic systems through their differing responses to changes in the intrinsic features of the system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Behavior of Cerium at an Indium Tin-Doped Oxide Electrode in Acidic Media

The redox behavior and speciation of cerium at mesoporous thin films composed of nanoparticles of indium tin-doped oxide (nITO) electrodes were characterized in pH 4.8, 0.1 M acetate buffer and both 0.1 and 1 M HNO 3 using electrochemical techniques and X-ray photoelectron spectroscopy. Anodic deposition of ceria species from Ce(III) to the nITO electrode was achieved under all solvent conditions via spontaneous condensation of electrochemically generated ceric hydroxide species. In 1 M nitric acid, the rate of CeO 2 dissolution is on the same order as CeO 2 deposition, resulting in negligible amounts of CeO 2 electrodeposited at the nITO surface. The cathodic stripping of CeO 2 from the nITO substrate deposited in 0.1 M nitric acid or pH 4.8 acetate buffer follows a 2-step process where Ce(IV)-oxide is initially reduced to an unstable Ce(III)-oxide species that rapidly undergoes acid catalyzed dissolution to yield soluble Ce(III) (aq) . These findings provide a foundation for the pH and anodic potential controlled deposition of CeO 2 thin films to ITO substrates, which can aid in the development of materials composed of ceria. As a result, they can also be used to infer likely analogous actinide redox behavior and speciation at these electrodes.

Cerium↗

Mechanistic Insights into Cell-Free Gene Expression through an Integrated -Omics Analysis of Extract Processing Methods

Cell-free systems derived from crude cell extracts have developed into tools for gene expression, with applications in prototyping, biosensing, and protein production. Key to the development of these systems is optimization of cell extract preparation methods. However, the applied nature of these optimizations often limits investigation into the complex nature of the extracts themselves, which contain thousands of proteins and reaction networks with hundreds of metabolites. In this report we sought to uncover the black box of proteins and metabolites in Escherichia coli cell-free reactions based on different extract preparation methods. We assess changes in transcription and translation activity from σ70 promoters in extracts prepared with acetate or glutamate buffer and the common post-lysis processing steps of a runoff incubation and dialysis. We then utilize proteomic and metabolomic analyses to uncover potential mechanisms behind these changes in gene expression, highlighting the impact of cold shock-like proteins and the role of buffer composition.

59 BASIC BIOLOGICAL SCIENCES↗

Photoelectrochemical Proton-Coupled Electron Transfer of TiO 2 Thin Films on Silicon

TiO 2 thin films are often used as protective layers on semiconductors for applications in photovoltaics, molecule–semiconductor hybrid photoelectrodes, and more. Experiments reported here show that TiO 2 thin films on silicon are electrochemically and photoelectrochemically reduced in buffered acetonitrile at potentials relevant to photoelectrocatalysis of CO 2 reduction, N 2 reduction, and H 2 evolution. On both n-type Si and irradiated p-type Si, TiO 2 reduction is proton-coupled with a 1e – :1H + stoichiometry, as demonstrated by the Nernstian dependence of the Ti 4+/3+ E 1/2 on the buffer pK a . Experiments were conducted with and without illumination, and a photovoltage of ∼0.6 V was observed across 20 orders of magnitude in proton activity. The 4 nm films are almost stoichiometrically reduced under mild conditions. The reduced films catalytically transfer protons and electrons to hydrogen atom acceptors, based on cyclic voltammogram, bulk electrolysis, and other mechanistic evidence. TiO 2 /Si thus has the potential to photoelectrochemically generate high-energy H atom carriers. Characterization of the TiO 2 films after reduction reveals restructuring with the formation of islands, rendering TiO 2 films as a potentially poor choice as protecting films or catalyst supports under reducing and protic conditions. Altogether, this work demonstrates that atomic layer deposition TiO 2 films on silicon photoelectrodes undergo both chemical and morphological changes upon application of potentials only modestly negative of RHE in these media. While the results should serve as a cautionary tale for researchers aiming to immobilize molecular monolayers on “protective” metal oxides, the robust proton-coupled electron transfer reactivity of the films introduces opportunities for the photoelectrochemical generation of reactive charge-carrying mediators.

Electrodes↗

Maximum Supersaturation in the Marine Boundary Layer Clouds Over the North Atlantic

Abstract The maximum supersaturation ( S x ) in clouds is a key parameter affecting the cloud's microphysical and radiative properties. We investigate the S x of the marine boundary layer clouds by combining airborne and surface observations in the Eastern North Atlantic. The cloud droplet number concentration ( N c ) in the least diluted cloud cores agrees well with the number concentration of particles larger than the Hoppel Minimum (HM) ( N >HM ) below clouds, indicating that the HM represents the average size threshold above which particles are activated to form cloud droplets. The S x values derived from surface observations vary from 0.10% to 0.50% from June 2017 to June 2018, with a clear seasonal variation exhibiting higher values during winter. Most of the S x variance (∼60%) can be explained by the cloud condensation nuclei (CCN) concentration and updraft velocity ( w ), with the CCN concentration playing a more important role than w in explaining the variation of S x . The influence of CCN concentration on S x leads to a buffered response of N c to aerosol perturbations. The response of N c to low aerosol concentration during winter is further buffered by the high w . The global Community Earth System Model (CESM) simulated S x values in the Azores have a positive bias compared to measured S x , likely due to overestimated w and underestimated CCN concentration. The CESM simulated S x exhibits higher values further north over the North Atlantic Ocean, which is attributed to stronger w . The suppression of S x by aerosol is also evident in regions with high CCN concentrations.

54 ENVIRONMENTAL SCIENCES↗

Characterizing Hydrogen Storage Potential in U.S. Underground Gas Storage Facilities

Abstract Underground hydrogen storage is a long‐duration energy storage option for a low‐carbon economy. Although research into the technical feasibility of underground hydrogen storage is ongoing, existing underground gas storage (UGS) facilities are appealing candidates for the technology because of their ability to store and deliver natural gas. We estimate that UGS facilities in the United States (U.S.) can store 327 TWh (9.8 MMT) of pure hydrogen. A complete transition to hydrogen storage would reduce the collective working‐gas energy of UGS facilities by ∼75%; however, most (73.2%) UGS facilities could maintain current energy demand using a 20% hydrogen‐natural gas blend. U.S. UGS facilities can buffer 23.9%–44.6% of the high and low hydrogen demand projected for 2050, respectively, which exceeds the current percentage of natural gas demand buffered by storage. Thus, transitioning UGS infrastructure to hydrogen could substantially reduce the number of new hydrogen storage facilities needed to support a hydrogen economy.

08 HYDROGEN↗

The Role of Bedrock Circulation Depth and Porosity in Mountain Streamflow Response to Prolonged Drought

Quantitative understanding is lacking on how the depth of active groundwater circulation in bedrock affects mountain streamflow response to a multi-year drought. We use an integrated hydrological model to explore the sensitivity of a variety of streamflow metrics to bedrock circulation depth and porosity under a plausible extreme drought scenario lasting up to 5 years. Endmember depth versus hydraulic conductivity relationships and porosity values for fractured crystalline rock are simulated. With drought, a deeper circulation system with higher drainable porosity more effectively buffers minimum flow and significantly limits perennial stream loss in comparison to a shallow circulation system. Streamflow buffering is accomplished through extensive groundwater storage loss. However, deeper circulation systems experience prolonged recovery from drought in comparison to storage-limited shallow systems. Research highlights the importance of characterizing the deeper bedrock hydrogeology in mountainous watersheds to better understand and predict drought impacts on stream ecosystem health and water resource sustainability.

54 ENVIRONMENTAL SCIENCES↗

Streamflow Response to Glacier Mass Loss Varies With Basin Precipitation Across Alaska

Abstract Diminishing glaciers affect streamflow, and given the extent of glaciers in Alaska and adjacent Canada, continued glacier mass loss is likely to have profound effects on ecosystems sensitive to runoff. The effects of glacier mass loss on streamflow are likely to vary across the wide ranges of basin size, glacier cover, and precipitation in this region. In this study, we use U.S. Geological Survey (USGS) streamflow data with satellite‐based glacier volume change estimates to quantify how glacier mass loss subsidized streamflow over the 2000–2019 period for 116 glacierized basins. We examine interannual variability in that subsidy at three USGS‐monitored glaciers to explore the ability of the subsidy to buffer streamflow derived solely from precipitation. We found the relative importance of percent glacier cover on streamflow magnitude increases in drier basins. In the driest basins, glaciers produced 40 times greater percent glacier mass loss subsidies to streamflow for the percent glacier cover compared to the wettest basins. While the subsidy from glacier mass loss buffers interannual variability in streamflow to varying degrees, it can also increase streamflow variability. Smaller amounts of percent glacier cover are needed to produce summer‐melt‐dominated seasonal flow regimes in drier basins than in wetter basins. Decreasing glacier cover will eventually decrease summer streamflow, increasing spring streamflow in drier basins, and attenuating seasonality with increasing spring and autumnal streamflow in wetter basins. Quantifying the downstream effects of continued glacier mass loss without the computational expense of a hydrological model is broadly applicable in this changing climate.

Curran, Janet H. [U.S. Geological Survey Alaska Sc↗

Thermo-mechanical characterization of shale using nanoindentation

Abstract Shale can be a potential buffer for high-level radioactive nuclear wastes. To be an effective buffer while subject to waste heat, shale's mechanical response at elevated temperature must be known. Many researchers have experimentally characterized the mechanical behavior of various shales at different length scales in adiabatic conditions. However, its mechanical performance at elevated temperatures at the nano-scale remains unknown. To investigate the temperature dependency of nanomechanical properties of shale, we conducted both experimental and numerical studies. In this study, we measured mechanical and fracture properties of shale, such as hardness, elastic modulus, anisotropy, and fracture toughness from 25 °C up to 300 °C at different bedding planes. Statistical analysis of the results suggests that hardness and fracture toughness significantly increased at temperatures from 100 to 300 °C; while, temperature does not have a significant impact on elastic modulus. Data also shows that the bedding plane orientations have a substantial impact on both mechanical and fracture properties of shale at the nano-scale leading to distinct anisotropic behavior at elevated temperature below 100 °C. Additionally, we numerically investigated the mechanical performance of the shale samples at room temperature to gain an insight into its mechanical response through the thickness. Numerical results were validated against the experimental results, confirming the simulation can be used to predict shale deformation at the nano-scale or potentially be used in multi-scale simulations.

36 MATERIALS SCIENCE↗

Role of electrolyte composition on the acid stability of mixed-metal oxygen evolution catalysts

Acid stability in catalysts that promote the oxygen evolution reaction (OER) may be achieved through either the introduction of electrolyte-modulated self-healing processes, or the fixation of OER active sites within stable, conductive oxide matricies. By varying the nature of the electrolyte, pH, buffer concentration, and ionic strength, the contributions of these two effects may be deconvoluted. In addition, we find that the nature of the buffer is capable of engendering OER with exceptional acid stability at moderate overpotentials.

14 SOLAR ENERGY↗

Modeling the electrochemical behavior and interfacial junction profiles of bipolar membranes at solar flux relevant operating current densities

A 1-dimensional, multi-physics model that accounts for the migration and diffusion of solution species, electrostatics, and chemical reactions, in particular water dissociation (WD), at bipolar membrane (BPM) interfaces was developed to study the electrochemical behavior of bipolar membranes (BPMs) at solar flux relevant operating current densities (tens of mA cm -2 ). Significant partial current densities for WD were observed at BPM voltages much less than the equilibrium voltage, e.g., 59 mV × ΔpH from both experiments and modeling. The co-ion leakage across the BPM at pH differentials accounted for the early presence of the partial current density for WD. Two distinctive electric field dependent WD pathways, the un-catalyzed pathway and the catalyzed pathway, were quantitatively and parametrically studied to improve the turn-on potential of the BPM. The catalyzed pathway accounted for the majority of the partial current density for WD at low voltages, while the un-catalyzed pathway dominated the WD at relatively high voltages. Significant WD was observed only within the interfacial CL (<5 nm), in which a large electric field was present. To improve the electrochemical behavior and the turn-on potential of BPMs, the impacts of the pKa of the immobilized WD catalysts, the electric-field dependent rate constant, the thickness of the catalyst layer and fixed charge density in BPMs on the partial current densities for WD were studied systematically. In addition, the electrochemical behavior and concentration profiles of BPMs in a buffered electrolyte were studied and contrasted with those in an un-buffered electrolyte from both modeling and experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optoelectronic property comparison for isostructural Cu 2 BaGeSe 4 and Cu 2 BaSnS 4 solar absorbers

To target mitigation of anti-site defect formation in Cu 2 ZnSnS 4–x Se x , a new class of chalcogenides, for which Ba or Sr (group 2) replace Zn (group 12), has recently been introduced for prospective solar absorber application. Cu 2 BaGeSe 4 (CBGSe) and Cu 2 BaSnS 4 (CBTS) are two such compounds, which share a common trigonal crystal structure (P3 1 space group) and similar quasi-direct band gap (~2 eV). While CBTS-based films have already been studied, there are no reports yet on films and solar cells based on related CBGSe. To identify key differences and similarities in the electronic properties between these two materials, electronic characteristics (e.g., carrier concentration, mobility, electron affinity, defect levels, recombination, and charge carrier kinetics) of vacuum-deposited CBGSe and CBTS films are compared using a variety of characterization methods. Hall effect measurements reveal that CBGSe films have relatively higher hole carrier concentration and lower mobility (3 × 10 15 cm –3 , 0.6 cm 2 V –1 s –1 ) compared to CBTS (5 × 10 12 cm –3 , 3.5 cm 2 V –1 s –1 ). Photoelectron spectroscopy yields low electron affinity values for both CBGSe (3.7 eV) and CBTS (3.3 eV), pointing to the necessity of pursuing low electron affinity buffer materials for both types of absorbers. At low temperatures, CBGSe films show free-exciton photoluminescence, as well as pronounced deep-level emission at ~1.4 eV, while CBTS films exhibit a strong bound-exciton signal with noticeably less intense deep-level emission than for CBGSe. Charge carrier kinetics, transport, and recombination properties of both types of films are also analyzed using optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity. The first CBGSe prototype solar cells (using chemical bath deposited CdS as a buffer layer) show a maximum of 1.5% efficiency with ~0.62 V open-circuit voltage. Furthermore, the measured properties point to possible limiting factors for CBGSe and related films for PV and optoelectronics and provide insights on possible approaches for improvement within this multinary chalcogenide family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pulsed-laser epitaxy of metallic delafossite PdCrO 2 films

Alternate stacking of a highly conducting metallic layer with a magnetic triangular layer found in delafossite PdCrO 2 provides an excellent platform for discovering intriguing correlated quantum phenomena. Thin film growth of delafossites may enable not only the tuning of the basic physical properties beyond what bulk materials can exhibit, but also the development of novel hybrid materials by interfacing with dissimilar materials, yet this has proven to be extremely challenging. Here, we report the epitaxial growth of metallic delafossite PdCrO 2 films by pulsed laser epitaxy (PLE). The fundamental role of the PLE growth conditions, epitaxial strain, and chemical and structural characteristics of the substrate is investigated by growing under various growth conditions and on various types of substrates. While strain plays a large role in improving the crystallinity, the direct growth of epitaxial PdCrO 2 films without impurity phases was not successful. We attribute this difficulty to both the chemical and structural dissimilarities with the substrate and volatile nature of the PdO sublayer, which make nucleation of the right phase difficult. This difficulty was overcome by growing CuCrO 2 buffer layers before PdCrO 2 films were grown. Unlike PdCrO 2 , CuCrO 2 films were readily grown with a relatively wide growth window. Only a monolayer thick buffer layer was sufficient to grow the correct PdCrO 2 phase. This result indicates that the epitaxy of Pd-based delafossites is extremely sensitive to the chemistry and structure of the interface, necessitating near perfect substrate materials. The resulting films are commensurately strained and show an antiferromagnetic transition at 40 K that persists down to as thin as 3.6 nm in thickness. This work provides key insights into advancing the epitaxial growth of the broader class of metallic delafossites for both studying the basic physical properties and developing new spintronic and computing devices.

36 MATERIALS SCIENCE↗