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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ion Gating in Nanopore Electrode Arrays with Hierarchically Organized pH-Responsive Block Copolymer Membranes

Inspired by biological ion channels, artificial nanopore-based architectures have been developed for smart ion/molecular transport control with potential applications to iontronics and energy conversion. Advances in nanofabrication technology enable simple, versatile construction methods, and post-fabrication functionalization delivers nanochannels with unique ion transport-control attributes. Here, we characterize a pH-responsive, charge-selective dual-gating block copolymer (BCP) membrane composed of polystyrene-b-poly(4-vinylpyridine) (PS 48400 -b-P4VP 21300 ), capable of self-organizing into highly ordered nanocylindrical domains. Because the PS-b-P4VP membrane exhibits pH-dependent structural transitions, it is suitable for designing intelligent pH-gated biomimetic channels, for example, exhibiting on–off transport switching at pH values near the pK a of P4VP with excellent anion permselectivity at pH < pK a . Introducing the BCP membrane onto nanopore electrode arrays (BCP@NEAs) allows the BCP to serve as a pH-responsive gate controlling ion transfer into the NEA nanopores. Such selectively transported and confined ions are detected by using a 100 nm gap dual-ring nanoelectrode structure capable of enhancing current output by efficient redox cycling with an amplification factor >10 2 . In addition, BCP@NEAs exhibit extraordinary pH-gated ion selectivity, resulting in a 3380-fold current difference between anion and cation probes at pH 3.0. Furthermore, this hierarchically organized BCP-gated NEA system can serve as a template for the development of other stimulus-responsive ion gates, for example, those based on temperature and ligand gating, thus exploiting the intrinsic advantages of NEAs, such as enhanced sensitivity based on redox cycling, which may lead to technological applications such as engineered biosensors and iontronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

The Q 10 of in situ microbial soil respiration varies with mean annual temperature, precipitation, pH, and plant cover: a meta-analysis and spatial prediction of Q 10

The temperature sensitivity of soil microbial respiration, commonly quantified using the Q 10 coefficient, is a key parameter in carbon cycle models. Uncovering how environmental factors affect in situ Q 10 values can therefore provide critical insight into potential shifts in global carbon stocks under climate change. We collected data from previously published field experiments that measured soil microbial respiration across a range of temperatures. We hypothesized that the Q 10 coefficient of in situ soil microbial respiration would vary based on environmental factors including mean annual temperature (MAT), mean annual precipitation (MAP), plant cover type, pH, soil C:N, and latitude. Linear regression revealed that Q 10 correlates negatively with MAT and MAP and positively with pH and absolute latitude. Additionally, average Q 10 varied significantly across different plant cover types; it was highest in mountain grasslands and lowest in tropical moist forests. Variation in microbial Q 10 across environmental factors may arise from underlying mechanisms such as enzyme kinetics, substrate availability and complexity, and microbial adaptation. To capture patterns in Q 10 more comprehensively, we developed a multiple linear regression model of Q 10 based on the most individually significant environmental drivers and applied it to public datasets to generate a global map of predicted Q 10 . Q 10 was higher in high-latitude and high-altitude regions, where large permafrost carbon stores are vulnerable to thawing and decomposition. We also compared fits between the Q 10 equation and a model produced from macromolecular rate theory (MMRT). We found that the MMRT model had the superior fit and may be better suited to model temperature sensitivity of complex biological reactions. Overall, our results emphasize that relationships between microbial Q 10 and environmental variables should be accounted for in climate models. Incorporating these variations in the Q 10 parameter, rather than using a fixed value, will help predict whether CO 2 emissions will be buffered or exacerbated by soil microbial respiration under climate change.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Surprising robustness of particle-hole symmetry for composite-fermion liquids

Here, we report on fixed phase diffusion Monte Carlo calculations that show that, even for a large amount of Landau level mixing, the energies of the Pfaffian and anti-Pfaffian phases remain very nearly the same, as also do the excitation gaps at 1/3 and 2/3. These results, combined with previous theoretical and experimental investigations, indicate that particle hole (PH) symmetry for composite fermion states is much more robust than a priori expected, emerging even in models that explicitly break PH symmetry. We provide insight into this fact by showing that the low energy physics of a generic repulsive 3-body interaction is captured, to a large extent and over a range of filling factors, by a mean field approximation that maps it into a PH symmetric 2-body interaction. This explains why Landau level mixing, which effectively generates such a generic 3-body interaction, is inefficient in breaking PH symmetry. As a byproduct, our results provide a systematic construction of a 2-body interaction which produces, to a good approximation, the Pfaffian wave function as its ground state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Environmental pH and peptide signaling control virulence of Streptococcus pyogenes via a quorum-sensing pathway

Bacteria control gene expression in concert with their population density by a process called quorum sensing, which is modulated by bacterial chemical signals and environmental factors. In the human pathogen Streptococcus pyogenes , production of secreted virulence factor SpeB is controlled by a quorum-sensing pathway and environmental pH. The quorum-sensing pathway consists of a secreted leaderless peptide signal (SIP), and its cognate receptor RopB. Here, we report that the SIP quorum-sensing pathway has a pH-sensing mechanism operative through a pH-sensitive histidine switch located at the base of the SIP-binding pocket of RopB. Environmental acidification induces protonation of His144 and reorganization of hydrogen bonding networks in RopB, which facilitates SIP recognition. The convergence of two disparate signals in the SIP signaling pathway results in induction of SpeB production and increased bacterial virulence. Our findings provide a model for investigating analogous crosstalk in other microorganisms.

Science & Technology - Other Topics↗
DOE OSTI2012

Modeling the chemical kinetics of atmospheric plasma for cell treatment in a liquid solution

Low temperature atmospheric pressure plasmas have been known to be effective for living cell inactivation in a liquid solution but it is not clear yet which species are key factors for the cell treatment. Using a global model, we elucidate the processes through which pH level in the solution is changed from neutral to acidic after plasma exposure and key components with pH and air variation. First, pH level in a liquid solution is changed by He{sup +} and He(2{sup 1}S) radicals. Second, O{sub 3} density decreases as pH level in the solution decreases and air concentration decreases. It can be a method of removing O{sub 3} that causes chest pain and damages lung tissue when the density is very high. H{sub 2}O{sub 2}, HO{sub 2}, and NO radicals are found to be key factors for cell inactivation in the solution with pH and air variation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Efficient myogenic differentiation of human adipose-derived stem cells by the transduction of engineered MyoD protein

Highlights: •MyoD was engineered to contain protein transduction domain and endosome-disruptive INF7 peptide. •The engineered MyoD-IT showed efficient nuclear targeting through an endosomal escape by INF7 peptide. •By applying MyoD-IT, human adipose-derived stem cells (hASCs) were differentiated into myogenic cells. •hASCs differentiated by applying MyoD-IT fused to myotubes through co-culturing with mouse myoblasts. •Myogenic differentiation using MyoD-IT is a safe method without the concern of altering the genome. -- Abstract: Human adipose-derived stem cells (hASCs) have great potential as cell sources for the treatment of muscle disorders. To provide a safe method for the myogenic differentiation of hASCs, we engineered the MyoD protein, a key transcription factor for myogenesis. The engineered MyoD (MyoD-IT) was designed to contain the TAT protein transduction domain for cell penetration and the membrane-disrupting INF7 peptide, which is an improved version of the HA2 peptide derived from influenza. MyoD-IT showed greatly improved nuclear targeting ability through an efficient endosomal escape induced by the pH-sensitive membrane disruption of the INF7 peptide. By applying MyoD-IT to a culture, hASCs were efficiently differentiated into long spindle-shaped myogenic cells expressing myosin heavy chains. Moreover, these cells differentiated by an application of MyoD-IT fused to myotubes with high efficiency through co-culturing with mouse C2C12 myoblasts. Because internalized proteins can be degraded in cells without altering the genome, the myogenic differentiation of hASCs using MyoD-IT would be a safe and clinically applicable method.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Evaluation of microalgae cultivation at air-CO 2 equilibrium pH for improving carbon utilization efficiency

Microalgae are often cultivated at near-neutral pH to optimize growth. However, this results in significant CO 2 loss through outgassing in open-pond cultivation systems, leading to low CO 2 utilization efficiency and higher biomass production costs. One potential solution is algal cultivation at air-CO 2 equilibrium pH, which minimizes CO 2 outgassing but may inhibit growth due to stresses at higher pH levels. In this study, we evaluated the viability of this approach by growing Picochlorum celeri and Tetraselmis striata under outdoor relevant conditions at equilibrium pH. Compared to pH 7 cultures, biomass productivity declined by 35 % for P. celeri and 57 % for T. striata. Although CO 2 outgassing could be minimized, the significant loss in productivity led to a higher overall minimum biomass selling price (MBSP). Increased ammonia toxicity at the higher pH was found to be one of the growth-limiting factors and was mitigated by reducing ammonium fertilizer concentration. This adjustment resulted in a more moderate productivity decline of 13 % (instead of 35 %) for T. striata, and consequently, a lower MBSP was achieved. These findings suggest that equilibrium pH cultivation may be a viable method for reducing CO 2 loss without significantly compromising biomass productivity. Depending on the strain, strategies to mitigate stressors, such as ammonia toxicity, may be necessary.

09 BIOMASS FUELS↗
DOE OSTI2020

Environmental stability impacts the differential sensitivity of marine microbiomes to increases in temperature and acidity

Ambient conditions shape microbiome responses to both short- and long-duration environment changes through processes including physiological acclimation, compositional shifts, and evolution. Here, we predict that microbial communities inhabiting locations with larger diel, episodic, and annual variability in temperature and pH should be less sensitive to shifts in these climate-change factors. To test this hypothesis, we compared responses of surface ocean microbes from more variable (nearshore) and more constant (offshore) sites to short-term factorial warming (+3 °C) and/or acidification (pH –0.3). In all cases, warming alone significantly altered microbial community composition, while acidification had a minor influence. Compared with nearshore microbes, warmed offshore microbiomes exhibited larger changes in community composition, phylotype abundances, respiration rates, and metatranscriptomes, suggesting increased sensitivity of microbes from the less-variable environment. Moreover, while warming increased respiration rates, offshore metatranscriptomes yielded evidence of thermal stress responses in protein synthesis, heat shock proteins, and regulation. Future oceans with warmer waters may enhance overall metabolic and biogeochemical rates, but they will host altered microbial communities, especially in relatively thermally stable regions of the oceans.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Laboratory Evaporation Testing Of Hanford Waste Treatment Plant Low Activity Waste Off-Gas Condensate Simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream, LAW Off-Gas Condensate, from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of canistered glass waste forms. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to be within acceptable concentration ranges in the LAW glass. Diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task examines the impact of potential future disposition of this stream in the Hanford tank farms, and investigates auxiliary evaporation to enable another disposition path. Unless an auxiliary evaporator is used, returning the stream to the tank farms would require evaporation in the 242-A evaporator. This stream is expected to be unusual because it will be very high in corrosive species that are volatile in the melter (chloride, fluoride, sulfur), will have high ammonia, and will contain carryover particulates of glass-former chemicals. These species have potential to cause corrosion of tanks and equipment, precipitation of solids, release of ammonia gas vapors, and scale in the tank farm evaporator. Routing this stream to the tank farms does not permanently divert it from recycling into the WTP, only temporarily stores it prior to reprocessing. Testing is normally performed to demonstrate acceptable conditions and limits for these compounds in wastes sent to the tank farms. The primary parameter of this phase of the test program was measuring the formation of solids during evaporation in order to assess the compatibility of the stream with the evaporator and transfer and storage equipment. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW facility melter offgas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet, and, thus, the composition will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. This report discusses results of evaporation testing of the simulant. Two conditions were tested, one with the simulant at near neutral pH, and a second at alkaline pH. The neutral pH test is comparable to the conditions in the Hanford Effluent Treatment Facility (ETF) evaporator, although that evaporator operates at near atmospheric pressure and tests were done under vacuum. For the alkaline test, the target pH was based on the tank farm corrosion control program requirements, and the test protocol and equipment was comparable to that used for routine evaluation of feed compatibility studies for the 242-A evaporator. One of the radionuclides that is volatile in the melter and expected to be in high concentration in this LAW Off-Gas Condensate stream is Technetium-99 (99Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are also expected to be in appreciable concentrations in the LAW Off-Gas Condensate are 129I, 90Sr, 137Cs, and 241Am. The concentrations of these radionuclides in this stream will be much lower than in the LAW, but they will still be higher than limits for some of the other disposition pathways currently available. At this time, these scoping tests did not evaluate the partitioning of the radionuclides to the evaporator condensate, since ample data are available separately from other experience in the DOE complex. Results from the evaporation testing show that the neutral SBS simulant first forms turbidity at ~7.5X concentration, while the alkaline-adjusted simulant became turbid at ~3X concentration. The major solid in both cases was Kogarkoite, Na3FSO4. Sodium and lithium fluorides were also detected. Minimal solids were formed in the evaporator bottoms until a substantial fraction of liquid was removed, indicating that evaporation could minimize storage volume issues. Achievable concentration factors without significant insoluble solids were 17X at alkaline pH, and 23X at neutral pH. In both runs, significant ammonia carried over and was captured in the condenser with the water condensate. Results also indicate that with low insoluble solids formation in the initial testing at neutral pH, the use of Reverse Osmosis is a potential alternate method for concentrating the solution, although an evaluation is needed to identify equipment that can tolerate insoluble solids. Most of the ammonia remains in the evaporator bottoms during the neutral pH evaporation, but partitions to the condensate during alkaline evaporation. Disposition of both streams needs to consider the management of ammonia vapor and its release. Since this is an initial phase of testing, additional tasks related to evaporation methods are expected to be identified for development. These tasks likely include evaluation and testing of composition variability testing and evaluations, corrosion and erosion testing, slurry storage and immobilization investigations, and evaporator condensate disposition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Two Independent Histidines One in Human Prolactin and One in Its Receptor Are Critical for pH-dependent Receptor Recognition and Activation

Human prolactin (hPRL), a member of the family of hematopoietic cytokines, functions as both an endocrine hormone and autocrine/paracrine growth factor. We have previously demonstrated that recognition of the hPRL-receptor depends strongly on solution acidity over the physiologic range from pH 6 to pH 8. The hPRL-receptor binding interface contains four histidines whose protonation is hypothesized to regulate pH-dependent receptor recognition. Here, we systematically dissect its molecular origin by characterizing the consequences of His to Ala mutations on pH-dependent receptor binding kinetics, site-specific histidine protonation, and high resolution structures of the intermolecular interface. Thermodynamic modeling of the pH dependence to receptor binding affinity reveals large changes in site-specific protonation constants for a majority of interface histidines upon complexation. Removal of individual His imidazoles reduces these perturbations in protonation constants, which is most likely explained by the introduction of solvent-filled, buried cavities in the crystallographic structures without inducing significant conformational rearrangements.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Soil pH mediates the balance between stochastic and deterministic assembly of bacteria

Little is known about the factors affecting the relative influence of stochastic and deterministic processes that governs the assembly of microbial communities in successional soils. Here, we conducted a meta-analysis of bacterial communities using six different successional soils data sets, scattered across different regions, with different pH conditions in early and late successional soils. We found that soil pH was the best predictor of bacterial community assembly and the relative importance of stochastic and deterministic processes along successional soils. Extreme acidic or alkaline pH conditions lead to assembly of phylogenetically more clustered bacterial communities through deterministic processes, whereas pH conditions close to neutral lead to phylogenetically less clustered bacterial communities with more stochasticity. We suggest that the influence of pH, rather than successional age, is the main driving force in producing trends in phylogenetic assembly of bacteria, and that pH also influences the relative balance of stochastic and deterministic processes along successional soils. Given that pH had a much stronger association with community assembly than did successional age, we evaluated whether the inferred influence of pH was maintained when studying globally-distributed samples collected without regard for successional age. This dataset confirmed the strong influence of pH, suggesting that the influence of soil pH on community assembly processes occurs globally. Extreme pH conditions likely exert more stringent limits on survival and fitness, imposing strong selective pressures through ecological and evolutionary time. Taken together, these findings suggest that the degree to which stochastic vs. deterministic processes shape soil bacterial community assembly is a consequence of soil pH rather than successional age.

Tripathi, Binu M.↗
DOE OSTI2019

Intercalation of Nanopolyaniline with Nanobentonite and Manganese Oxide Nanoparticles as a Novel Nanocomposite to Remediate Cobalt/Zinc and Their Radioactive Nuclides {sup 60}Co/{sup 65}Zn

A novel nanocomposite based on the combination of nanobentonite with nanopolyaniline and nanomanganese oxide (N-Bent–NPANI–NMn{sub 3}O{sub 4}) was synthesized and investigated to extract Co/Zn ions from water using batch technique and {sup 60}Co/{sup 65}Zn radionuclides from radioactive wastewater using column techniques. Characterization was established by High resolution-transmission electron microscopy (HR-TEM), Scanning electron microscope, X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and Fourier transform infrared spectrophotometer. The image of HR-TEM indicated that the produced nanocomposite was ranged from 59.07 to 83.38 nm. Solution pH, time of reaction, amount of solid and metal concentration, all of these parameters were inspected and optimized as fundamental factors during the extraction process. The obtained results implied that the ideal conditions for extraction were pH 6 and 7, reaction time 10 and 20 min, for Co and Zn ions, respectively. The highest removal capacities were found 255.28 and 202.22 mg g{sup −1} for Co and Zn, respectively by using 5 mg nanocomposite. Excellent recoveries were obtained as 94.0–94.5% and 92.0–93.0% for removal of Co–{sup 60}Co and of Zn–{sup 65}Zn ions, respectively from the examined samples. Graphical Abstract: .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Assessment of TMT Labeling Efficiency in Large-Scale Quantitative Proteomics: The Critical Effect of Sample pH

Isobaric labeling via tandem mass tag (TMT) reagents enables sample multiplexing prior to LC–MS/MS, facilitating high-throughput large-scale quantitative proteomics. Consistent and efficient labeling reactions are essential to achieve robust quantification; therefore, embedded in our clinical proteomic protocol is a quality control (QC) sample that contains a small aliquot from each sample within a TMT set, referred to as “Mixing QC.” This Mixing QC enables the detection of TMT labeling issues by LC–MS/MS before combining the full samples to allow for salvaging of poor TMT labeling reactions. While TMT labeling is a valuable tool, factors leading to poor reactions are not fully studied. We observed that relabeling does not necessarily rescue TMT reactions and that peptide samples sometimes remained acidic after resuspending in 50 mM HEPES buffer (pH 8.5), which coincided with low labeling efficiency (LE) and relatively low median reporter ion intensities (MRIIs). To obtain a more resilient TMT labeling procedure, we investigated LE, reporter ion missingness, the ratio of mean TMT set MRII to individual channel MRII, and the distribution of log 2 reporter ion ratios of Mixing QC samples. We discovered that sample pH is a critical factor in LE, and increasing the buffer concentration in poorly labeled samples before relabeling resulted in the successful rescue of TMT labeling reactions. Moreover, resuspending peptides in 500 mM HEPES buffer for TMT labeling resulted in consistently higher LE and lower missing data. By better controlling the sample pH for labeling and implementing multiple methods for assessing labeling quality before combining samples, we demonstrate that robust TMT labeling for large-scale quantitative studies is achievable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Controls on Barite (BaSO 4 ) Precipitation in Unconventional Reservoirs

Barite (BaSO 4 ) precipitation is one of the most ubiquitous examples of secondary sulfate mineral scaling in shale oil and gas reservoirs. Often, a suite of chemical additives is used during fracturing operations to inhibit the accumulation of mineral scales, though their efficacy is widely varied and poorly understood. This study combines experimental data and multi-component numerical reactive transport modeling to offer a more comprehensive understanding of the geochemical behavior of barite accumulation in shale matrices under conditions typical of fracturing operations. A variety of additives and conditions are individually tested in batch reactor experiments to identify the factors controlling barite precipitation. Our experimental results demonstrate a pH dependence in the rate of barite precipitation, which we use to develop a predictive model including a pH-dependent term that satisfactorily reproduces our observations. Further, this model is then extended to consider the behavior of three major shale samples of highly variable mineralogy (Eagle Ford, Marcellus, and Barnett). This data-validated model offers a reliable tool to predict and ultimately mitigate against secondary mineral accumulation in unconventional shale reservoirs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Molecular Chemistry of Atmospheric Brown Carbon Inferred from a Nationwide Biomass Burning Event

Lag Ba'Omer, a nationwide bonfire festival in Israel, was chosen as a case study to investigate the influence of a major biomass burning event on the light absorption properties of atmospheric brown carbon (BrC). The chemical composition and optical properties of BrC chromophores were investigated using a high performance liquid chromatography (HPLC) platform coupled to photo diode array (PDA) and high resolution mass spectrometry (HRMS) detectors. Substantial increase of BrC light absorption coefficient was observed during the night-long biomass burning event. Most chromophores observed during the event were attributed to nitroaromatic compounds, comprising 28 elemental formulas of at least 63 structural isomers. The NAC, in combination, accounted for 50-80% of the total visible light absorption (> 400 nm) by solvent extractable BrC. The results highlight that NAC, particular nitrophenols, are important light absorption contributors of biomass burning organic aerosol (BBOA), suggesting that night time chemistry of ·NO 3 and N 2 O 5 with particles may play a significant role in atmospheric transformations of BrC. Nitrophenols and related compounds were especially important chromophores of BBOA. The absorption spectra of the BrC chromophores are influenced by the extraction solvent and solution pH, implying that the aerosol acidity is an important factor controlling the light absorption properties of BrC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Surface-Enhanced Raman Scattering Study of the Kinetics of Self-Assembly of Carboxylate-Terminated n -Alkanethiols on Silver

Adsorption of 11-mercaptoundecanoic acid (MUA) on silver from methanol and aqueous solutions was monitored in situ by surface-enhanced Raman scattering (SRES) spectroscopy. While adsorption of MUA from methanol is a one-step formation of a thiol-bound monolayer, SERS spectra reveal that monolayer formation from aqueous solution involves interactions of both carboxylate and thiol groups of MUA with the silver surface. Several Raman scattering bands, including the ν(C–S), ν s (COO – ), and ν(C–C), were used to investigate the evolution of the structure of adsorbed MUA on silver surfaces. The time-dependent profiles of these bands for assembly from aqueous solution indicate a multistep process, which is initiated by the binding of both carboxylate and thiol groups to silver, producing a mixture of gauche and trans conformations. In a subsequent step, the COO–Ag interactions are displaced by stronger S–Ag bonds, leading to ordering of the resulting monolayer with formation of a complete SAM with all-trans conformations. The results also showed that the adsorption process depended strongly on the solution pH and surface potential of the metal. Furthermore, these factors can significantly affect the participation and displacement of –COO – during self-assembly of MUA from aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Highly quaternized polystyrene ionomers for high performance anion exchange membrane water electrolysers

Alkaline anion exchange membrane (AEM) electrolysers to produce hydrogen from water remain at an early stage of development, and their performance is far lower than that of systems based on proton exchange membranes. Here, we report an ammonium-enriched anion exchange ionomer that improves the performance of an AEM electrolyser to levels approaching that of state-of-the-art proton exchange membrane electrolysers. Using rotating-disk electrode experiments, we show that a high pH (>13) in the electrode binder is the critical factor for improving the activity of the hydrogen- and oxygen-evolution reactions in AEM electrolysers. Based on this observation, we prepared and tested several quaternized polystyrene electrode binders in an AEM electrolyser. Using the binder with the highest ionic concentration and a NiFe oxygen evolution catalyst, we demonstrated performance of 2.7 A cm -2 at 1.8 V without a corrosive circulating alkaline solution. The limited durability of the AEM electrolyser remains a challenge to be addressed in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Formation of Algae Growth Constitutive Relations for Improved Algae Modeling

This SAND report summarizes research conducted as a part of a two year Laboratory Directed Research and Development (LDRD) project to improve our abilities to model algal cultivation. Algae-based biofuels have generated much excitement due to their potentially large oil yield from relatively small land use and without interfering with the food or water supply. Algae mitigate atmospheric CO 2 through metabolism. Efficient production of algal biofuels could reduce dependence on foreign oil by providing a domestic renewable energy source. Important factors controlling algal productivity include temperature, nutrient concentrations, salinity, pH, and the light-to-biomass conversion rate. Computational models allow for inexpensive predictions of algae growth kinetics in these non-ideal conditions for various bioreactor sizes and geometries without the need for multiple expensive measurement setups. However, these models need to be calibrated for each algal strain. In this work, we conduct a parametric study of key marine algae strains and apply the findings to a computational model.

Gharagozloo, Patricia E.↗