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At least 109 records · Page 6

Deep Learning Approaches for Predicting the Surface Tension of Ionic Liquids

Ionic liquids (ILs) are a novel class of solvents that have attracted significant attention due to their unique and tunable properties. Among their physiochemical characteristics, surface tension plays a critical role in various industrial applications including electrolytes, heat transfer fluids, and separation processes. However, because of the exploratory nature of IL design and the vast combinatorial space of possible anion–cation pairs, the experimental determination of these properties is often impractical, being both time-consuming and costly. To overcome these challenges, computational approaches are increasingly employed to develop accurate predictive models that can accelerate IL discovery and design. In this study, we present two deep learning (DL) models for predicting the surface tension of ILs across a broad temperature range at a constant pressure. The models use simplified molecular input line entry system, SMILES, representations of ILs to extract molecular features as inputs. Both DL models demonstrate excellent agreement with experimental data, achieving an R 2 value of 0.990 and a root-mean-square error of 0.792 mN/m. In conclusion, these results offer valuable insights for the rapid screening and rational design of ILs with tailored surface tension values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thirsty Walls: A New Paradigm for Air Revitalization in Life Support

This Phase I project Summary will be formatted as a series of summary statements, with additional comments. The summary statements are intended to focus on the most significant findings and discoveries – things that the project team knows now, but we didn’t know at the beginning of the project: 1) Direct Contact Between Gases is an ECLS (Environmental Control and Life Support) System enabling capability; 2) CO2 capture using liquid sorbents in microgravity is feasible; 3) There are other ways to contact gases and liquids – but thin film capillary techniques are new, exciting, and have amazing potential; 4) ECLS system reliability is the key to exploration missions – the key to reliability is having system attributes that favor reliability; 5) The processes with favorable reliability attributes tend to be biological; 6) The single greatest impact on launch mass of an ECLS system is water. The best way to enable biological water processing is to develop a capillary based method of urine capture that doesn’t use pretreat chemicals; 7) There is good, promising, forward design and development work – but no fundamental “show stoppers” – to develop a thin film liquid sorbent CO2 capture system; 8) The most capable Ionic Liquids are not presently feasible, but other chemically active liquids can be used to make an effective thin film CO2 capture device; 9) The C9 reduced gravity flight showed feasibility – and taught us about flow instability issues; 10) Capillary fluid management has ECLS system wide implications.

CO2↗

Irreversible Trace Metal Binding to Goethite Controlled by the Ion Size

The dynamics of trace metals at mineral surfaces influence their fate and bioaccessibility in the environment. Trace metals on iron (oxyhydr)oxide surfaces display adsorption–desorption hysteresis, suggesting entrapment after aging. However, desorption experiments may perturb the coordination environment of adsorbed metals, the distribution of labile Fe(III), and mineral aggregation properties, influencing the interpretation of labile metal fractions. Here, in this study, we investigated irreversible binding of nickel, zinc, and cadmium to goethite after aging times of 2–120 days using isotope exchange. Dissolved and adsorbed metal pools exchange rapidly, with half times <90 min, but all metals display a solid-associated fraction inaccessible to isotope exchange. The size of this nonlabile pool is the largest for nickel, with the smallest ionic radius, and the smallest for cadmium, with the largest ionic radius. Spectroscopy and extractions suggest that the irreversibly bound metals are incorporated in the goethite structure. Rapid exchange of labile solid-associated metals with solution demonstrates that adsorbed metals can sustain the dissolved pool in response to biological uptake or fluid flow. Trace metal fractions that irreversibly bind following adsorption provide a contaminant sequestration pathway, limit the availability of micronutrients, and record metal isotope signatures of environmental processes.

58 GEOSCIENCES↗

Co-Extrusion (CoEx) for Cost Reduction of Advanced High-Energy-and-Power Battery Electrode Manufacturing

Co-Extrusion (CoEx) is a deposition technology developed at PARC that uses engineered fluidic channels to cause multiple streams of dissimilar fluids to impart shape to one another. Here, we describe the use of CoEx to produce structured cathode electrode films to improve electrochemical performance of thick electrode films. CoEx enables us to create structured electrode films that have periodic regions of enhanced ionic conductivity, enabling higher utilization of thicker cathode films at high discharge rates. While increasing electrode thickness is a known method for increasing energy density of battery electrodes, this increase in energy density typically also results in reduced power density. This project, a collaboration between the Palo Alto Research Center, Oak Ridge National Laboratories, and Ford Motor Company, seeks to first validate the benefits of CoEx at the coin cell level, before performing the necessary R&D effort to scale production up to large (10+ Ah) pouch cells that will show increased energy density without a reduction in power density. We used conventional battery materials (commercially available NMC, PVDF, carbon black, and graphite) to produce structured electrodes via CoEx and compared them to thick and thin conventionally produced (unstructured) battery electrodes. CoEx electrodes show improved high rate performance compared to unstructured electrodes, resulting in higher energy density pouch cells compared to the baseline electrode of 7 and 11% in volumetric and gravimetric energy density, respectively. These electrodes also showed substantially improved electrochemical performance at high discharge rates compared to thick conventional electrodes.

25 ENERGY STORAGE↗

Irreversible Trace Metal Binding to Goethite Controlled by the Ion Size

The dynamics of trace metals at mineral surfaces influence their fate and bioaccessibility in the environment. Trace metals on iron (oxyhydr)oxide surfaces display adsorption–desorption hysteresis, suggesting entrapment after aging. However, desorption experiments may perturb the coordination environment of adsorbed metals, the distribution of labile Fe(III), and mineral aggregation properties, influencing the interpretation of labile metal fractions. In this study, we investigated irreversible binding of nickel, zinc, and cadmium to goethite after aging times of 2–120 days using isotope exchange. Dissolved and adsorbed metal pools exchange rapidly, with half times <90 min, but all metals display a solid-associated fraction inaccessible to isotope exchange. The size of this nonlabile pool is the largest for nickel, with the smallest ionic radius, and the smallest for cadmium, with the largest ionic radius. Spectroscopy and extractions suggest that the irreversibly bound metals are incorporated in the goethite structure. Rapid exchange of labile solid-associated metals with solution demonstrates that adsorbed metals can sustain the dissolved pool in response to biological uptake or fluid flow. Trace metal fractions that irreversibly bind following adsorption provide a contaminant sequestration pathway, limit the availability of micronutrients, and record metal isotope signatures of environmental processes.

58 GEOSCIENCES↗

Thermodynamics and phase separation of dense fully-ionized hydrogen-helium fluid mixtures

The free energy of a hydrogen-helium fluid mixture is evaluated for the temperatures and densities appropriate to the deep interior of a giant planet such as Jupiter. The electrons are assumed to be fully pressure-ionized and degenerate. In this regime, an appropriate first approximation to the ionic distribution functions can be found by assuming hard sphere interactions. Corrections to this approximation are incorporated by means of the perturbation theory of Anderson and Chandler. Approximations for the three-body interactions and the nonlinear response of the electron gas to the ions are included. It is predicted that a hydrogen-helium mixture, containing 10% by number of helium ions, separates into hydrogen-rich and helium-rich phases below about 8000 K, at the pressures relevant to Jupiter (4-40 Megabars). It is also predicted that the alloy occupies less volume per ion than the separated phases. The equations of state and other thermodynamic derivatives are tabulated. Implications of these results are discussed.

Stevenson, D. J.↗

Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California

High temperature alteration of sedimentary organic matter associated with marine hydrothermal systems involves complex physical and chemical processes that are not easily measured in most natural systems. Many of these processes can be evaluated indirectly by examining the geochemistry of the hydrothermal system in the laboratory. In this investigation, an experimental organic geochemical approach to studying pyrolysis of sedimentary organic matter is applied to the hydrothermal system in the Guaymas Basin, Gulf of California. A general survey of hydrothermal oils and extractable organic matter (bitumen) in hydrothermally altered sediments identified several homologous series of alkanones associated with a high temperature hydrothermal origin. The alkanones range in carbon number from C11 to C30 with no carbon number preference. Alkan-2-ones are in highest concentrations, with lower amounts of 3-, 4-, 5- (and higher) homologs. The alkanones appear to be pyrolysis products synthesized under extreme hydrothermal conditions. Hydrous pyrolysis and confinement pyrolysis experiments were performed to simulate thermally enhanced diagenetic and catagenetic changes in the immature sedimentary organic matter. The extent of alteration was measured by monitoring the n-alkanes, acyclic isoprenoids, steroid and triterpenoid biomarkers, polycyclic aromatic hydrocarbons and alkanones. The results were compared to bitumen extracts from sediments which have been naturally altered by a sill intrusion and accompanied hydrothermal fluid flow. These pyrolysis experiments duplicated many of the organic matter transformations observed in the natural system. Full hopane and sterane maturation occurred after 48 hr in experiments at 330 deg C with low water/rock mass ratios (0.29). A variety of radical and ionic reactions are responsible for the organic compound conversions which occur under extreme hydrothermal conditions. Short duration pyrolysis experiments revealed that a portion of the hydrocarbons generated from kerogen was observed to go through alkene intermediates, and the rate of alkene isomerization was influenced by the ionic strength and catalytic mineral phases. Confinement of the organic pyrolysate to the bulk sediment accelerated the rates of the biomarker epimerization reactions, suggesting that these reactions are influenced strongly by the association of the inorganic matrix, and that the relative rates of some ionic and radical reactions can be influenced by the water/rock ratio during the pyrolysis experiments.

Leif, Roald N.↗

Precision Cleaning of Oxygen Systems and Components

Currently, NASA uses Dichloropentafluoropropane (HCFC-225), a Class II ozone depleting substance (ODs), to clean contaminated oxygen systems. Starting in 20 15, the Montreal Protocols and Clean Air Act prohibit the production and importation of all hydrochlorofluorocarbons (HCFC), except for limited use in refrigeration applications. Thus, a new non-ozone depleting solvent needs to be developed for use in cleaning. Optimally, such a solvent should also be environmentally benign or green to avoid needing to replace the new solvent with yet another solvent in the future due to other environmental concerns. Work for the first year consisted of two parts. The first part was developing a method of testing the cleaning efficiency of potential solvents. Stainless steel coupons were contaminated with a known weight of various contaminants and contaminant combinations and then immersed in solvent for ten minutes. The coupons were then removed and dried in an oven until all solvent had evaporated. Once dry, the coupons were weighed and the mass of the non-volatile residue (NVR) left on the coupon was determined. The cleaning efficiency of the solvents is reported as percent cleaning, with 100% cleaning being zero NVR left on the test coupon. The second half of the first goal was to use the develop method to perform baseline testing on current solvents. The second part of the work was to begin exploring alternative cleaning solvents. A variety of hydrofluorocarbons (HFCs) were tested. Preliminary testing was also performed with ionic liquids and aqueous surfactant solutions. Once potential solvents were identified, an analysis of the performance and environmental characteristics of each was to be conducted. Four contaminants were specified for use in testing. These are Mil-Spec-H-5606 (5606), a hydraulic fluid, Mil-H-83282B (83282), another hydraulic fluid, diethylhexyl sebacate (Sebacate), and WD-40. The structures of these contaminants are all similar, with long aliphatic hydrocarbon chains of lengths between fifteen and fifty. Contaminants were tested both individually and in combination. All combinations were done with equal weights of the constituent contaminants.

McLaughlin, Russell↗

Extending Magnetohydrodynamics to the Slow Dynamics of Collisionless Plasmas

A fluid approach aimed to provide a consistent description of the slow dynamics of a collisionless plasma, is presented. In this regime, both Landau damping and finite Larmor radius effects cannot be ignored. Two models are discussed; one retains the dynamics at sub-ionic scales, while the other is restricted to scales larger than the ion gyroscale. Special attention is paid to the capability of these approaches to accurately reproduce the properties of linear waves that are known to play an important role, for example, in the small-scale dynamics of solar wind turbulence.

Passot, T.↗

Meso-Structured Polymer Electrolyte Fuel Cell Electrode

Increasing the utilization of Pt and Pt alloy catalysts in polymer electrolyte fuel cell cathodes is critical to improving the high power density operation, particularly at low Pt loadings. State of the art electrodes are fabricated in an ink deposition process that leads to uncontrolled electrode architecture with random aggregates of functional domains (catalyst, ionomer, and pore volume) (1). The randomness in the domains induces high tortuosity transport pathways for ions and fluids, which cause severe transport resistance during high current density operation. Thin ionomer films cause additional transport resistance and poisoning of the Pt catalyst, which becomes more significant at low Pt loadings. Reducing the amount of ionomer in the catalyst domain without affecting the ionic transport resistance is key to improving the utilization of the Pt and reducing the transport resistance at low Pt loading. Rational design of the electrode structure with controlled low tortuous ionic transport pathways could improve performance. The introduction of the ionomer pathways could also enable reduction of the ionomer volume in the catalyst domain, reducing the transport resistance. Middelmen et al. proposed electrode structures consisting of aligned components in a low tortuosity configuration to improve performance (2). In this work, we present an alternative electrode structure based on a vertically aligned array of Nafion pillars in the cathode catalyst layer, as shown in Figure 1a. Figure 1b shows the SEM image of the Nafion pillars. Furthermore, Pt supported on carbon catalyst was deposited on the Nafion pillars to fabricate a meso-structured electrode. Nafion pillars provide high conductive and low tortuous pathways for protons, reducing the effective transport distance, and enabling reduction of the ionomer binder in the catalyst domain.

25 ENERGY STORAGE↗

Species-Selective Detection of Volatile Organic Compounds by Ionic Liquid-Based Electrolyte Using Electrochemical Methods

The detection of volatile organic compounds (VOCs) is an important topic for environmental safety and public health. However, the current commercial VOC detectors suffer from cross-sensitivity and low reproducibility. In this work, we present species-selective detection for VOCs using an electrochemical cell based on ionic liquid (IL) electrolytes with features of high selectivity and reliability. The voltammograms measured with the IL-based electrolyte absorbing different VOCs exhibited species-selective features that were extracted and classified by linear discriminant analysis (LDA). The detection system could identify as many as four types of VOCs, including methanol, ethanol, acetone, formaldehyde, and additional water. A mixture of methanol and formaldehyde was detected as well. The sample required for the VOCs classification system was 50 μL, or 1.164 mmol, on average. The response time for each VOC measurement is as fast as 24 s. The volume of VOCs such as formaldehyde in solution could also be quantified by LDA and electrochemical impedance spectroscopy techniques, respectively. The system showed a tunable detection range for 1.6 and 16% (w/v) CH 2 O solution by adjusting the composition of the electrolyte. The limit of detection was as low as 1 μL. For the 1.6% CH 2 O solution, the linearity calibration range was determined to be from 5.30 to 53.00 μmol with a limit of detection at 0.53 μmol. The mechanisms for VOCs determination and quantification are also thoroughly discussed. Finally, it is expected that this work could provide a new insight into the concept of electrochemical detection of VOCs with machine learning analysis and be applied to both VOCs gas monitoring and fluid detection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poly( N -vinylpyrrolidone)- block -Poly(dimethylsiloxane)- block -Poly( N -vinylpyrrolidone) Triblock Copolymer Polymersomes for Delivery of PARP1 siRNA to Breast Cancers

Nearly 20% of HER2-positive breast cancers develop resistance to HER2-targeted therapies requiring the use of advanced therapies. Silencing RNA therapy may be a powerful modality for treating resistant HER2 cancers due to its high specificity and low toxicity. However, the systemic administration of siRNAs requires a safe and efficient delivery platform because of siRNA’s low stability in physiological fluids, inefficient cellular uptake, immunoreactivity, and rapid clearance. We have developed theranostic polymeric vesicles to overcome these hurdles for encapsulation and delivery of small functional molecules and PARP1 siRNA for in vivo delivery to breast cancer tumors. The 100 nm polymer vesicles were assembled from biodegradable and non-ionic poly(N-vinylpyrrolidone) 14 -block-poly(dimethylsiloxane) 47 -block-poly(N-vinylpyrrolidone) 14 triblock copolymer PVPON 14 -PDMS 47 -PVPON 14 using nanoprecipitation and thin-film hydration. We demonstrated that the vesicles assembled from the copolymer covalently tagged with the Cy5.5 fluorescent dye for in vivo imaging could also encapsulate the model drug with high loading efficiency (40%). The dye-loaded vesicles were accumulated in tumors after 18 h circulation in 4TR breast tumor-bearing mice via passive targeting. We found that PARP1 siRNA encapsulated into the vesicles was released intact (13%) into solution by the therapeutic ultrasound treatment as quantified by gel electrophoresis. Additionally, the PARP1 siRNA-loaded polymersomes inhibited the proliferation of MDA-MB-361TR cells by 34% after 6 days of treatment by suppressing the NF-kB signaling pathway, unlike their scrambled siRNA-loaded counterparts. Finally, the treatment by PARP1 siRNA-loaded vesicles prolonged the survival of the mice bearing 4T1 breast cancer xenografts, with the 4-fold survival increase, unlike the untreated mice after 3 weeks following the treatment. These biodegradable, non-ionic PVPON 14 -PDMS 47 -PVPON 14 polymeric nanovesicles capable of the efficient encapsulation and delivery of PARP1 siRNA to successfully knock down PARP1 in vivo can provide an advanced platform for the development of precision-targeted therapeutic carriers, which could help develop highly effective drug delivery nanovehicles for breast cancer gene therapy.

60 APPLIED LIFE SCIENCES↗

Development of Ionic Liquid-Additized, GF-5/6 Compatible Low-Viscosity Oils for Automotive Engine and Rear Axle Lubrication for 4% Improved Fuel Economy

This joint project among ORNL, GM, and DRO successfully developed ionic liquid-additized low viscosity lubricants, SAE 0W-12 and 70W-80, for both IC engine and rear axle lubrication, respectively, and demonstrated combined vehicle fuel economy improvement (FEI). Phosphonium-alkylphosphate ILs have been found to be the most effective among the candidates in protecting surface damage from both sliding wear and rolling contact fatigue, and optimal IL concentrations have been determined. The IL’s impact on three-way catalyst seems to be significantly less adverse than the conventional ZDDP. Oil formulations were optimized for both energy efficiency and wear protection. Tribological bench testing of the IL-additized low-viscosity oils showed at least 40% lower boundary friction, more than 60% lower elastohydrodynamic friction, and greater than 50% less wear compared with commercial baselines. IL-additized lubricants have demonstrated FEI by 9.9% in engine dynamometer tests under extreme conditions and 6.9% increased power output in gear rig tests. Prototype IL-additized engine oil and rear axle fluid exhibited combined FEI of 1.39% and 3.24% benchmarked against the state-of-the-art baselines in vehicle testing of fresh oils under the Federal Test Procedure (FTP) city cycle and Highway Fuel Economy Driving Schedule (HWFET), respectively. Used oil analysis suggested that the IL-additized low-viscosity oils produced less wear than the commercial baselines. The gained fundamental understanding and demonstrated FEI in this work pave the way for future development and implementation of the ionic liquid technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.

Aubrecht, Filip J.↗

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗

An in situ shearing x-ray measurement system for exploring structures and dynamics at the solid–liquid interface

Revealing interfacial structure and dynamics has been one of the essential thematic topics in material science and condensed matter physics. Synchrotron-based x-ray scattering techniques can deliver unique and insightful probing of interfacial structures and dynamics, in particular, in reflection geometries with higher surface and interfacial sensitivity than transmission geometries. We demonstrate the design and implementation of an in situ shearing x-ray measurement system, equipped with both inline parallel-plate and cone-and-plate shearing setups and operated at the advanced photon source at Argonne National Laboratory, to investigate the structures and dynamics of end-tethered polymers at the solid-liquid interface. With a precise lifting motor, a micrometer-scale gap can be produced by aligning two surfaces of a rotating upper shaft and a lower sample substrate. A torsional shear flow forms in the gap and applies tangential shear forces on the sample surface. The technical combination with nanoscale rheology and the utilization of in situ x-ray scattering allow us to gain fundamental insights into the complex dynamics in soft interfaces under shearing. In this work, we demonstrate the technical scope and experimental capability of the in situ shearing x-ray system through the measurements of charged polymers at both flat and curved interfaces upon shearing. Furthermore, through the in situ shearing x-ray scattering experiments integrated with theoretical simulations, we aim to develop a detailed understanding of the short-range molecular structure and mesoscale ionic aggregate morphology, as well as ion transport and dynamics in soft interfaces, thereby providing fundamental insight into a long-standing challenge in ionic polymer brushes with a significant technological impact.

36 MATERIALS SCIENCE↗

Free-zone electrophoresis of animal cells. 1: Experiments on cell-cell interactions

The electrophoretically migrating zones wasa monitored. The absence of fluid flows in the direction of migration permits direct measurement of electrophoretic velocities of any material. Sedimentation is orthogonal to electrokinetic motion and the effects of particle-particle interaction on electrophoretic mobility is studied by free zone electrophoresis. Fixed erythrocytes at high concentrations, mixtures of fixed erythrocytes from different animal species, and mixtures of cultured human cells were studied in low ionic strength buffers. The electrophoretic velocity of fixed erythrocytes was not altered by increasing cell concentration or by the mixing of erythrocytes from different species. When zones containing cultured human glial cells and neuroblastoma cells are permitted to interact during electrophoresis, altered migration patterns occur. It is found that cell-cell interactions depends upon cell type.

Todd, P. W.↗

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗