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At least 37 records · Page 2

Hydrophobic Treatment Enabling Analysis of Wettable Surfaces using a Liquid Microjunction Surface Sampling Probe/Electrospray Ionization-Mass Spectrometry System

An aerosol application procedure involving one or more commercially available silicone based products was developed to create hydrophobic surfaces that enable analysis of otherwise wettable, absorbent surfaces using a liquid microjunction surface sampling probe/electrospray ionization mass spectrometry system. The treatment process resulted in a hydrophobic surface that enabled formation of the requisite probe - to - surface liquid microjunction for sampling and allowed efficient extraction of the analytes from the surface, but did not contribute significant chemical background in the mass spectra. The utility of this treatment process was demonstrated with the treatment of wettable high performance thin layer chromatography plates, post plate development, and their subsequent analysis with the sampling probe. The surface treatment process for different surface types was described and explained and the effectiveness of the treatment and subsequent analysis was illustrated using alkaloids from Goldenseal (Hydrastis canadensis) root separated on a normal phase silica gel 60 F254S plate and peptides from protein tryptic digests separated on a Protochrom HPTLC Silica gel 60 F254S plate and a Protochrom HPTLC cellulose sheet. This simple surface treatment process significantly expands the analytical surfaces that can be analyzed with the liquid microjunction surface sampling probe, and therefore, also expands the analytical utility of this liquid extraction based surface sampling approach.

Walworth, Matthew J↗

Extraction efficiency and implications for absolute quantitation of propranolol in mouse brain, liver and kidney thin tissue sections using droplet-based liquid microjunction surface sampling-HPLC ESI-MS/MS

Currently, absolute quantitation aspects of droplet-based surface sampling for thin tissue analysis using a fully automated autosampler/HPLC-ESI-MS/MS system are not fully evaluated. Knowledge of extraction efficiency and its reproducibility is required to judge the potential of the method for absolute quantitation of analytes from thin tissue sections. Methods: Adjacent thin tissue sections of propranolol dosed mouse brain (10- μm-thick), kidney (10- μm-thick) and liver (8-, 10-, 16- and 24- μm-thick) were obtained. Absolute concentration of propranolol was determined in tissue punches from serial sections using standard bulk tissue extraction protocols and subsequent HPLC separations and tandem mass spectrometric analysis. These values were used to determine propranolol extraction efficiency from the tissues with the droplet-based surface sampling approach. Results: Extraction efficiency of propranolol using 10- μm-thick brain, kidney and liver thin tissues using droplet-based surface sampling varied between ~45-63%. Extraction efficiency decreased from ~65% to ~36% with liver thickness increasing from 8 μm to 24 μm. Randomly selecting half of the samples as standards, precision and accuracy of propranolol concentrations obtained for the other half of samples as quality control metrics were determined. Resulting precision ( ±15%) and accuracy ( ±3%) values, respectively, were within acceptable limits. In conclusion, comparative quantitation of adjacent mouse thin tissue sections of different organs and of various thicknesses by droplet-based surface sampling and by bulk extraction of tissue punches showed that extraction efficiency was incomplete using the former method, and that it depended on the organ and tissue thickness. However, once extraction efficiency was determined and applied, the droplet-based approach provided the required quantitation accuracy and precision for assay validations. Furthermore, this means that once the extraction efficiency was calibrated for a given tissue type and drug, the droplet-based approach provides a non-labor intensive and high-throughput means to acquire spatially resolved quantitative analysis of multiple samples of the same type.

59 BASIC BIOLOGICAL SCIENCES↗

Laser Ablation Sampling of Materials Directly into the Formed Liquid Microjunction of a Continuous Flow Surface Sampling Probe/Electrospray Ionization Emitter for Mass Spectral Analysis and Imaging

Transmission geometry laser ablation directly into a formed liquid microjunction of a continuous flow liquid microjunction surface sampling probe/electrospray ionization emitter was utilized for molecular and elemental detection and mass spectrometry imaging. The ability to efficiently capture and ionize ablated material was demonstrated by the detection of various small soluble n-mers of polyaniline and silver ion solvent clusters formed from laser ablation of electropolymerized polyaniline and silver thin films, respectively. In addition, analysis of surfaces that contain soluble components was accomplished by coating or laminating the sample with an insoluble film to enable liquid junction formation without directly extracting material from the surface. The ability to perform mass spectrometry imaging at a spatial resolution of about 50 m was illustrated by using laminated inked patterns on a microscope slide. In general, these data demonstrate at least an order of magnitude signal enhancement compared to the non-contact, laser ablation droplet capture-based surface sampling/ionization approaches that have been previously presented.

electrospray ionization (ESI)↗

Kinetics, Products, and Brown Carbon Formation by Aqueous-Phase Reactions of Glycolaldehyde with Atmospheric Amines and Ammonium Sulfate

Glycolaldehyde (GAld) is a C 2 water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde’s aqueous-phase reactions with AS, methylamine, and glycine. Reaction rate constants are smaller than those of respective glyoxal and methylglyoxal reactions in the pH range of 3–6. In follow-up cloud chamber experiments, deliquesced glycine and AS seed particles were found to take up glycolaldehyde and methylamine and form brown carbon. At very high relative humidity, these changes were more than 2 orders of magnitude faster than predicted by our bulk liquid NMR kinetics measurements, suggesting that reactions involving surface-active species at crowded air–water interfaces may play an important role. The high-resolution liquid chromatography–electrospray ionization–mass spectrometric analysis of filter extracts of unprocessed AS + GAld seed particles identified sugar-like C 6 and C 12 GAld oligomers, including proposed product 3-deoxyglucosone, with and without modification by reactions with ammonia to diimine and imidazole forms. Chamber exposure to methylamine gas, cloud processing, and simulated sunlight increased the incorporation of both ammonia and methylamine into oligomers. Many C 4 –C 16 imidazole derivatives were detected in an extract of chamber-exposed aerosol along with a predominance of N-derivatized C 6 and C 12 glycolaldehyde oligomers, suggesting that GAld is capable of forming brown carbon SOA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of this coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.

Laser Ablation↗

Transient analysis of advancing contact angle measurements on polished rock surfaces

We report that contact angle measurements for gas-liquid-rock systems are important for modeling multi-phase flow and transport in the subsurface. These data are needed in applications such as the extraction of oil and gas resources, geologic sequestration of carbon dioxide, contaminant fate and transport, and aquifer recharge through the vadose zone. Contact angles are frequently measured with the sessile drop method. Previous research has largely ignored the dynamic behavior of sessile droplets on geologic materials. This study investigates the dynamic behavior of sessile water droplets on prepared rock surfaces in the presence of air. Droplet diameter and advancing contact angle were determined at 0.5 s intervals for ~90 s on flat polished disks of Burlington limestone, Crossville sandstone, Mancos shale, Sierra White granite, Vermilion Bay granite, and Westerly granite using a Krüss DSA 30 Drop Shape Analyzer. The droplet diameter and advancing contact angle data sets were nonlinearly regressed against time using two different two-parameter models. The median coefficients of determination for the fits were 0.85 and 0.96, respectively. The resulting parameter estimates were used to compute the apparent equilibrium contact angle, θ e , for each disk following droplet diameter stabilization. Estimates of θ e ranged from 37.2° for Mancos shale to 75.6° for Burlington limestone. Analysis of variance indicated statistically significant differences in θ e between the rock types at the 95% confidence level. The variability of θe on the polished rock surfaces, as quantified by the coefficient of variation (CV) for θ e , varied between ~3 and ~9%; there were no significant differences in CV between the rock types. Neutron radiography indicated changes droplet morphology over time were due to the spontaneous imbibition of water into the rock matrix. Finally, the transient analysis employed in this study permits a more meaningful estimate of the equilibrium contact angle for rocks than taking the initial value or averaging over time as is frequently done.

58 GEOSCIENCES↗

Spatial profiling of stapled α–helical peptide ATSP-7041 in mouse whole-body thin tissue sections using droplet-based liquid microjunction surface sampling-HPLC-ESI–MS/MS

Here, the application of a fully automated autosampler/HPLC-ESI–MS/MS system for spatially resolved quantitative droplet-based liquid extraction surface sampling/profiling of stapled α–helical peptide ATSP-7041 in mouse whole-body thin tissue sections is reported. 20-μm-thick serial tissue sections of an ATSP-7041 dosed mouse were prepared and the absolute concentration of the targeted peptide was first determined in different organs using 2.3-mm diameter tissue punches, standard bulk tissue extraction protocols, and subsequent HPLC separation and tandem mass spectrometric analysis. The same organs/locations were then analyzed in neighboring tissue sections using the droplet-based surface sampling approach. The observed ATSP-7041 concentration using this method was always significantly lower than that measured by the tissue punch workflow at the same tissue location of a serial section. Calculated extraction efficiencies were 10.7 ± 0.5% (brain), 11.0 ± 3.2% (liver spot 1), 10.7 ± 2.6% (liver spot 2), 15.0 ± 0.6% (lung) and 12.9 ± 0.7% (blood). While these extraction efficiency values were low, they were reproducible within a given organ. This suggests that once the extraction efficiency is established for a given tissue type and drug, the reproducibility of the droplet-based approach could provide a non-labor intensive and high-throughput means to acquire spatially resolved quantitative analysis of multiple samples of the same type.

60 APPLIED LIFE SCIENCES↗

Multiphase Species Transport Modeling for Molten Salt Reactors in the System Analysis Module: Generation, Decay, Deposition, and Extraction of Insoluble Fission Products

With the increase of interests in the design and deployment of advanced reactor systems, a desire for simulation tools supporting system analysis of reactor operation and safety is rising. Molten salt reactors (MSRs), one of the advanced reactor systems, utilize liquid fused salt fuel as both coolant and fuel. During operation, MSR generates insoluble fission products, including noble metals and gases. The buildup of these species in fuel salt presents safety concerns as they may deposit on surfaces of critical components and produce excessive decay heat, causing the failure of system components. Timely removal of these noble metals and gases would ensure the safe operation of the reactor system. The dynamic nature of salt fuel system, involving the generation, decay, deposition, and extraction of noble metals and gases, calls for robust species transport models to facilitate system analysis and monitoring, and design of efficient species removal components. This paper concentrates on the development of a computational framework for species transport, consisting of multiphase transport model formulation, mass transfer between phases, numerical implementation in MOOSE environment, verification through Method of Manufacture Solutions (MMS) and validation against experimental data from the Molten Salt Reactor Experiment (MSRE). Integrating this framework into the System Analysis Module (SAM) code further enhances SAM’s capabilities for advanced reactor analysis in the future.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

A study of DC electrical breakdown in liquid helium through analysis of the empirical breakdown field distributions

Here we report results from a study on electrical breakdown in liquid helium using near-uniform-field stainless steel electrodes with a stressed area of ~0.7cm 2 . The distribution of the breakdown field is obtained for temperatures between 1.7 K and 4.0 K, pressures between the saturated vapor pressure and 626 Torr, and with electrodes of different surface polishes. A data-based approach for determining the electrode-surface-area scaling of the breakdown field is presented. The dependence of the breakdown probability on the field strength as extracted from the breakdown field distribution data is used to show that breakdown is a surface phenomenon closely correlated with Fowler–Nordheim field emission from asperities on the cathode. We show that the results from this analysis provide an explanation for the supposed electrode gap-size effect and also allow for a determination of the breakdown-field distribution for arbitrary shaped electrodes. Most importantly, the analysis method presented in this work can be extended to other noble liquids to explore the dependencies for electrical breakdown in those media.

74 ATOMIC AND MOLECULAR PHYSICS↗

Characterization of Solids Deposited on the Modular Caustic-Side Solvent Extraction Unit (MCU) Strip Effluent (SE) Coalescer Media Removed in April 2015

On June 2015, Savannah River National Laboratory (SRNL) received a Strip Effluent (SE) coalescer (FLT-304) from MCU. That coalescer was first installed at MCU in late October 2014 and removed in April 2015. While processing approximately 48,700 gallons of strip solution, the pressure drop steadily increased linearly from 1 psi to near 16 psi (the administrative limit is 17 psi) with the total filtrate volume (2.1E-4 psi/gal of filtrate). The linear behavior is due to the combined effect of a constant deposition of material that starts from the closed-end to the mid-section of the coalescer reducing the available surface area of the coalescer for fluid passage (linearly with filtrate volume) and the formation of a secondary emulsion (water in NG-CSSX) on the fibers of the coalescer media. Both effects reduced the coalescer porosity by at least 13% (after processing 48,700 gallons). Before the coalescer was removed, it was flushed with a 10 mM boric acid solution to reduce the dose level. To determine the nature of the deposited material, a physical and chemical analysis of the coalescer was conducted. Characterization of this coalescer revealed the adsorption of organic containing amines (secondary amides and primary amines), TiDG, degraded modifier (with no hydroxyl group), MaxCalix, and oxidized hydrocarbon (possibly from Isopar™L or from lubricant used at MCU) onto the coalescer media. The amide and amines are possibly from the decomposition of the suppressor (TiDG). The modifier and MaxCalix were the largest components of the deposited organic material, as determined from leaching the coalescer with dichloromethane. Both the Fourier-Transformed Infrared (FTIR) and Fourier-Transformed Hydrogen Nuclear Magnetic Resonance (FT-HNMR) results indicated that some of the modifier was degraded (missing their OH groups). The modifier was observed everywhere in the examined coalescer pieces (FTIR), while the TiDG and its decomposition products were observed at the entrance discs of the coalescer. A solvent trim (a cocktail of solvent components with a high concentration of modifier) was added to the solvent on 2/22/2015. It is believed that the trim did not mix completely with the solvent and that it was subsequently spread around the MCU components including the coalescers, where it may have deposited. Chronologically, the modifier, the TiDG’s decomposition products and silicates deposited on the entrance discs first and after the pressure drop increased significantly, parts of the coalescer media detached itself from the central porous steel mandrel and a significant amount of steel debris, mercury, titanium, and additional aluminum and silicates deposited on the coalescer.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Instrument for Solvent Extraction and Analysis (ISEE) of Organics from Regolith Simulant Using Supercritical Fluid Extraction and Chromatography

ISEE is an instrument with the potential to perform extractions from regolith found on the surface of asteroids and planets, followed by characterization and quantitation of the extracts using supercritical fluid extraction (SFE) and chromatography (SFC). SFE is a developed technique proven to extract a wide range of organic compounds. SFC is similar to High Performance Liquid Chromatography (HPLC) but has the advantage of performing chiral separations without needing to derivatize the chiral compounds. CO2 will be the solvent for both stages as it is readily available in the Mars atmosphere. ISEE will capture CO2 from the environment, and use it for SFE and SFC. If successful, this would allow ISEE to perform analysis of organic compounds without using consumables. This paper will present results on a preliminary, proof-of-principle effort to use SFE and SFC to extract and analyze lunar regolith simulant spiked with organic compounds representing a range of organics that ISEE would expect to characterize. An optimization of variables for the extraction of the organics from the spiked regolith was successfully developed, using 138 bar pressure and 40 C temperature. The extraction flow rate was optimized at 2% SLPM with 30% methanol modifier. The extractions were successful with a value of 77.3+/- 0.9% of organics extracted. However, the recovery of organics after the extraction was very low with only 48.5+/-14.2%. Moreover, three columns were selected to analyze multiple samples at a time; two of them are Viridis HSS C18 SB and Torus DIOL, and the third column, specific for chiral separations, has not yet been selected yet.

Franco, Carolina↗

Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

Getty, Stephanie A.↗

Sorted-cell proteomics reveals an AT1-associated epithelial cornification phenotype and suggests endothelial redox imbalance in human bronchopulmonary dysplasia

Bronchopulmonary dysplasia (BPD) is a neonatal lung disease characterized by inflammation and scarring leading to long-term tissue damage. Previous whole tissue proteomics identified BPD-specific proteome changes and cell type shifts. Little is known about the proteome-level changes within specific cell populations in disease. Here, we sorted epithelial (EPI) and endothelial (ENDO) cell populations based on their differential surface markers from normal and BPD human lungs. Using a low-input compatible sample preparation method (MicroPOT), proteins were extracted and digested into peptides and subjected to liquid chromatography-tandem mass spectrometry (LC-MS/MS) proteome analysis. Of the 4,970 proteins detected, 293 were modulated in abundance or detection in the EPI population and 422 were modulated in ENDO cells. Modulation of proteins associated with actin-cytoskeletal function, such as SCEL, LMO7, and TBA1B was observed in the BPD EPIs. Using confocal imaging and analysis, we validated the presence of aberrant multilayer-like structures comprising SCEL and LMO7, known to be associated with epidermal cornification, in the human BPD lung. This is the first report of the accumulation of cornification-associated proteins in BPD. Their localization in the alveolar parenchyma, primarily associated with alveolar type 1 (AT1) cells, suggests a role in the BPD postinjury response. In the ENDOs, redox balance and mitochondrial function pathways were modulated. Alternative mRNA splicing and cell proliferative functions were elevated in both populations, suggesting potential dysregulation of cell progenitor fate. This study characterized the proteome of epithelial and endothelial cells from the BPD lung for the first time, identifying population-specific changes in BPD pathogenesis.

BPD↗

Water balance model (WBM) v.1.0.0: a scalable gridded global hydrologic model with water-tracking functionality

Abstract. This paper describes the University of New Hampshire Water Balance Model, WBM, a process-based gridded global hydrologic model that simulates the land surface components of the global water cycle and includes water extraction for use in agriculture and domestic sectors. The WBM was first published in 1989; here, we describe the first fully open-source WBM version (v.1.0.0). Earlier descriptions of WBM methods provide the foundation for the most recent model version that is detailed here. We present an overview of the model functionality, utility, and evaluation of simulated global river discharge and irrigation water use. This new version adds a novel suite of water source tracking modules that enable the analysis of flow-path histories on water supply. A key feature of WBM v.1.0.0 is the ability to identify the partitioning of sources for each stock or flux within the model. Three different categories of tracking are available: (1) primary inputs of water to the surface of the terrestrial hydrologic cycle (liquid precipitation, snowmelt, glacier melt, and unsustainable groundwater); (2) water that has been extracted for human use and returned to the terrestrial hydrologic system; and (3) runoff originating from user-defined spatial land units. Such component tracking provides a more fully transparent model in that users can identify the underlying mechanisms generating the simulated behavior. We find that WBM v.1.0.0 simulates global river discharge and irrigation water withdrawals well, even with default parameter settings, and for the first time, we are able to show how the simulation arrives at these fluxes by using the novel tracking functions.

54 ENVIRONMENTAL SCIENCES↗

Systems and methods for laser assisted sample transfer to solution for chemical analysis

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Systems and methods for laser assisted sample transfer to solution for chemical analysis

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Systems and methods for laser assisted sample transfer to solution for chemical analysis

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

47 OTHER INSTRUMENTATION↗

Quantitation of repaglinide and metabolites in mouse whole-body thin tissue sections using droplet-based liquid microjunction surface sampling-high-performance liquid chromatography-electrospray ionization tandem mass spectrometry

Herein, quantitation aspects of a fully automated autosampler/HPLC-MS/MS system applied for unattended droplet-based surface sampling of repaglinide dosed thin tissue sections with subsequent HPLC separation and mass spectrometric analysis of parent drug and various drug metabolites was studied. Major organs (brain, lung, liver, kidney, muscle) from whole-body thin tissue sections and corresponding organ homogenates prepared from repaglinide dosed mice were sampled by surface sampling and by bulk extraction, respectively, and analyzed by HPLC-MS/MS. A semi-quantitative agreement between data obtained by surface sampling and that by employing organ homogenate extraction was observed. Drug concentrations obtained by the two methods followed the same patterns for post-dose time points (0.25, 0.5, 1 and 2 h). Drug amounts determined in the specific tissues was typically higher when analyzing extracts from the organ homogenates. Furthermore, relative comparison of the levels of individual metabolites between the two analytical methods also revealed good semi-quantitative agreement.

59 BASIC BIOLOGICAL SCIENCES↗