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Sample records for 96-well solid phase

  1. 96-well plate-to-plate gravity fluorous solid-phase extraction (F-SPE) for solution-phase library purification.

    PubMed

    Zhang, Wei; Lu, Yimin

    2007-01-01

    Large particle size (125_210 microm) fluorous silica gel bonded with a -SiCH2CH2C8F17 stationary phase has been employed for gravity-driven fluorous solid-phase extraction (F-SPE) on two types of 96-well plates. A 1 or 0.75 g portion of fluorous silica is packed to each well of the 3.5-mL Ex-Blok and the 2.2-mL deep-well filtration plates, respectively. Up to 50 mg of reaction mixture is loaded and then eluted with a fluorophobic solvent (DMSO, DMF, or 85:15 DMF-H2O). Products collected in 96-well receiving plates are directly concentrated on a GeneVac vacuum centrifuge. This simple and highly efficient plate-to-plate F-SPE technique has been demonstrated in the purification of four 96-compound libraries produced by scavenging reactions with 1-(perfluoroctyl)propyl isatoic anhydride (F-IA), amide coupling reactions with 2-chloro-4,6-bis[(perfluorooctyl)propyloxy]-1,3,5-triazine (F-CDMT) or 2,4-dichloro-6-(perfluorooctyl)propyloxy-1,3,5-triazine (F-DCT), and Mitsunobu reactions with fluorous diethyl azodicarboxylate (F-DEAD) and triphenylphosphine (F-TPP). Approximately 80% of products in each library have greater than 85% purity after F-SPE without conducting chromatography.

  2. A new approach to the application of solid phase extraction disks with LC-MS/MS for the analysis of drugs on a 96-well plate format.

    PubMed

    Cudjoe, Erasmus; Pawliszyn, Janusz

    2009-11-01

    A new 96-well disk solid phase extraction sample preparation technique which does not involve vacuum pumps integrated with liquid chromatographic tandem mass spectrometric (LC-MS/MS) was developed for high throughput determination of benzodiazepines (nordiazepam, diazepam, lorazepam and oxazepam). In addition, the method completely allows the re-use of the SPE disk membranes for subsequent analyses after re-conditioning. The method utilizes a robotic autosampler for parallel extractions in a 96-well plate format. Results have been presented for independent extractions from three matrices; phosphate buffer solution, urine, and plasma. Factors affecting data reproducibility, extraction kinetics, sample throughput, and reliability of the system were investigated and optimized. A total time required per sample was 0.94 min using 96-well format. Method reproducibility was < or =9% relative standard deviation for all three matrices. Limits of detection and quantitation recorded were respectively in the range 0.02-0.15 and 0.2-2.0 ng/mL with linearity ranging from 0.2 to 500 ng/mL for all matrices.

  3. A high-throughput approach for the determination of pesticide residues in cucumber samples using solid-phase microextraction on 96-well plate.

    PubMed

    Bagheri, Habib; Es'haghi, Ali; Es-haghi, Ali; Mesbahi, Noushin

    2012-08-31

    A high-throughput solid-phase microextraction (SPME) on 96-well plate together with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of some selected pesticides in cucumber samples. Pieces with the length of 1.0 cm of silicon tubing were precisely prepared and then coated on the end part of stainless steel wires. The prepared fibers were positioned in a home-made polytetrafluoroethylene (PTFE)-based constructed ninety-six holes block to have the possibility of simultaneous immersion of the SPME fibers into the center of individual wells. Pesticides such as diazinon, penconazol, tebuconazol, bitertanol, malathion, phosalone and chlorpyrifos-methyl were selected for their highly application in cucumber field. The performances of the SPME fibers, such as intra and inter-fibers reproducibility, were evaluated and the results showed a good similarity in extraction yields. A volume of 1 mL of the aquatic supernatant of the cucumber samples was transferred into the 96-well plate and the array of SPME fibers was applied for the extraction of the selected pesticides. The important parameters influencing the whole extraction process including, organic solvent percent, salt addition, dilution factor, stirring rate and extraction time were optimized. The inter- and intra-day RSD% were found to be less than 15.4%. Limits of detection (LOD) and limits of quantification (LOQ) were below 60 and 180 μg kg(-1), respectively. The coefficient of determination was satisfactory (r(2)>0.99) for all the studied analytes. The developed method was successfully applied to the monitoring of several samples gathered from local markets.

  4. Comparison of turbulent-flow chromatography with automated solid-phase extraction in 96-well plates and liquid-liquid extraction used as plasma sample preparation techniques for liquid chromatography-tandem mass spectrometry.

    PubMed

    Zimmer, D; Pickard, V; Czembor, W; Müller, C

    1999-08-27

    Turbulent flow chromatography (TFC) combined with the high selectivity and sensitivity of tandem mass spectrometry (MS-MS) is a new technique for the fast direct analysis of drugs from crude plasma. TFC in the 96-well plate format reduces significantly the time required for sample clean-up in the laboratory. For example, for 100 samples the workload for a technician is reduced from about 8 h by a manual liquid-liquid extraction (LLE) assay to about 1 h in the case of TFC. Sample clean-up and analysis are performed on-line on the same column. Similar chromatographic performance and validation results were achieved using HTLC Turbo-C18 columns (Cohesive Technologies) and Oasis HLB extraction columns (Waters). One 96-well plate with 96 plasma samples is analyzed within 5.25 h, corresponding to 3.3 min per sample. Compared to this LLE and analysis of 96 samples takes about 16 h. Two structurally different and highly protein bound compounds, drug A and drug B, were analyzed under identical TFC conditions and the assays were fully validated for the application to toxicokinetics studies (compliant with Good Laboratory Practices-GLP). The limit of quantitation was 1.00 microg/l and the linear working range covered three orders of magnitude for both drugs. In the case of drug A the quality of analysis by TFC was similar to the reference LLE assay and slightly better than automated solid-phase extraction in 96-well plates. The accuracy was -3.1 to 6.7% and the precision was 3.1 to 6.8% in the case of drug A determined for dog plasma by TFC-MS-MS. For drug B the accuracy was -3.7 to 3.5% and the precision was 1.6 to 5.4% for rat plasma, which is even slightly better than what was achieved with the validated protein precipitation assay.

  5. Automated 96-well solid phase extraction and hydrophilic interaction liquid chromatography-tandem mass spectrometric method for the analysis of cetirizine (ZYRTEC) in human plasma--with emphasis on method ruggedness.

    PubMed

    Song, Qi; Junga, Heiko; Tang, Yong; Li, Austin C; Addison, Tom; McCort-Tipton, Melanie; Beato, Brian; Naidong, Weng

    2005-01-05

    A high-throughput bioanalytical method based on automated sample transfer, automated solid phase extraction, and hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) analysis, has been developed for the determination of cetirizine, a selective H(1)-receptor antagonist. Deuterated cetirizine (cetirizine-d(8)) was synthesized as described and was used as the internal standard. Samples were transferred into 96-well plates using an automated sample handling system. Automated solid phase extraction was carried out using a 96-channel programmable liquid-handling workstation. Solid phase extraction 96-well plate on polymer sorbent (Strata X) was used to extract the analyte. The extracted samples were injected onto a Betasil silica column (50 x 3, 5 microm) using a mobile phase of acetonitrile-water-acetic acid-trifluroacetic acid (93:7:1:0.025, v/v/v/v) at a flow rate of 0.5 ml/min. The chromatographic run time is 2.0 min per injection, with retention time of cetirizine and cetirizine-d(8) both at 1.1 min. The system consisted of a Shimadzu HPLC system and a PE Sciex API 3000 or API 4000 tandem mass spectrometer with (+) ESI. The method has been validated over the concentration range of 1.00-1000 ng/ml cetirizine in human plasma, based on a 0.10-ml sample size. The inter-day precision and accuracy of the quality control (QC) samples demonstrated <3.0% relative standard deviation (R.S.D.) and <6.0% relative error (RE). Stability of cetirizine in stock solution, in plasma, and in reconstitution solution was established. The absolute extraction recovery was 85.8%, 84.5%, and 88.0% at 3, 40, and 800 ng/ml, respectively. The recovery for the internal standard was 84.1%. No adverse matrix effects were noticed for this assay. The automation of the sample preparation steps not only increased the analysis throughput, but also increased method ruggedness. The use of a stable isotope-labeled internal standard further improved the method ruggedness

  6. Validation of a sensitive and automated 96-well solid-phase extraction liquid chromatography-tandem mass spectrometry method for the determination of desloratadine and 3-hydroxydesloratadine in human plasma.

    PubMed

    Yang, Liyu; Clement, Robert P; Kantesaria, Bhavna; Reyderman, Larisa; Beaudry, Francis; Grandmaison, Charles; Di Donato, Lorella; Masse, Robert; Rudewicz, Patrick J

    2003-07-25

    To support clinical development, a liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed and validated for the determination of desloratadine (descarboethoxyloratadine) and 3-OH desloratadine (3-hydroxydescarboethoxyloratadine) concentrations in human plasma. The method consisted of automated 96-well solid-phase extraction for sample preparation and liquid chromatography/turbo ionspray tandem mass spectrometry for analysis. [2H(4)]Desloratadine and [2H(4)]3-OH desloratadine were used as internal standards (I.S.). A quadratic regression (weighted 1/concentration(2)) gave the best fit for calibration curves over the concentration range of 25-10000 pg/ml for both desloratadine and 3-OH desloratadine. There was no interference from endogenous components in the blank plasma tested. The accuracy (%bias) at the lower limit of quantitation (LLOQ) was -12.8 and +3.4% for desloratadine and 3-OH desloratadine, respectively. The precision (%CV) for samples at the LLOQ was 15.1 and 10.9% for desloratadine and 3-OH desloratadine, respectively. For quality control samples at 75, 1000 and 7500 pg/ml, the between run %CV was

  7. High-throughput, semi-automated determination of a cyclooxygenase II inhibitor in human plasma and urine using solid-phase extraction in the 96-well format and high-performance liquid chromatography with post-column photochemical derivatization-fluorescence detection.

    PubMed

    Matthews, C Z; Woolf, E J; Lin, L; Fang, W; Hsieh, J; Ha, S; Simpson, R; Matuszewski, B K

    2001-02-25

    Compound I, 5-chloro-3-(4-methanesulfonylphenyl)-6'-methyl-[2,3']bipyridinyl, has been found to be a specific inhibitor of the enzyme cyclooxygenase II (COX II). The anti-inflammatory properties of this compound are currently being investigated. HPLC assays for the determination of this analyte in human plasma and human urine have been developed. Isolation of I and the internal standard (II) was achieved by solid-phase extraction (SPE) in the 96-well format. A C8 SPE plate was used for the extraction of the drug from human plasma (recovery >90%) while a mixed-mode (C8/Cation) SPE plate was used to isolate the analytes from human urine (recovery approximately 71%). The analyte and internal standard were chromatographed on a Keystone Scientific Prism-RP guard column (20 x 4.6 mm) connected to a Prism-RP analytical column (150 x 4.6 mm), using a mobile phase consisting of 45% acetonitrile in 10 mM acetate buffer (pH = 4); the analytes eluted at retention times of 5.2 and 6.9 min for I and II, respectively. Compounds I and II were found to form highly fluorescent products after exposure to UV light (254 nm). Thus, the analytes were detected by fluorescence (lambda(ex) = 260 nm, lambda(em) =375 nm) following post-column photochemical derivatization. Eight point calibration curves over the concentration range of 5-500 ng/ml for human plasma and human urine yielded a linear response (R2>0.99) when a 1/y weighted linear regression model was employed. Based on the replicate analyses (n = 5) of spiked standards, the within-day precision for both assays was better than 7% C.V. at all points on the calibration curve; within-day accuracy was within 5% of nominal at all standard concentrations. The between-run precision and accuracy of the assays, as calculated from the results of the analysis of quality control samples, was better than 8% C.V. and within 8% of nominal. I was found to be stable in human plasma and urine for at least 8 and 2 months, respectively. In addition, the

  8. High-throughput 96-well solvent mediated sonic blending synthesis and on-plate solid/solution stability characterization of pharmaceutical cocrystals.

    PubMed

    Luu, Van; Jona, Janan; Stanton, Mary K; Peterson, Matthew L; Morrison, Henry G; Nagapudi, Karthik; Tan, Helming

    2013-01-30

    A 96-well high-throughput cocrystal screening workflow has been developed consisting of solvent-mediated sonic blending synthesis and on-plate solid/solution stability characterization by XRPD. A strategy of cocrystallization screening in selected blend solvents including water mixtures is proposed to not only manipulate solubility of the cocrystal components but also differentiate physical stability of the cocrystal products. Caffeine-oxalic acid and theophylline-oxalic acid cocrystals were prepared and evaluated in relation to saturation levels of the cocrystal components and stability of the cocrystal products in anhydrous and hydrous solvents. AMG 517 was screened with a number of coformers, and solid/solution stability of the resulting cocrystals on the 96-well plate was investigated. A stability trend was observed and confirmed that cocrystals comprised of lower aqueous solubility coformers tended to be more stable in water. Furthermore, cocrystals which could be isolated under hydrous solvent blending condition exhibited superior physical stability to those which could only be obtained under anhydrous condition. This integrated HTS workflow provides an efficient route in an API-sparing approach to screen and identify cocrystal candidates with proper solubility and solid/solution stability properties.

  9. Liquid chromatography/tandem mass spectrometric bioanalysis using normal-phase columns with aqueous/organic mobile phases - a novel approach of eliminating evaporation and reconstitution steps in 96-well SPE.

    PubMed

    Naidong, Weng; Shou, Wilson Z; Addison, Thomas; Maleki, Saber; Jiang, Xiangyu

    2002-01-01

    Bioanalytical methods using automated 96-well solid-phase extraction (SPE) and liquid chromatography with electrospray tandem mass spectrometry (LC/MS/MS) are widely used in the pharmaceutical industry. SPE methods typically require manual steps of drying of the eluates and reconstituting of the analytes with a suitable injection solvent possessing elution strength weaker than the mobile phase. In this study, we demonstrated a novel approach of eliminating these two steps in 96-well SPE by using normal-phase LC/MS/MS methods with low aqueous/high organic mobile phases, which consisted of 70-95% organic solvent, 5-30% water, and small amount of volatile acid or buffer. While the commonly used SPE elution solvents (i.e. acetonitrile and methanol) have stronger elution strength than a mobile phase on reversed-phase chromatography, they are weaker elution solvents than a mobile phase for normal-phase LC/MS/MS and therefore can be injected directly. Analytical methods for a range of polar pharmaceutical compounds, namely, omeprazole, metoprolol, fexofenadine, pseudoephedrine as well as rifampin and its metabolite 25-desacetyl-rifampin, in biological fluids, were developed and optimized based on the foregoing principles. As a result of the time saving, a batch of 96 samples could be processed in one hour. These bioanalytical LC/MS/MS methods were validated according to "Guidance for Industry - Bioanalytical Method Validation" recommended by the Food and Drug Administration (FDA) of the United States.

  10. Evaluation of drug load and polymer by using a 96-well plate vacuum dry system for amorphous solid dispersion drug delivery.

    PubMed

    Chiang, Po-Chang; Ran, Yingqing; Chou, Kang-Jye; Cui, Yong; Sambrone, Amy; Chan, Connie; Hart, Ryan

    2012-06-01

    It is well recognized that poor dissolution rate and solubility of drug candidates are key limiting factors for oral bioavailability. While numerous technologies have been developed to enhance solubility of the drug candidates, poor water solubility continuously remains a challenge for drug delivery. Among those technologies, amorphous solid dispersions (SD) have been successfully employed to enhance both dissolution rate and solubility of poorly water-soluble drugs. This research reports a high-throughput screening technology developed by utilizing a 96-well plate system to identify optimal drug load and polymer using a solvent casting approach. A minimal amount of drug was required to evaluate optimal drug load in three different polymers with respect to solubility improvement and solid-state stability of the amorphous drug-polymer system. Validation of this method was demonstrated with three marketed drugs as well as with one internal compound. Scale up of the internal compound SD by spray drying further confirmed the validity of this method, and its quality was comparable to a larger scale process. Here, we demonstrate that our system is highly efficient, cost-effective, and robust to evaluate the feasibility of spray drying technology to produce amorphous solid dispersions.

  11. Electrothermal micromixing in 96 well plate

    NASA Astrophysics Data System (ADS)

    Kauffmann, Paul; Loire, Sophie; Mezic, Igor

    2011-11-01

    Diagnostic and pharmacology processes could be greatly accelerated by appropriate mixing. Here electrothermal flows are explored to provide mixing of conductive physiological solutions (=1.6 S/m) in a 96 well plate. Three interdigitated electrodes provide an electric field (< 15Vpp, 1MHz) beneath each well. Polarization and conduction phenomenon of the fluid in a well will be first modeled numerically and compared to an electrical circuit model. Due to high conductivity and permittivity of the fluid, the impedance of the array of filled wells collapse dramatically (96 wells: R = 1Ohm, C=250nF). The power supply challenges accordingly raised by arrays of electrothermal micromixers will be then analyzed. The efficiency of different methods of mixing in those wells will be also compared: the addition of low frequency signal leading to AC electro-osmotic perturbations, a blinking vortices method. The experimental results will be compared to simulations.

  12. An automated 96-well-plate loader for FACScan.

    PubMed

    Illges, H

    1999-01-01

    Staining multiple samples for data acquisition with a flow cytometer is done in 96-well plates to save time and make large data assessment in one working day possible. However, the inability of the FACScan to take up the samples from 96-well plates is a major drawback. In order to avoid the individual transfer of samples to tubes, we have developed a system, which allows using the FACScan with 96-well plates. The machine consists of a programmable control module and a loader which moves the 96-well plate in 3 axis well by well along the sample collector. The machine is equipped with a wash buffer tank to avoid cross contamination of samples and a shaking option to avoid sedimentation of cells during acquisition. The machine can be further developed into a full automatic loader if connected to the FACS Station. In 24 hours about 7,000 samples with 10,000 cells each can be acquired.

  13. Solid phases of tenoxicam.

    PubMed

    Cantera, Rodrigo G; Leza, María G; Bachiller, Carmen M

    2002-10-01

    In this report we describe the preparation and characterization of four polymorphic forms of tenoxicam; they are, three 1:1 stoichiometric solvates with acetonitrile, dioxane, and N,N-dimethylformamide, and an amorphous phase obtained by recrystallization in various solvents. Polymorph IV and solvates with dioxane and N,N-dimethylformamide are reported for the first time in this paper. In addition, three solvates were crystallized in acetone, ethyl acetate, and isopropyl alcohol. These solid forms were characterized by X-ray powder diffraction, differential scanning calorimetry, infrared spectroscopy, thermogravimetry, optical microscopy, and elemental analysis. Solid-state properties, intrinsic dissolution rate, and dissolution kinetics from formulated tablets are also provided.

  14. Solid phase extraction membrane

    DOEpatents

    Carlson, Kurt C [Nashville, TN; Langer, Roger L [Hudson, WI

    2002-11-05

    A wet-laid, porous solid phase extraction sheet material that contains both active particles and binder and that possesses excellent wet strength is described. The binder is present in a relatively small amount while the particles are present in a relatively large amount. The sheet material is sufficiently strong and flexible so as to be pleatable so that, for example, it can be used in a cartridge device.

  15. 96-well electroporation method for transfection of mammalian central neurons.

    PubMed

    Buchser, William J; Pardinas, Jose R; Shi, Yan; Bixby, John L; Lemmon, Vance P

    2006-11-01

    Manipulating gene expression in primary neurons has been a goal for many scientists for over 20 years. Vertebrate central nervous system neurons are classically difficult to transfect. Most lipid reagents are inefficient and toxic to the cells, and time-consuming methods such as viral infections are often required to obtain better efficiencies. We have developed an efficient method for the transfection of cerebellar granule neurons and hippocampal neurons with standard plasmid vectors. Using 96-well electroporation plates, square-wave pulses can introduce 96 different plasmids into neurons in a single step. The procedure results in greater than 20% transfection efficiencies and requires only simple solutions of nominal cost. In addition to enabling the rapid optimization of experimental protocols with multiple parameters, this procedure enables the use of high content screening methods to characterize neuronal phenotypes.

  16. 96-Well electroporation method for transfection of mammalian central neurons

    PubMed Central

    Buchser, William J.; Pardinas, Jose R.; Shi, Yan; Bixby, John L.; Lemmon, Vance P.

    2008-01-01

    Manipulating gene expression in primary neurons has been a goal for many scientists for over 20 years. Vertebrate central nervous system neurons are classically difficult to transfect. Most lipid reagents are inefficient and toxic to the cells, and time-consuming methods such as viral infections are often required to obtain better efficiencies. We have developed an efficient method for the transfection of cerebellar granule neurons and hippocampal neurons with standard plasmid vectors. Using 96-well electroporation plates, square-wave pulses can introduce 96 different plasmids into neurons in a single step. The procedure results in greater than 20% transfection efficiencies and requires only simple solutions of nominal cost. In addition to enabling the rapid optimization of experimental protocols with multiple parameters, this procedure enables the use of high content screening methods to characterize neuronal phenotypes. PMID:17140120

  17. Solid phase microextraction field kit

    DOEpatents

    Nunes, Peter J.; Andresen, Brian D.

    2005-08-16

    A field kit for the collection, isolation and concentration of trace amounts of high explosives (HE), biological weapons (BW) and chemical weapons (CW) residues in air, soil, vegetation, swipe, and liquid samples. The field kit includes a number of Solid Phase Microextraction (SPME) fiber and syringe assemblies in a hermetically sealed transportation container or tubes which includes a sampling port, a number of extra SPME fiber and syringe assemblies, the fiber and syringe assemblies including a protective cap for the fiber, and an extractor for the protective cap, along with other items including spare parts, protective glove, and an instruction manual, all located in an airtight container.

  18. Colorimetric Solid-Phase Extractor

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The heart of a colorimetric solid phase extractor (CSPE) test kit quickly measures the concentration of the biocides silver or iodine in astronauts' drinking water to determine whether concentrations are safe. When 10 milliliters (ml) of water is drawn through the disk, the disk will turn color (yellow in this picture for iodine) indicating the presence of the biocides. The device could someday be used to test water safety at reservoirs and water treatment plants on Earth. (photo credit: Microanalytical Instrumentation Center, Iowa State University).

  19. Equilibrium drug solubility measurements in 96-well plates reveal similar drug solubilities in phosphate buffer pH 6.8 and human intestinal fluid.

    PubMed

    Heikkilä, Tiina; Karjalainen, Milja; Ojala, Krista; Partola, Kirsi; Lammert, Frank; Augustijns, Patrick; Urtti, Arto; Yliperttula, Marjo; Peltonen, Leena; Hirvonen, Jouni

    2011-02-28

    This study was conducted to develop a high throughput screening (HTS) method for the assessment of equilibrium solubility of drugs. Solid-state compounds were precipitated from methanol in 96-well plates, in order to eliminate the effect of co-solvent. Solubility of twenty model drugs was analyzed in water and aqueous solutions (pH 1.2 and 6.8) in 96-well plates and in shake-flasks (UV detection). The results obtained with the 96-well plate method correlated well (R(2)=0.93) between the shake-flask and 96-well plates over the wide concentration scale of 0.002-169.2mg/ml. Thereafter, the solubility tests in 96-well plates were performed using fasted state human intestinal fluid (HIF) from duodenum of healthy volunteers. The values of solubility were similar in phosphate buffer solution (pH 6.8) and HIF over the solubility range of 10(2)-10(5)μg/ml. The new 96-well plate method is useful for the screening of equilibrium drug solubility during the drug discovery process and it also allows the use of human intestinal fluid in solubility screening.

  20. Solid Phase Characterization of Solids Recovered from Failed Sluicer Arm

    SciTech Connect

    Cooke, Gary A.

    2015-03-09

    The Enclosure to this memo discusses the solid phase characterization of a solid sample that was retrieved from the single-shell Tank 241-C-111 extended reach sluicer #2. This sluicer, removed from riser #3 on September 25, 2014, was found to have approximately 0.4 gallons of solid tank waste adhering to the nozzle area.

  1. HIGHLY SENSITIVE ASSAY FOR ANTICHOLINESTERASE COMPOUNDS USING 96 WELL PLATE FORMAT

    EPA Science Inventory

    The rapid and sensitive detection of organophosphate insecticides using a 96 well plate format is reported. Several features of this assay make it attractive for development as a laboratory-based or field screening assay. Acetylcholinesterase (AChE) was stabilized in a gelati...

  2. A comparison of observables for solid-solid phase transitions

    SciTech Connect

    Smilowitz, Laura B; Henson, Bryan F; Romero, Jerry J

    2009-01-01

    The study of solid-solid phase transformations is hindered by the difficulty of finding a volumetric probe to use as a progress variable. Solids are typically optically opaque and heterogeneous. Over the past several years, second harmonic generation (SHG) has been used as a kinetic probe for a solid-solid phase transition in which the initial and final phases have different symmetries. Bulk generation of SHG is allowed by symmetry only in noncentrosymmetric crystallographic space groups. For the organic energetic nitramine octahydro-1,3 ,5,7 -tetranitro-1,3 ,5,7 -tatrazocine (HMX), the beta phase is centro symmetric (space group P2{sub 1}/c) and the delta phase iS noncentrosymmetric (space group P6{sub 1}22) making SHG an extremely sensitive, essentially zero background probe of the phase change progress. We have used SHG as a tool to follow the progress of the transformation from beta to delta phase during the solid-solid transformation. However, kinetic models of the transformation derived using different observables from several other groups have differed, showing later onset for the phase change and faster progression to completion. In this work, we have intercompared several techniques to understand these differences. The three techniques discussed are second harmonic generation, Raman spectroscopy, and differential scanning calorimetry (DSC). The progress of the beta to delta phase transition in HMX observed with each of these different probes will be discussed and advantages and disadvantages of each technique described. This paper compares several different observables for use in measuring the kinetics of solid-solid phase transitions. Relative advantages and disadvantages for each technique are described and a direct comparison of results is made for the beta to delta polymorphic phase transition of the energetic nitramine, octahydro-1,3,5,7-tetranitro-1,3,5,7-tatrazocine.

  3. An improved 96-well turbidity assay for T4 lysozyme activity

    PubMed Central

    Toro, Tasha B.; Nguyen, Thao P.; Watt, Terry J.

    2015-01-01

    T4 lysozyme (T4L) is an important model system for investigating the relationship between protein structure and function. Despite being extensively studied, a reliable, quantitative activity assay for T4L has not been developed. Here, we present an improved T4L turbidity assay as well as an affinity-based T4L expression and purification protocol. This assay is designed for 96-well format and utilizes conditions amenable for both T4L and other lysozymes. This protocol enables easy, efficient, and quantitative characterization of T4L variants and allows comparison between different lysozymes. Our method: • Is applicable for all lysozymes, with enhanced sensitivity for T4 lysozyme compared to other 96-well plate turbidity assays; • Utilizes standardized conditions for comparing T4 lysozyme variants and other lysozymes; and • Incorporates a simplified expression and purification protocol for T4 lysozyme. PMID:26150996

  4. 96-Well plate assays for measuring collagenase activity using (3)H-acetylated collagen.

    PubMed

    Koshy, P J; Rowan, A D; Life, P F; Cawston, T E

    1999-11-15

    We describe two alternative assays for measuring collagenolytic activity using (3)H-acetylated collagen. Both assays have been developed for the 96-well plate format and measure the amount of radiolabeled collagen fragments released into the supernatant from an insoluble (3)H-acetylated collagen fibril preparation. The first method separates digested solubilized fragments from the intact fibril by sedimentation of the undigested collagen by centrifugation. The second method achieves this separation by filtration of the supernatant through the membrane of a 96-well filtration plate which retains the undigested collagen fibril. Both methods give linear dose- and time-dependent responses of collagenase activity > or = 70% of total collagen lysis. In addition, both assays can be simply modified to measure tissue inhibitors of metalloproteinases (TIMPs) inhibitory activity, which is also linear between 20 and 75% of total collagen lysis with the amount of TIMP added.

  5. A 96-well plate assay for CYP4503A induction using cryopreserved human hepatocytes.

    PubMed

    Kamiguchi, Naomi; Aoyama, Eiji; Okuda, Teruaki; Moriwaki, Toshiya

    2010-11-01

    A reliable and practical CYP3A induction assay with cryopreserved human hepatocytes in a 96-well format was developed. Various 96-well plates with different basement membrane were evaluated using prototypical inducers, rifampicin, phenytoin, and carbamazepine. Thin-layer (TL) Matrigel was found to yield the highest basal and induced levels of CYP3A activity as determined by testosterone 6β-hydroxylation. Concentration-dependent CYP3A induction of rifampicin was reproducible with the EC(50) values of 0.36 ± 0.28 μM from four batches of human hepatocytes using the 96-well plate with TL Matrigel. The rank order of induction potency for nine inducers or noninducers at a concentration of 10 μM were well comparable among the multiple donors, by expressing the results as percentage of change compared with the positive control, 10 μM rifampicin. Cotreatment of avasimibe or efavirenz with 10 μM rifampicin was found to reduce CYP3A activities induced by rifampicin at a lower rate than treatment with rifampicin alone, whereas treatment with phenobarbital and carbamazepine had no effect. From a comparison of induced CYP3A activities and gene expression levels, there were compounds that would cause induction of CYP3A4 mRNA but not activity, presumably due to their inhibitory effect on CYP3A activity. The cotreatment assay of test compound with rifampicin allows us to exclude the false-negative results caused by the cytotoxicity and/or the mechanism-based inactivation, when the drug candidate's ability for CYP3A induction is evaluating the enzyme activity. This 96-well plate assay, which is robust, reproducible, and convenient, has demonstrated the paramount applicability to the early drug discovery stage.

  6. Stretch Injury of Human Induced Pluripotent Stem Cell Derived Neurons in a 96 Well Format

    PubMed Central

    Sherman, Sydney A.; Phillips, Jack K.; Costa, J. Tighe; Cho, Frances S.; Oungoulian, Sevan R.; Finan, John D.

    2016-01-01

    Traumatic brain injury (TBI) is a major cause of mortality and morbidity with limited therapeutic options. Traumatic axonal injury (TAI) is an important component of TBI pathology. It is difficult to reproduce TAI in animal models of closed head injury, but in vitro stretch injury models reproduce clinical TAI pathology. Existing in vitro models employ primary rodent neurons or human cancer cell line cells in low throughput formats. This in vitro neuronal stretch injury model employs human induced pluripotent stem cell-derived neurons (hiPSCNs) in a 96 well format. Silicone membranes were attached to 96 well plate tops to create stretchable, culture substrates. A custom-built device was designed and validated to apply repeatable, biofidelic strains and strain rates to these plates. A high content approach was used to measure injury in a hypothesis-free manner. These measurements are shown to provide a sensitive, dose-dependent, multi-modal description of the response to mechanical insult. hiPSCNs transition from healthy to injured phenotype at approximately 35% Lagrangian strain. Continued development of this model may create novel opportunities for drug discovery and exploration of the role of human genotype in TAI pathology. PMID:27671211

  7. Solid phase thermodynamic perturbation theory: test and application to multiple solid phases.

    PubMed

    Zhou, Shiqi

    2007-08-28

    A simple procedure for the determination of hard sphere (HS) solid phase radial distribution function (rdf) is proposed, which, thanks to its physical foundation, allows for extension to other crystal structures besides the fcc structure. The validity of the procedure is confirmed by comparing (1) the predicted HS solid phase rdf's with corresponding simulation data and (2) the predicted non-HS solid phase Helmholtz free energy by the present solid phase first-order thermodynamic perturbation theory (TPT) whose numerical implementation depends on the HS solid phase rdf's as input, with the corresponding predictions also by the first-order TPT but the required HS solid phase rdf is given by an "exact" empirical simulation-fitted formula. The present solid phase first-order TPT predicts isostructural fcc-fcc transition of a hard core attractive Yukawa fluid, in very satisfactory agreement with the corresponding simulation data and is far more accurate than a recent thermodynamically consistent density functional perturbation theory. The present solid phase first-order TPT is employed to investigate multiple solid phases. It is found that a short-ranged potential, even if it is continuous and differentiable or is superimposed over a long-ranged potential, is sufficient to induce the multiple solid phases. When the potential range is short enough, not only isostructural fcc-fcc transition but also isostructural bcc-bcc transition, simple cubic (sc)-sc transition, or even fcc-bcc, fcc-sc, and bcc-sc transitions can be induced. Even triple point involving three solid phases becomes possible. The multiple solid phases can be stable or metastable depending on the potential parameters.

  8. Binary Solid-Liquid Phase Equilibria

    ERIC Educational Resources Information Center

    Ellison, Herbert R.

    1978-01-01

    Indicates some of the information that may be obtained from a binary solid-liquid phase equilibria experiment and a method to write a computer program that will plot an ideal phase diagram to which the experimental results may be compared. (Author/CP)

  9. High throughput preparation of fly genomic DNA in 96-well format using a paint-shaker.

    PubMed

    Lang, Michael; Nagy, Olga; Lang, Claus; Orgogozo, Virginie

    2015-01-01

    Sample homogenization is an essential step for genomic DNA extraction, with multiple downstream applications in Molecular Biology. Genotyping hundreds or thousands of samples requires an automation of this homogenization step, and high throughput homogenizer equipment currently costs 7000 euros or more. We present an apparatus for homogenization of individual Drosophila adult flies in 96-well micro-titer dishes, which was built from a small portable paint-shaker (F5 portable paint-shaker, Ushake). Single flies are disrupted in each well that contains extraction buffer and a 4-mm metal ball. Our apparatus can hold up to five 96-well micro-titer plates. Construction of the homogenizer apparatus takes about 3-4 days, and all equipment can be obtained from a home improvement store. The total material cost is approximately 700 euros including the paint-shaker. We tested the performance of our apparatus using the ZR-96 Quick-gDNA™ kit (Zymo Research) homogenization buffer and achieved nearly complete tissue homogenization after 15 minutes of shaking. PCR tests did not detect any cross contamination between samples of neighboring wells. We obtained on average 138 ng of genomic DNA per fly, and DNA quality was adequate for standard PCR applications. In principle, our tissue homogenizer can be used for isolation of DNA suitable for library production and high throughput genotyping by Multiplexed Shotgun Genotyping (MSG), as well as RNA isolation from single flies. The sample adapter can also hold and shake other items, such as centrifuge tubes (15-50 mL) or small bottles.

  10. High throughput preparation of fly genomic DNA in 96-well format using a paint-shaker

    PubMed Central

    Lang, Michael; Nagy, Olga; Lang, Claus; Orgogozo, Virginie

    2015-01-01

    Sample homogenization is an essential step for genomic DNA extraction, with multiple downstream applications in Molecular Biology. Genotyping hundreds or thousands of samples requires an automation of this homogenization step, and high throughput homogenizer equipment currently costs 7000 euros or more. We present an apparatus for homogenization of individual Drosophila adult flies in 96-well micro-titer dishes, which was built from a small portable paint-shaker (F5 portable paint-shaker, Ushake). Single flies are disrupted in each well that contains extraction buffer and a 4-mm metal ball. Our apparatus can hold up to five 96-well micro-titer plates. Construction of the homogenizer apparatus takes about 3–4 days, and all equipment can be obtained from a home improvement store. The total material cost is approximately 700 euros including the paint-shaker. We tested the performance of our apparatus using the ZR-96 Quick-gDNA™ kit (Zymo Research) homogenization buffer and achieved nearly complete tissue homogenization after 15 minutes of shaking. PCR tests did not detect any cross contamination between samples of neighboring wells. We obtained on average 138 ng of genomic DNA per fly, and DNA quality was adequate for standard PCR applications. In principle, our tissue homogenizer can be used for isolation of DNA suitable for library production and high throughput genotyping by Multiplexed Shotgun Genotyping (MSG), as well as RNA isolation from single flies. The sample adapter can also hold and shake other items, such as centrifuge tubes (15–50 mL) or small bottles. PMID:26818699

  11. Solid phase sequencing of biopolymers

    SciTech Connect

    Cantor, Charles R.; Hubert, Koster

    2014-06-24

    This invention relates to methods for detecting and sequencing target nucleic acid sequences, to mass modified nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probes comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Probes may be affixed to a solid support such as a hybridization chip to facilitate automated molecular weight analysis and identification of the target sequence.

  12. Solid phase sequencing of biopolymers

    DOEpatents

    Cantor, Charles; Koster, Hubert

    2010-09-28

    This invention relates to methods for detecting and sequencing target nucleic acid sequences, to mass modified nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probes comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include DNA or RNA in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated molecular weight analysis and identification of the target sequence.

  13. Nonthermal solid-to-solid phase transitions in tungsten

    NASA Astrophysics Data System (ADS)

    Giret, Yvelin; Daraszewicz, Szymon L.; Duffy, Dorothy M.; Shluger, Alexander L.; Tanimura, Katsumi

    2014-09-01

    The ab initio calculations of phonon dispersions and nonthermal forces along structural deformation paths were used to study nonthermal solid-to-solid phase transitions in photoexcited tungsten. We assumed that electronic excitation can be described by an electronic temperature and demonstrated that nonthermal, i.e., caused purely by electronic excitation, bcc-to-fcc and bcc-to-hcp phase transitions can occur for electronic temperatures between 1.7 and 4.3 eV. These transitions result from soft modes along the Σ line of the Brillouin zone. Structural path calculations at different electronic temperatures indicate that both transitions are likely to take place in nonequilibrium conditions. We further predict that transient fcc and hcp phases of tungsten could be observed for several ps.

  14. Solid-liquid phase transition in argon

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Tang, H. T.

    1978-01-01

    Starting from the Lennard-Jones interatomic potential, a modified cell theory has been used to describe the solid-liquid phase transition in argon. The cell-size variations may be evaluated by a self-consistent condition. With the inclusion of cell-size variations, the transition temperature, the solid and liquid densities, and the liquid-phase radial-distribution functions have been calculated. These ab initio results are in satisfactory agreement with molecular-dynamics calculations as well as experimental data on argon.

  15. Enzyme activity assay of glycoprotein enzymes based on a boronate affinity molecularly imprinted 96-well microplate.

    PubMed

    Bi, Xiaodong; Liu, Zhen

    2014-12-16

    Enzyme activity assay is an important method in clinical diagnostics. However, conventional enzyme activity assay suffers from apparent interference from the sample matrix. Herein, we present a new format of enzyme activity assay that can effectively eliminate the effects of the sample matrix. The key is a 96-well microplate modified with molecularly imprinted polymer (MIP) prepared according to a newly proposed method called boronate affinity-based oriented surface imprinting. Alkaline phosphatase (ALP), a glycoprotein enzyme that has been routinely used as an indicator for several diseases in clinical tests, was taken as a representative target enzyme. The prepared MIP exhibited strong affinity toward the template enzyme (with a dissociation constant of 10(-10) M) as well as superb tolerance for interference. Thus, the enzyme molecules in a complicated sample matrix could be specifically captured and cleaned up for enzyme activity assay, which eliminated the interference from the sample matrix. On the other hand, because the boronate affinity MIP could well retain the enzymatic activity of glycoprotein enzymes, the enzyme captured by the MIP was directly used for activity assay. Thus, additional assay time and possible enzyme or activity loss due to an enzyme release step required by other methods were avoided. Assay of ALP in human serum was successfully demonstrated, suggesting a promising prospect of the proposed method in real-world applications.

  16. A Microfabricated 96-Well 3D Assay Enabling High-Throughput Quantification of Cellular Invasion Capabilities

    PubMed Central

    Hao, Rui; Wei, Yuanchen; Li, Chaobo; Chen, Feng; Chen, Deyong; Zhao, Xiaoting; Luan, Shaoliang; Fan, Beiyuan; Guo, Wei; Wang, Junbo; Chen, Jian

    2017-01-01

    This paper presents a 96-well microfabricated assay to study three-dimensional (3D) invasion of tumor cells. A 3D cluster of tumor cells was first generated within each well by seeding cells onto a micro-patterned surface consisting of a central fibronectin-coated area that promotes cellular attachment, surrounded by a poly ethylene glycol (PEG) coated area that is resistant to cellular attachment. Following the formation of the 3D cell clusters, a 3D collagen extracellular matrix was formed in each well by thermal-triggered gelation. Invasion of the tumor cells into the extracellular matrix was subsequently initiated and monitored. Two modes of cellular infiltration were observed: A549 cells invaded into the extracellular matrix following the surfaces previously coated with PEG molecules in a pseudo-2D manner, while H1299 cells invaded into the extracellular matrix in a truly 3D manner including multiple directions. Based on the processing of 2D microscopic images, a key parameter, namely, equivalent invasion distance (the area of invaded cells divided by the circumference of the initial cell cluster) was obtained to quantify migration capabilities of these two cell types. These results validate the feasibility of the proposed platform, which may function as a high-throughput 3D cellular invasion assay. PMID:28240272

  17. A Microfabricated 96-Well 3D Assay Enabling High-Throughput Quantification of Cellular Invasion Capabilities.

    PubMed

    Hao, Rui; Wei, Yuanchen; Li, Chaobo; Chen, Feng; Chen, Deyong; Zhao, Xiaoting; Luan, Shaoliang; Fan, Beiyuan; Guo, Wei; Wang, Junbo; Chen, Jian

    2017-02-27

    This paper presents a 96-well microfabricated assay to study three-dimensional (3D) invasion of tumor cells. A 3D cluster of tumor cells was first generated within each well by seeding cells onto a micro-patterned surface consisting of a central fibronectin-coated area that promotes cellular attachment, surrounded by a poly ethylene glycol (PEG) coated area that is resistant to cellular attachment. Following the formation of the 3D cell clusters, a 3D collagen extracellular matrix was formed in each well by thermal-triggered gelation. Invasion of the tumor cells into the extracellular matrix was subsequently initiated and monitored. Two modes of cellular infiltration were observed: A549 cells invaded into the extracellular matrix following the surfaces previously coated with PEG molecules in a pseudo-2D manner, while H1299 cells invaded into the extracellular matrix in a truly 3D manner including multiple directions. Based on the processing of 2D microscopic images, a key parameter, namely, equivalent invasion distance (the area of invaded cells divided by the circumference of the initial cell cluster) was obtained to quantify migration capabilities of these two cell types. These results validate the feasibility of the proposed platform, which may function as a high-throughput 3D cellular invasion assay.

  18. Thermodynamic equilibrium solubility measurements in simulated fluids by 96-well plate method in early drug discovery.

    PubMed

    Bharate, Sonali S; Vishwakarma, Ram A

    2015-04-01

    An early prediction of solubility in physiological media (PBS, SGF and SIF) is useful to predict qualitatively bioavailability and absorption of lead candidates. Despite of the availability of multiple solubility estimation methods, none of the reported method involves simplified fixed protocol for diverse set of compounds. Therefore, a simple and medium-throughput solubility estimation protocol is highly desirable during lead optimization stage. The present work introduces a rapid method for assessment of thermodynamic equilibrium solubility of compounds in aqueous media using 96-well microplate. The developed protocol is straightforward to set up and takes advantage of the sensitivity of UV spectroscopy. The compound, in stock solution in methanol, is introduced in microgram quantities into microplate wells followed by drying at an ambient temperature. Microplates were shaken upon addition of test media and the supernatant was analyzed by UV method. A plot of absorbance versus concentration of a sample provides saturation point, which is thermodynamic equilibrium solubility of a sample. The established protocol was validated using a large panel of commercially available drugs and with conventional miniaturized shake flask method (r(2)>0.84). Additionally, the statistically significant QSPR models were established using experimental solubility values of 52 compounds.

  19. Urine sample preparation in 96-well filter plates for quantitative clinical proteomics.

    PubMed

    Yu, Yanbao; Suh, Moo-Jin; Sikorski, Patricia; Kwon, Keehwan; Nelson, Karen E; Pieper, Rembert

    2014-06-03

    Urine is an important, noninvasively collected body fluid source for the diagnosis and prognosis of human diseases. Liquid chromatography mass spectrometry (LC-MS) based shotgun proteomics has evolved as a sensitive and informative technique to discover candidate disease biomarkers from urine specimens. Filter-aided sample preparation (FASP) generates peptide samples from protein mixtures of cell lysate or body fluid origin. Here, we describe a FASP method adapted to 96-well filter plates, named 96FASP. Soluble urine concentrates containing ~10 μg of total protein were processed by 96FASP and LC-MS resulting in 700-900 protein identifications at a 1% false discovery rate (FDR). The experimental repeatability, as assessed by label-free quantification and Pearson correlation analysis for shared proteins among replicates, was high (R ≥ 0.97). Application to urinary pellet lysates which is of particular interest in the context of urinary tract infection analysis was also demonstrated. On average, 1700 proteins (±398) were identified in five experiments. In a pilot study using 96FASP for analysis of eight soluble urine samples, we demonstrated that protein profiles of technical replicates invariably clustered; the protein profiles for distinct urine donors were very different from each other. Robust, highly parallel methods to generate peptide mixtures from urine and other body fluids are critical to increase cost-effectiveness in clinical proteomics projects. This 96FASP method has potential to become a gold standard for high-throughput quantitative clinical proteomics.

  20. Urine Sample Preparation in 96-Well Filter Plates for Quantitative Clinical Proteomics

    PubMed Central

    2015-01-01

    Urine is an important, noninvasively collected body fluid source for the diagnosis and prognosis of human diseases. Liquid chromatography mass spectrometry (LC-MS) based shotgun proteomics has evolved as a sensitive and informative technique to discover candidate disease biomarkers from urine specimens. Filter-aided sample preparation (FASP) generates peptide samples from protein mixtures of cell lysate or body fluid origin. Here, we describe a FASP method adapted to 96-well filter plates, named 96FASP. Soluble urine concentrates containing ∼10 μg of total protein were processed by 96FASP and LC-MS resulting in 700–900 protein identifications at a 1% false discovery rate (FDR). The experimental repeatability, as assessed by label-free quantification and Pearson correlation analysis for shared proteins among replicates, was high (R ≥ 0.97). Application to urinary pellet lysates which is of particular interest in the context of urinary tract infection analysis was also demonstrated. On average, 1700 proteins (±398) were identified in five experiments. In a pilot study using 96FASP for analysis of eight soluble urine samples, we demonstrated that protein profiles of technical replicates invariably clustered; the protein profiles for distinct urine donors were very different from each other. Robust, highly parallel methods to generate peptide mixtures from urine and other body fluids are critical to increase cost-effectiveness in clinical proteomics projects. This 96FASP method has potential to become a gold standard for high-throughput quantitative clinical proteomics. PMID:24797144

  1. A rapid solid-phase protein microsequencer.

    PubMed Central

    Walker, J E; Fearnley, I M; Blows, R A

    1986-01-01

    A solid-phase protein microsequencer is described that has been designed to determine protein sequences with subnanomolar quantities of protein. Its utility has been demonstrated by the determination of many sequences in subunits of mitochondrial F1-ATPase, in a protein isolated from mouse gap junctions and in the mitochondrial phosphate-transporter protein. It has a number of advantages over liquid- and gas-phase sequencers. Firstly, the degradation cycle takes 24 min, more than twice as fast as any other sequencer. This helps to reduce exposure of proteins to inimical reagents and increases throughput of samples. Secondly, polar amino acids such as phosphoserine, and polar derivatives formed by active-site photoaffinity labelling with 8-azido-ATP, are recovered quantitatively from the reaction column and can be positively identified. In other types of sequencer these polar derivatives, being somewhat insoluble in butyl chloride, tend to remain in the reaction chamber of the instrument and so are more difficult to identify. The solid-phase protein sequencer is also more suited than the liquid-phase instrument for analysis of proteolipids from membranes. These hydrophobic proteins tend to dissolve in organic solvents during washing steps in the liquid-phase instrument and are lost. Covalent attachment as used in the solid-phase instrument solves this problem. PMID:3800890

  2. Multiplexed Colorimetric Solid-Phase Extraction

    NASA Technical Reports Server (NTRS)

    Gazda, Daniel B.; Fritz, James S.; Porter, Marc D.

    2009-01-01

    Multiplexed colorimetric solid-phase extraction (MC-SPE) is an extension of colorimetric solid-phase extraction (C-SPE) an analytical platform that combines colorimetric reagents, solid phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water. In CSPE, analytes are extracted and complexed on the surface of an extraction membrane impregnated with a colorimetric reagent. The analytes are then quantified directly on the membrane surface using a handheld diffuse reflectance spectrophotometer. Importantly, the use of solid-phase extraction membranes as the matrix for impregnation of the colorimetric reagents creates a concentration factor that enables the detection of low concentrations of analytes in small sample volumes. In extending C-SPE to a multiplexed format, a filter holder that incorporates discrete analysis channels and a jig that facilitates the concurrent operation of multiple sample syringes have been designed, enabling the simultaneous determination of multiple analytes. Separate, single analyte membranes, placed in a readout cartridge create unique, analyte-specific addresses at the exit of each channel. Following sample exposure, the diffuse reflectance spectrum of each address is collected serially and the Kubelka-Munk function is used to quantify each water quality parameter via calibration curves. In a demonstration, MC-SPE was used to measure the pH of a sample and quantitate Ag(I) and Ni(II).

  3. Development of a rapid, 96-well alkaline based differential DNA extraction method for sexual assault evidence.

    PubMed

    Hudlow, William R; Buoncristiani, Martin R

    2012-01-01

    We present a rapid alkaline lysis procedure for the extraction of DNA from sexual assault evidence that generates purified sperm fraction extracts that yield STR typing results similar to those obtained from the traditional organic/dithiothreitol differential extraction. Specifically, a sodium hydroxide based differential extraction method has been developed in a single-tube format and further optimized in a 96-well format. The method yields purified extracts from a small sample set (≈ 2-6 swabs) in approximately 2h and from a larger sample set (up to 96 swabs) in approximately 4h. While conventional differential extraction methods require vigorous sample manipulation to remove the spermatozoa from the substrate, the method described here exploits the propensity of sperm to adhere to a substrate and does not require any manipulation of the substrate after it is sampled. For swabs, sample handling is minimized by employing a process where the tip of the swab, including the shaft, is transferred to the appropriate vessel eliminating the need for potentially hazardous scalpels to separate the swab material from the shaft. The absence of multiple handling steps allows the process to be semi-automated, however the procedure as described here does not require use of a robotic system. This method may provide forensic laboratories a cost-effective tool for the eradication of backlogs of sexual assault evidence, and more timely service to their client agencies. In addition, we have demonstrated that a modification of the procedure can be used to retrieve residual sperm-cell DNA from previously extracted swabs.

  4. Megabar pressure phases of solid hydrogen

    NASA Astrophysics Data System (ADS)

    Chen, Nancy Hueling

    The behavior of solid Hsb2, Dsb2, and HD at low temperatures high pressures was investigated. The experimental data were obtained by combining high pressure diamond anvil cell apparatus with cryogenic and spectroscopic techniques. Megabar pressures (1 bar = 10sp5 Pa) and liquid helium temperatures were accessible. The observed phases and phase lines are discussed with respect to orientational order, crystal structure, and electronic properties. The orientational order-disorder phase transition in HD was studied by Raman spectroscopy. Due to the distinguishability of the nuclei in an HD molecule, the observed phase line exhibits surprising behavior relative to that expected for the homonuclear molecules Hsb2 and Dsb2. The megabar pressure phase diagram of solid Dsb2 was investigated by infrared and Raman spectroscopy. The broken symmetry phase (BSP) transition line and the D-A phase line were observed to meet at a triple point. The relative arrangement of phase lines in P-T space, combined with group theoretical analysis of observed infrared and Raman spectra within the phases, sets symmetry restrictions on the allowed crystal structures. The electronic properties of the high pressure H-A and D-A phases were examined, since these recently discovered phases were suspected of being metallic. Acquired broadband infrared absorption spectra extending to 10 mum were analyzed in terms of the Drude model for metals. No evidence indicating metallic behavior was found. Refinements in high pressure techniques were explored, in order to increase the maximum pressures attainable. A method of extending ruby fluorescence pressure measurements to multimegabar pressures was developed, which involved excitation of ruby fluorescence with red, rather than blue or green laser light.

  5. Phospholipid removal combined with a semi-automated 96-well SPE application for determination of budesonide in human plasma with LC-MS/MS.

    PubMed

    Nilsson, Karin; Andersson, Maria; Beck, Olof

    2014-11-01

    A semi-automated method for quantification of budesonide in human plasma was developed, validated, and applied for high-volume analysis of samples in connection with a pharmacokinetic study. Protein and phospholipid removal was performed using an Ostro 96-well filter plate and subsequently combined with C18 solid-phase extraction on a Hamilton Microlab STARlet automation robot. The final extracts were evaporated to dryness and redissolved in 20% acetonitrile/water. The procedure used budesonide-d8 as internal standard and gave a 3.5-fold concentration of plasma to extract. The final extracts (5 μL injected) were analyzed with selected reaction monitoring liquid chromatography-tandem mass spectrometry (LC-MS/MS) using electrospray ionization in positive mode. The chromatography system used a 100 mm ACQUITY BEH UPLC column and a gradient system consisting of aqueous 0.1% formic acid and acetonitrile as organic modifier. Phospholipid removal was found to be needed during method development in order to reduce ion suppression effects from matrix and to increase method sensitivity. The measuring range was 50-5000 pg/mL with and LOD 24 pg/mL. Calibration response showed good linearity (correlation coefficients<0.99) over the measuring range. The absolute recovery over the sample preparation procedure was estimated to 67%. Total imprecision was <9% at three levels and accuracy was between 98.9 and 103%. The method was successfully applied for analysis of 864 study samples in a short time. The quality control samples at concentration levels 200 and 2000 pg/mL gave a total imprecision of 7.4% and 4.2%, respectively, (n=95).

  6. Solid phase synthesis of bifunctional antibodies.

    PubMed

    DeSilva, B S; Wilson, G S

    1995-12-15

    Bifunctional antibodies were prepared using the principle of solid-phase synthesis. The two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')2 fragments from intact IgG were prepared using an immobilized pepsin column. Goat, mouse and human antibodies were digested completely within 4 h. The F(ab')2 fragments thus produced did not contain any IgG impurities. The Fab' fragments were produced by reducing the inter-heavy chain disulfide bonds using 2-mercaptoethylamine. The use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of the bifunctional antibody preparation and the rapid optimization of reaction conditions.

  7. Solid-solid phase transition measurements in iron

    SciTech Connect

    Schwartz, Cynthia Louise

    2010-01-01

    Previously, dynamic experiments on iron have observed a non-zero transition time and width in the solid-solid {alpha}-{var_epsilon} phase transition. Using Proton Radiography at the Los Alamos Neutron Science Center, we have performed plate impact experiments on iron to further study the {alpha}-{var_epsilon} phase transition which occurs at 13GPa. A 40mm bore powder gun was coupled to a proton radiography beam line and imaging system and synchronized to the impact of the projectile on the target sample with the proton beam pattern. A typical experimental configuration for the iron study, as shown below in 3 color-enhanced radiographs, is a 40mm diameter aluminum sabot impacting a 40mm diameter of polycrystalline ARMCO iron. The iron is backed by a sapphire optical window for velocimetry measurements. The aluminum flyer on the left of the iron is barely visible for visual display purposes. Direct density jumps were measured which corresponded to calculations to within 1% using a Wondy mUlti-phase equation of state model. In addition, shock velocities were measured using an edge fitting technique and followed that edge movement from radiograph to radiograph, where radiographs are separated in time by 500 ns. Preliminary measurements give a shock velocity (P1 wave) of 5.251 km/s. The projectile velocity was 0.725 km/s which translate to a peak stress of 17.5 GPa. Assuming the P1 wave is instantaneous, we are able to calibrate the chromatic, motion, object and camera blur by measuring the width of the P1 wave. This approximation works in this case since each of the two density jumps are small compared to the density of the object. Subtracting the measured width of the P1 wave in quadrature from the width of the P2 wave gives a preliminary measurement of the transition length of 265 {mu}m. Therefore, a preliminary measured phase transition relaxation time {tau} = transition length/u{sub s} = 265 {mu}m/5.251 km/s = 50 ns. Both Boettger and Jensen conclude that the

  8. Kinetics of Solid-Solid Phase Transition in Iron (u)

    SciTech Connect

    Schwartz, Cynthia, L

    2011-01-27

    Previously, dynamic experiments on iron have observed a non-zero transition time and width in the solid-solid {alpha}-{var_epsilon} phase transition. Using Proton Radiography at the los Alamos Neutron Science Center, we have performed plate impact experiments on iron to further study the {alpha}-{var_epsilon} phase transition which occurs at 13GPa. A 40mm bore powder gun was coupled to a proton radiography beam line and imaging system and synchronized to the impact of the projectile on the target sample with the proton beam pattern. A typical experimental configuration for the iron study, as shown below in 3 color-enhanced radiographs, is a 40mm diameter aluminum sabot impacting a 40mm diameter of polycrystalline ARMCO iron. The iron is backed by a sapphire optical window for velocimetry measurements. The aluminum flyer on the left of the iron is barely visible for visual display purposes. Direct density jumps were measured which corresponded to calculations to within 1% using a Wondy multi-phase equation of state model. In addition, shock velocities were measured using an edge fitting technique and followed that edge movement from radiograph to radiograph, where rad iographs are separated in time by 500 ns. Preliminary measurements give a shock velocity (P1 wave) of 5.251 km/s. The projectile velocity was 0.725 km/s which translate to a peak stress of 17.5 GPa. Assuming the P1 wave is instantaneous, we are able to calibrate the chromatic, motion, object and camera blur by measuring the width of the P1 wave. This approximation works in this case since each of the two density jumps are small compared to the density of the object. Subtracting the measured width of the P1 wave in quadrature from the width of the P2 wave gives a preliminary measurement of the transition length of 265 {micro}m. Therefore, a preliminary measured phase transition relaxation time {tau} = transition length/u{sub s} = 265 {micro}m/5.251 km/s = 50 ns. Both Boettger1 & Jensen2 conclude that

  9. Assessment of a 96-Well Plate Assay of Quantitative Drug Susceptibility Testing for Mycobacterium Tuberculosis Complex in China

    PubMed Central

    Xia, Hui; Zheng, Yang; Zhao, Bing; van den Hof, Susan; Cobelens, Frank; Zhao, YanLin

    2017-01-01

    Objective To evaluate the performance of the Sensitire MYCOTB MIC Plate (MYCOTB) which could measure the twelve anti-tuberculosis drugs susceptibility on one 96-wells plate. Methods A total of 140 MDR-TB strains and 60 non-MDR strains were sub-cultured and 193 strains were finally tested for drug resistance using MYCOTB and agar proportion method (APM) and another 7 strains failed of subculture. The drugs included ofloxacin (Ofx), moxifloxacin (Mfx), rifampin (RFP), amikacin (Am), rifabutin (Rfb), para-aminosalicylic acid (PAS), ethionamide (Eth), isoniazid (INH), kanamycin (Km), ethambutol (EMB), streptomycin (Sm), and cycloserine(Cs). The categorical agreement, conditional agreement, sensitivity and specificity of MYCOTB were assessed in comparison with APM. For strains with inconsistent results between MYCOTB and APM, the drug resistance related gene fragments were amplified and sequenced: gyrA for Ofx and Mfx; rpoB for RFP and Rfb; embB for EMB; rpsl for Sm; katG and the promoter region of inhA for INH, ethA and the promoter region of inhA for Eth. The sequence results were compared with results of MYCOTB and APM to analyze the consistency between sequence results and MYCOTB or APM. Results The categorical agreement between two methods for each drug ranged from 88.6% to 100%. It was the lowest for INH (88.6%). The sensitivity and specificity of MYCOTB ranged from 71.4% to 100% and 84.3% to 100%, respectively. The sensitivity was lowest for Cs(71.4%), EMB at 10μg/ml (80.0%) and INH at 10.0μg/ml (84.6%). The specificity was lowest for Rfb (84.3%). Overall discordance between the two phenotypic methods was observed for 96 strains, of which 63 (65.6%) were found susceptible with APM and resistant with MYCOTB and the remaining 33(34.4%) strains were resistant by APM and susceptible with MYCOTB. 34/52 (65.4%) sequenced APM susceptible and MYCOTB resistant(APM-S/MYCOTB-R) strains had mutations or insertions in the amplified regions. 20/30 (66.7%) sequenced APM

  10. Solid-phase extraction in segmented flow.

    PubMed

    Rendl, Martin; Brandstetter, Thomas; Rühe, Jürgen

    2014-11-04

    Two-phase flow systems are increasingly popular for miniaturized, high-throughput performance of analytical or chemical reactions. In this contribution, we extend a previously described method that allows to increase the range of applications of heterogeneous reactions in two-phase flow, i.e., reactions that rely on isolation and purification of the compound of interest for downstream analysis. Our concept is based on liquid plugs, which serve as miniaturized compartments for the analytical reactions. Purification of the target compound is achieved by extracting the analyte from the aqueous compartments using magnetic beads as solid carriers. In the present paper, we elucidate the influence of parameters such as the polarity of the liquid/liquid and solid/liquid interfaces, the magnetic forces and the fluidic conditions onto the extraction performance. The conditions for reliable extraction and purification of the target compounds are determined. Furthermore, we investigate how to facilitate breaking of the plugs through reduction of the surface tension of the solid/liquid interface. When a lower surface tension is employed, a smaller number of beads is required for the extraction process, which implies a higher sensitivity of the device. In addition, we generate channels with different surface chemistries, which are able to manipulate the flow of the two immiscible liquids. We describe a very simple way to generate such devices and show that we can achieve a transition from segmented flow of plugs to a side-by side flow of the two immiscible liquids, a key requirement for the purification of the compounds.

  11. Density-functional theory for fluid-solid and solid-solid phase transitions

    NASA Astrophysics Data System (ADS)

    Bharadwaj, Atul S.; Singh, Yashwant

    2017-03-01

    We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u (r ) =ɛ "close="1 /n )">σ /r n , where parameter n measures softness of the potential. We find that for 1 /n ≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.

  12. High-throughput synthesis of conopeptides: a safety-catch linker approach enabling disulfide formation in 96-well format.

    PubMed

    Brust, Andreas; Tickle, Alice E

    2007-02-01

    Conotoxins exhibit a high degree of selectivity and potency for a range of pharmacologically relevant targets. The rapid access to libraries of conotoxin analogues, containing multiple intramolecular disulfide bridges for use in drug development, can be a very labor intensive, multi-step task. This work describes a high-throughput method for the synthesis of cystine-bridged conopeptides. Peptides were assembled on a peptide synthesizer employing the Fmoc solid-phase strategy using a safety-catch amide linker (SCAL). Side-chain protecting groups were removed on solid phase before SCAL activation with ammonium iodide in TFA, finally releasing the peptide into the TFA solution. Disulfide bond formation was performed in the cleavage mixture employing DMSO. This improved method allows mixtures of oxidized peptides to be obtained in parallel directly from a peptide synthesizer. A single HPLC purification of the resulting crude oxidized material produced peptides of > 95% purity.

  13. Solvent-assisted dispersive solid phase extraction.

    PubMed

    Jamali, Mohammad Reza; Firouzjah, Ahmad; Rahnama, Reyhaneh

    2013-11-15

    In this research, a novel extraction technique termed solvent-assisted dispersive solid phase extraction (SADSPE) was developed for the first time. The new method was based on the dispersion of the sorbent into the sample to maximize the contact surface. In this method, the dispersion of the sorbent at a very low milligram level was achieved by injecting a solution of the sorbent into the aqueous sample. Thereby, a cloudy solution formed. The cloudy state resulted from the dispersion of the fine particles of the sorbent in the bulk aqueous sample. After extraction, phase separation was performed by centrifugation and the enriched analyte in the sedimented phase could be determined by instrumental methods. The performance of SADSPE was illustrated with the determination of the trace amounts of cobalt(II) as a test analyte in food and environmental water samples by using flame atomic absorption spectrometry detection. Some key parameters for SADSPE, such as sorbent selection and amount, type and volume of dispersive solvent, pH, chelating agent concentration, and salt concentration, were investigated. Under the most favorable conditions, good limit of detection (as low as 0.2 µg L(-1)) and repeatability of extraction (RSD below 2.2%, n=10) was obtained. The accuracy of the method was tested with standard reference material (SRM-1643e and SRM-1640a) and spiked addition. The advantages of SADSPE method are simplicity of operation, rapidity, low cost, high recovery, and enrichment factor.

  14. Offline solid phase microextraction sampling system

    DOEpatents

    Harvey, Chris A.

    2008-12-16

    An offline solid phase microextraction (SPME) sampling apparatus for enabling SPME samples to be taken a number of times from a previously collected fluid sample (e.g. sample atmosphere) stored in a fused silica lined bottle which keeps volatile organics in the fluid sample stable for weeks at a time. The offline SPME sampling apparatus has a hollow body surrounding a sampling chamber, with multiple ports through which a portion of a previously collected fluid sample may be (a) released into the sampling chamber, (b) SPME sampled to collect analytes for subsequent GC analysis, and (c) flushed/purged using a fluidically connected vacuum source and purging fluid source to prepare the sampling chamber for additional SPME samplings of the same original fluid sample, such as may have been collected in situ from a headspace.

  15. Solid phase microextraction device using aerogel

    DOEpatents

    Miller, Fred S.; Andresen, Brian D.

    2005-06-14

    A sample collection substrate of aerogel and/or xerogel materials bound to a support structure is used as a solid phase microextraction (SPME) device. The xerogels and aerogels may be organic or inorganic and doped with metals or other compounds to target specific chemical analytes. The support structure is typically formed of a glass fiber or a metal wire (stainless steel or kovar). The devices are made by applying gel solution to the support structures and drying the solution to form aerogel or xerogel. Aerogel particles may be attached to the wet layer before drying to increase sample collection surface area. These devices are robust, stable in fields of high radiation, and highly effective at collecting gas and liquid samples while maintaining superior mechanical and thermal stability during routine use. Aerogel SPME devices are advantageous for use in GC/MS analyses due to their lack of interfering background and tolerance of GC thermal cycling.

  16. Nitrotyrosine Density of Rabbit Urinary Bladder Muscle and Mucosa Measured via Western Blotting and 96-Well Plate Analysis.

    PubMed

    Fitzpatrick, Brittany; Schuler, Catherine; Leggett, Robert E; Levin, Robert M

    2012-01-01

    Purpose. Nitrotyrosine was quantitated in rabbit bladder muscle and mucosa using two analytical systems: Western blotting analyses and a 96-well plate quantitative analysis kit. Materials and Methods. Rabbit bladder muscle and mucosa were obtained from control rabbits. For the Western analysis, the samples were loaded into a SDS page gel and then transferred to a PVDF membrane. The optical density was measured using a Kodak Scanner. Using the 96-well plate, the samples and standards were loaded, incubated with primary and secondary antibody, washed and vacuumed with 10x wash buffer three times between each incubation period. Stop buffer was added to the plate and the results were quantified via the plate reader. Results. For both muscle and mucosa tissue, the optical density readings were linear with tissue concentration; the concentration of nitrotyrosine in the mucosa was significantly higher than in the muscle. However, whereas the Western blot analysis is based on relative optical densities, the 96-well plate kit provides a truly quantitative analysis. Discussion. Mucosa tissue displayed a higher density of nitrotyrosine than did detrusor muscle tissue. This may well be due to the significantly higher metabolic activity of the mucosa compared to the muscle.

  17. Solid-phase microextraction in biomedical analysis.

    PubMed

    Ulrich, S

    2000-12-01

    Chromatographic methods are preferred in the analysis of organic molecules with lower molecular mass (<500 g/mol) in body fluids, i.e., the assay of drugs, metabolites, endogenous substances and poisons as well as of environmental exposure by gas chromatography (GC) and liquid chromatography (LC), for example. Sample preparation in biomedical analysis is mainly performed by liquid-liquid extraction and solid-phase extraction. However, new methods are investigated with the aim to increase the sample throughput and to improve the quality of analytical methods. Solid-phase microextraction (SPME) was introduced about a decade ago and it was mainly applied to environmental and food analysis. All steps of sample preparation, i.e., extraction, concentration, derivatization and transfer to the chromatograph, are integrated in one step and in one device. This is accomplished by the intelligent combination of an immobilized extraction solvent (a polymer) with a special geometry (a fiber within a syringe). It was a challenge to test this novel principle in biomedical analysis. Thus, an introduction is provided to the theory of SPME in the present paper. A critical review of the first applications to biomedical analyses is presented in the main paragraph. The optimization of SPME as well as advantages and disadvantages are discussed. It is concluded that, because of some unique characteristics, SPME can be introduced with benefit into several areas of biomedical analysis. In particular, the application of headspace SPME-GC-MS in forensic toxicology and environmental medicine appears to be promising. However, it seems that SPME will not become a universal method. Thus, on-line SPE-LC coupling with column-switching technique may be a good alternative if an analytical problem cannot be sufficiently dealt with by SPME.

  18. A 96-well screen filter plate for high-throughput biological sample preparation and LC-MS/MS analysis.

    PubMed

    Peng, Sean X; Cousineau, Martin; Juzwin, Stephen J; Ritchie, David M

    2006-01-01

    A novel 96-well screen filter plate (patent pending) has been invented to eliminate a time-consuming and labor-intensive step in preparation of in vivo study samples--to remove blood or plasma clots. These clots plug the pipet tips during a manual or automated sample-transfer step causing inaccurate pipetting or total pipetting failure. Traditionally, these blood and plasma clots are removed by picking them out manually one by one from each sample tube before any sample transfer can be made. This has significantly slowed the sample preparation process and has become a bottleneck for automated high-throughput sample preparation using robotic liquid handlers. Our novel screen filter plate was developed to solve this problem. The 96-well screen filter plate consists of 96 stainless steel wire-mesh screen tubes connected to the 96 openings of a top plate so that the screen filter plate can be readily inserted into a 96-well sample storage plate. Upon insertion, the blood and plasma clots are excluded from entering the screen tube while clear sample solutions flow freely into it. In this way, sample transfer can be easily completed by either manual or automated pipetting methods. In this report, three structurally diverse compounds were selected to evaluate and validate the use of the screen filter plate. The plasma samples of these compounds were transferred and processed in the presence and absence of the screen filter plate and then analyzed by LC-MS/MS methods. Our results showed a good agreement between the samples prepared with and without the screen filter plate, demonstrating the utility and efficiency of this novel device for preparation of blood and plasma samples. The device is simple, easy to use, and reusable. It can be employed for sample preparation of other biological fluids that contain floating particulates or aggregates.

  19. Ice-Cap: a method for growing Arabidopsis and tomato plants in 96-well plates for high-throughput genotyping.

    PubMed

    Su, Shih-Heng; Clark, Katie A; Gibbs, Nicole M; Bush, Susan M; Krysan, Patrick J

    2011-11-09

    It is becoming common for plant scientists to develop projects that require the genotyping of large numbers of plants. The first step in any genotyping project is to collect a tissue sample from each individual plant. The traditional approach to this task is to sample plants one-at-a-time. If one wishes to genotype hundreds or thousands of individuals, however, using this strategy results in a significant bottleneck in the genotyping pipeline. The Ice-Cap method that we describe here provides a high-throughput solution to this challenge by allowing one scientist to collect tissue from several thousand seedlings in a single day (1,2). This level of throughput is made possible by the fact that tissue is harvested from plants 96-at-a-time, rather than one-at-a-time. The Ice-Cap method provides an integrated platform for performing seedling growth, tissue harvest, and DNA extraction. The basis for Ice-Cap is the growth of seedlings in a stacked pair of 96-well plates. The wells of the upper plate contain plugs of agar growth media on which individual seedlings germinate. The roots grow down through the agar media, exit the upper plate through a hole, and pass into a lower plate containing water. To harvest tissue for DNA extraction, the water in the lower plate containing root tissue is rapidly frozen while the seedlings in the upper plate remain at room temperature. The upper plate is then peeled away from the lower plate, yielding one plate with 96 root tissue samples frozen in ice and one plate with 96 viable seedlings. The technique is named "Ice-Cap" because it uses ice to capture the root tissue. The 96-well plate containing the seedlings can then wrapped in foil and transferred to low temperature. This process suspends further growth of the seedlings, but does not affect their viability. Once genotype analysis has been completed, seedlings with the desired genotype can be transferred from the 96-well plate to soil for further propagation. We have demonstrated

  20. Streptomycetes in micro-cultures: growth, production of secondary metabolites, and storage and retrieval in the 96-well format.

    PubMed

    Minas, W; Bailey, J E; Duetz, W

    2000-12-01

    Mycelium-forming Streptomyces strains were grown in one milliliter liquid micro-cultures in square deep-well microtiter plates. Growth was evaluated with respect to biomass formation and production of secondary metabolites which were found to be very similar in the micro-cultures, bioreactor, and shake flask cultivations, respectively. Despite repetitive sampling and extensive growth on the walls of the wells, no cross contamination occurred. Furthermore, we successfully employed cold storage at -20 degrees C of spore suspensions (in the 96-well format), directly prepared from cultures grown on agar in the microtitre plate. Cultures were retrieved by replicating aliquots from the frozen spore suspensions.

  1. Solid-phase synthesis of quinolinone library.

    PubMed

    Kwak, Seung-Hwa; Kim, Min Jeong; Lee, So-Deok; You, Hyun; Kim, Yong-Chul; Ko, Hyojin

    2015-01-12

    Quinolinones have various biological activities, including antibacterial, anticancer, and antiviral properties. The 3-substituted amide quinolin-2(1H)-ones not only show antibacterial activity, but also act as immunomodulators, 5-HT4 receptor agonists, cannabinoid receptor inverse agonists, and AchE and, BuchE inhibitors. To investigate the potent biological activity of 3-substituted amide quinolin-2(1H)-ones, a large number of 3,5-amide substituted-2-oxoquinolinones were prepared by parallel solid-phase synthesis. The compound 5-amino-1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinoline-3-carboxylic acid was loaded onto 4-formyl-3,5-dimethoxyphenoxy (PL-FDMP) resin by reductive amination with high efficiency. Various building blocks were attached to the 3 and 5 positions to yield 3,5-disubstituted-2-oxoquinolinones with high purity and good yield. The ability some of these compound to inhibit the release of IL-1β, a cytokine involved in the immune response was measured, and they showed about 50% inhibition at 10 μM.

  2. Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

    NASA Technical Reports Server (NTRS)

    Hill, Carol M.; Street, Kenneth W.; Tanner, Stephen P.; Philipp, Warren H.

    2000-01-01

    Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.

  3. A Novel 96well-formatted Micro-gap Plate Enabling Drug Response Profiling on Primary Tumour Samples

    NASA Astrophysics Data System (ADS)

    Ma, Wei-Yuan; Hsiung, Lo-Chang; Wang, Chen-Ho; Chiang, Chi-Ling; Lin, Ching-Hung; Huang, Chiun-Sheng; Wo, Andrew M.

    2015-04-01

    Drug-based treatments are the most widely used interventions for cancer management. Personalized drug response profiling remains inherently challenging with low cell count harvested from tumour sample. We present a 96well-formatted microfluidic plate with built-in micro-gap that preserves up to 99.2% of cells during multiple assay/wash operation and only 9,000 cells needed for a single reagent test (i.e. 1,000 cells per test spot x 3 selected concentration x triplication), enabling drug screening and compatibility with conventional automated workstations. Results with MCF7 and MDA-MB-231 cell lines showed that no statistical significance was found in dose-response between the device and conventional 96-well plate control. Primary tumour samples from breast cancer patients tested in the device also showed good IC50 prediction. With drug screening of primary cancer cells must consider a wide range of scenarios, e.g. suspended/attached cell types and rare/abundant cell availability, the device enables high throughput screening even for suspended cells with low cell count since the signature microfluidic cell-trapping feature ensures cell preservation in a multiple solution exchange protocol.

  4. Protocol: high throughput silica-based purification of RNA from Arabidopsis seedlings in a 96-well format

    PubMed Central

    2011-01-01

    The increasing popularity of systems-based approaches to plant research has resulted in a demand for high throughput (HTP) methods to be developed. RNA extraction from multiple samples in an experiment is a significant bottleneck in performing systems-level genomic studies. Therefore we have established a high throughput method of RNA extraction from Arabidopsis thaliana to facilitate gene expression studies in this widely used plant model. We present optimised manual and automated protocols for the extraction of total RNA from 9-day-old Arabidopsis seedlings in a 96 well plate format using silica membrane-based methodology. Consistent and reproducible yields of high quality RNA are isolated averaging 8.9 μg total RNA per sample (~20 mg plant tissue). The purified RNA is suitable for subsequent qPCR analysis of the expression of over 500 genes in triplicate from each sample. Using the automated procedure, 192 samples (2 × 96 well plates) can easily be fully processed (samples homogenised, RNA purified and quantified) in less than half a day. Additionally we demonstrate that plant samples can be stored in RNAlater at -20°C (but not 4°C) for 10 months prior to extraction with no significant effect on RNA yield or quality. Additionally, disrupted samples can be stored in the lysis buffer at -20°C for at least 6 months prior to completion of the extraction procedure providing a flexible sampling and storage scheme to facilitate complex time series experiments. PMID:22136293

  5. Mass Spectrometric N-Glycan Analysis of Haptoglobin from Patient Serum Samples Using a 96-Well Plate Format.

    PubMed

    Zhu, Jianhui; Wu, Jing; Yin, Haidi; Marrero, Jorge; Lubman, David M

    2015-11-06

    Alterations in glycosylation of serum glycoproteins can provide unique and highly specific fingerprints of malignancy. Our previous mass spectrometric study revealed that the bifucosylation level of serum haptoglobin was distinctly increased in hepatocellular carcinoma (HCC) patients versus liver cirrhosis of all three major etiologies. We have thus developed a method for the analysis of large numbers of serum samples based on a 96-well plate platform for the evaluation of fucosylation changes of serum haptoglobin between HCC versus cirrhosis. Haptoglobin was isolated from the serum of individual patient samples based on an HPLC column immobilized with antihaptoglobin antibody via hydrazide immobilization chemistry. Only 10 μL of serum was required for glycan extraction and processing for MALDI-QIT mass spectrometry analysis using the 96-well plate format. The bifucosylation degrees of haptoglobin in individuals were calculated using a quantitative glycomics method. The MS data confirmed that the bifucosylated tetra-anntenary glycan was upregulated in HCC samples of all etiologies. This study provides a parallel method for processing glycan content for haptoglobin and evaluating detailed changes in glycan structures for a potentially large cohort of clinical serum samples.

  6. Solid-solid phase transitions determined by differential scanning calorimetry.

    NASA Technical Reports Server (NTRS)

    Murrill, E.; Whitehead, M. E.; Breed, L.

    1972-01-01

    Data are presented to show that tris(hydroxymethyl)acetic acid, monochloropentaerythritol, monofluoropentaerythritol, difluoropentaerythritol, monoaminopentaerythritol, and diaminopentaerythritol exhibit solid-state transitions to a plastic crystalline state. Transitional enthalpies in many of these substances are lower than might be expected by analogy with related structures, suggesting that some configurational contributions to their entropy increments have been inhibited.

  7. Air sampling with solid phase microextraction

    NASA Astrophysics Data System (ADS)

    Martos, Perry Anthony

    There is an increasing need for simple yet accurate air sampling methods. The acceptance of new air sampling methods requires compatibility with conventional chromatographic equipment, and the new methods have to be environmentally friendly, simple to use, yet with equal, or better, detection limits, accuracy and precision than standard methods. Solid phase microextraction (SPME) satisfies the conditions for new air sampling methods. Analyte detection limits, accuracy and precision of analysis with SPME are typically better than with any conventional air sampling methods. Yet, air sampling with SPME requires no pumps, solvents, is re-usable, extremely simple to use, is completely compatible with current chromatographic equipment, and requires a small capital investment. The first SPME fiber coating used in this study was poly(dimethylsiloxane) (PDMS), a hydrophobic liquid film, to sample a large range of airborne hydrocarbons such as benzene and octane. Quantification without an external calibration procedure is possible with this coating. Well understood are the physical and chemical properties of this coating, which are quite similar to those of the siloxane stationary phase used in capillary columns. The log of analyte distribution coefficients for PDMS are linearly related to chromatographic retention indices and to the inverse of temperature. Therefore, the actual chromatogram from the analysis of the PDMS air sampler will yield the calibration parameters which are used to quantify unknown airborne analyte concentrations (ppb v to ppm v range). The second fiber coating used in this study was PDMS/divinyl benzene (PDMS/DVB) onto which o-(2,3,4,5,6- pentafluorobenzyl) hydroxylamine (PFBHA) was adsorbed for the on-fiber derivatization of gaseous formaldehyde (ppb v range), with and without external calibration. The oxime formed from the reaction can be detected with conventional gas chromatographic detectors. Typical grab sampling times were as small as 5 seconds

  8. Performance evaluation of 3D polystyrene 96-well plates with human neural stem cells in a calcium assay.

    PubMed

    Lai, Yinzhi; Kisaalita, William S

    2012-08-01

    In this study, we have generated a high-throughput screening (HTS)-compatible 3D cell culture platform by chemically "welding" polystyrene scaffolds into standard 2D polystyrene 96-well plates. The variability of scaffolds was minimized by introducing automation into the fabrication process. The fabricated 3D cell culture plates were compared with several commercially available 3D cell culture platforms with light and scanning electron microscopy. Voltage-gated calcium channel functionality was used to access the Z' factors of all plates, including a 2D standard plate control. It was found that with the No-Wash Fluo-4 calcium assay and neural progenitor cells, all plates display acceptable Z' factors for use in HTS. The plates with "welded" polystyrene scaffolds have several advantages, such as being versatile and economical, and are ready to use off the shelf. These characteristics are especially desired in HTS preclinical drug discovery applications.

  9. Development and validation of a 96-well cellular assay for the discovery of ALDH1A1 inhibitors.

    PubMed

    Ming, Wenyu; Ma, Wenzhen; Chen, Lisa H; Volk, Catherine; Michael, Mervyn Dodson; Xu, Yanping; Zhang, Fang; Wang, Xiaojun

    2013-07-01

    Retinoic acid, the active metabolite of vitamin A, plays important roles in various physiological and pathological processes. The two-step production of retinoic acid from vitamin A (retinol) is catalyzed by alcohol dehydrogenases and aldehyde dehydrogenases, which are potential therapeutic targets for numerous diseases, such as obesity, diabetes, and cancer. Currently, the lack of a suitable high-throughput cellular assay hinders efforts to identify therapeutic small molecular inhibitors of aldehyde dehydrogenase, such as ALDH1A1. In this report, we utilized high-content imaging technology and a commercially available cell permeable ALDH substrate to develop a 96-well cellular ALDH1A1 assay. This assay has a robust and sensitive readout and is amenable to automation. With this cellular assay, we identified potent selective ALDH1A1 inhibitors to explore the role of retinoic acid production in various preclinical disease models.

  10. High-throughput determination of fudosteine in human plasma by liquid chromatography-tandem mass spectrometry, following protein precipitation in the 96-well plate format.

    PubMed

    Wen, Jun; Wu, Yiwen; Zhang, Linli; Qi, Yunpeng; Fan, Guorong; Wu, Yutian; Li, Zhen

    2008-05-01

    A 96-well protein precipitation, liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been developed and fully validated for the determination of fudosteine in human plasma. After protein precipitation of the plasma samples (50 microL) by the methanol (150 microL) containing the internal standard (IS), erdosteine, the 96-well plate was vortexed for 5 min and centrifuged for 15 min. The 100 microL supernatant and 100 microL mobile phase were added to another plate and mixed and then the mixture was directly injected into the LC-MS/MS system in the negative ionization mode. The separation was performed on a XB-CN column for 3.0 min per sample using an eluent of methanol-water (60:40, v/v) containing 0.005% formic acid. Multiple reaction monitoring (MRM) using the precursor-product ion transitions m/z 178-->91 and m/z 284-->91 was performed to quantify fudosteine and erdosteine, respectively. The method was sensitive with a lower limit of quantification (LLOQ) of 0.02 microg mL(-1), with good linearity (r>0.999) over the linear range of 0.02-10 microg mL(-1). The within- and between-run precision was less than 5.5% and accuracy ranged from 94.2 to 106.7% for quality control (QC) samples at three concentrations of 0.05, 1 and 8 microg mL(-1). The method was employed in the clinical pharmacokinetic study of fudosteine formulation product after oral administration to healthy volunteers.

  11. Development of a novel bead-based 96-well filtration plate competitive immunoassay for the detection of Gentamycin.

    PubMed

    Ho, Tien Yu Jessica; Chan, Chia-Chung; Chan, KinGho; Wang, Yu Chieh; Lin, Jing-Tang; Chang, Cheng-Ming; Chen, Chien-Sheng

    2013-11-15

    We developed a sensitive, simple, inexpensive and rapid bead-based immunoassay platform, composed of liposomal nanovesicle amplification system, Gentamycin sulfate beads and 96-well filtration plates. In the beginning of the assay, Gentamycin sulfate beads, Gentamycin sulfate and Gentamycin specific antibody were incubated in a bottom-sealed 96-well filtration plate. After incubation, washing was done by running washing buffer through the unsealed filtration plate with only gravity and the antibody-Gentamycin bead complexes were retained in the plate. Fluorescent dye-loaded protein G-liposomal nanovesicles were then added to specifically bind to antibodies on the retained beads. After washing unbound nanovesicles, millions of fluorescent dye molecules were released by adding a detergent solution to lyse liposomal nanovesicles. The limit of detection (LOD) of this novel detection platform in TBS and in skim milk were 52.65 ng/mL and 14.16 ng/mL, which are both sufficient for detecting the 200 ng/mL Codex maximum residual level (MRL). The dynamic ranges were both from each of their LODs to 100 μg/mL. The 50% inhibition concentrations (IC50) in TBS and skim milk were 199.66 ng/mL and 360.81 ng/mL, respectively. We also demonstrated the good specificity of this platform by comparing detection results between pure Gentamycin solution and a mixture solution of 6 different antibiotics including Gentamycin in skim milk. The entire assay with 60 samples was conducted within 2h. In sum, this novel biosensing platform not only fulfilled most benefits of magnetic bead-based assays, but also was inexpensive and convenient by replacing the magnetic separation with filtration plate separation.

  12. Scalable 96-well Plate Based iPSC Culture and Production Using a Robotic Liquid Handling System.

    PubMed

    Conway, Michael K; Gerger, Michael J; Balay, Erin E; O'Connell, Rachel; Hanson, Seth; Daily, Neil J; Wakatsuki, Tetsuro

    2015-05-14

    Continued advancement in pluripotent stem cell culture is closing the gap between bench and bedside for using these cells in regenerative medicine, drug discovery and safety testing. In order to produce stem cell derived biopharmaceutics and cells for tissue engineering and transplantation, a cost-effective cell-manufacturing technology is essential. Maintenance of pluripotency and stable performance of cells in downstream applications (e.g., cell differentiation) over time is paramount to large scale cell production. Yet that can be difficult to achieve especially if cells are cultured manually where the operator can introduce significant variability as well as be prohibitively expensive to scale-up. To enable high-throughput, large-scale stem cell production and remove operator influence novel stem cell culture protocols using a bench-top multi-channel liquid handling robot were developed that require minimal technician involvement or experience. With these protocols human induced pluripotent stem cells (iPSCs) were cultured in feeder-free conditions directly from a frozen stock and maintained in 96-well plates. Depending on cell line and desired scale-up rate, the operator can easily determine when to passage based on a series of images showing the optimal colony densities for splitting. Then the necessary reagents are prepared to perform a colony split to new plates without a centrifugation step. After 20 passages (~3 months), two iPSC lines maintained stable karyotypes, expressed stem cell markers, and differentiated into cardiomyocytes with high efficiency. The system can perform subsequent high-throughput screening of new differentiation protocols or genetic manipulation designed for 96-well plates. This technology will reduce the labor and technical burden to produce large numbers of identical stem cells for a myriad of applications.

  13. Scalable 96-well Plate Based iPSC Culture and Production Using a Robotic Liquid Handling System

    PubMed Central

    Conway, Michael K.; Gerger, Michael J.; Balay, Erin E.; O'Connell, Rachel; Hanson, Seth; Daily, Neil J.; Wakatsuki, Tetsuro

    2015-01-01

    Continued advancement in pluripotent stem cell culture is closing the gap between bench and bedside for using these cells in regenerative medicine, drug discovery and safety testing. In order to produce stem cell derived biopharmaceutics and cells for tissue engineering and transplantation, a cost-effective cell-manufacturing technology is essential. Maintenance of pluripotency and stable performance of cells in downstream applications (e.g., cell differentiation) over time is paramount to large scale cell production. Yet that can be difficult to achieve especially if cells are cultured manually where the operator can introduce significant variability as well as be prohibitively expensive to scale-up. To enable high-throughput, large-scale stem cell production and remove operator influence novel stem cell culture protocols using a bench-top multi-channel liquid handling robot were developed that require minimal technician involvement or experience. With these protocols human induced pluripotent stem cells (iPSCs) were cultured in feeder-free conditions directly from a frozen stock and maintained in 96-well plates. Depending on cell line and desired scale-up rate, the operator can easily determine when to passage based on a series of images showing the optimal colony densities for splitting. Then the necessary reagents are prepared to perform a colony split to new plates without a centrifugation step. After 20 passages (~3 months), two iPSC lines maintained stable karyotypes, expressed stem cell markers, and differentiated into cardiomyocytes with high efficiency. The system can perform subsequent high-throughput screening of new differentiation protocols or genetic manipulation designed for 96-well plates. This technology will reduce the labor and technical burden to produce large numbers of identical stem cells for a myriad of applications. PMID:26068617

  14. 96-Well Plate Colorimetric Assay for K(sub i) Determination of (plusmn)-2-Benzylsuccinic Acid, an Inhibitor of Carboxypeptidase A

    ERIC Educational Resources Information Center

    Wentland, Mark P.; Raza, Shaan; Yingtong Gao

    2004-01-01

    An appropriate assay to determine the inhibition potency of carboxypeptidase A (CPA) in 96-well format to illustrate how high throughput screening is used in modern drug discovery to identify bioactive molecules is developed. Efforts in developing a colorimetric 96-well plate assay for determination of the K(sub i) for inhibition of CPA by…

  15. Stability of solid phases in the dipolar hard sphere system

    NASA Astrophysics Data System (ADS)

    Levesque, D.; Weis, J.-J.

    2011-12-01

    Free energy differences between solid phases of dipolar hard spheres are estimated by Monte Carlo simulation using a nonequilibrium work method. These calculations allow one to determine which of the considered phases has the minimum free energy. The phase diagram which we obtain is confirmed by simulations in the isothermal-isobaric ensemble over a wide region of the density and temperature domain.

  16. Solid lubrication design methodology, phase 2

    NASA Technical Reports Server (NTRS)

    Pallini, R. A.; Wedeven, L. D.; Ragen, M. A.; Aggarwal, B. B.

    1986-01-01

    The high temperature performance of solid lubricated rolling elements was conducted with a specially designed traction (friction) test apparatus. Graphite lubricants containing three additives (silver, phosphate glass, and zinc orthophosphate) were evaluated from room temperature to 540 C. Two hard coats were also evaluated. The evaluation of these lubricants, using a burnishing method of application, shows a reasonable transfer of lubricant and wear protection for short duration testing except in the 200 C temperature range. The graphite lubricants containing silver and zinc orthophosphate additives were more effective than the phosphate glass material over the test conditions examined. Traction coefficients ranged from a low of 0.07 to a high of 0.6. By curve fitting the traction data, empirical equations for slope and maximum traction coefficient as a function of contact pressure (P), rolling speed (U), and temperature (T) can be developed for each lubricant. A solid lubricant traction model was incorporated into an advanced bearing analysis code (SHABERTH). For comparison purposes, preliminary heat generation calculations were made for both oil and solid lubricated bearing operation. A preliminary analysis indicated a significantly higher heat generation for a solid lubricated ball bearing in a deep groove configuration. An analysis of a cylindrical roller bearing configuration showed a potential for a low friction solid lubricated bearing.

  17. The solid-phase Nicholas reaction: scope and limitations.

    PubMed

    Gachkova, Natalie; Cassel, Johan; Leue, Stefanie; Kann, Nina

    2005-01-01

    Two libraries of alpha-substituted alkynes has been prepared on solid phase using a sequential Sonogashira/Nicholas reaction approach. The scope of nucleophiles in the Nicholas reaction on solid phase has been investigated, including carbon, oxygen, nitrogen, sulfur, fluoride, and hydride nucleophiles. The conditions for the reaction sequence have been optimized in terms of Lewis acid, catalyst for the Sonogashira step, temperature, reaction time, and decomplexation method, enabling the five-step sequence to be performed in 1 day.

  18. Solid-Phase Synthesis of 2-Aminoethyl Glucosamine Sulfoforms

    PubMed Central

    Liu, Runhui

    2012-01-01

    Mono- and disaccharides of sulfonated glucosamines (GlcN sulfoforms) conjugated to 2-aminoethyl linkers were generated by solid-phase synthesis. Orthogonally protected intermediates were tethered onto tritylated polystyrene resin beads, subjected to a modular sequence of deprotection and sulfonation steps, then cleaved from solid support without degradation of N- or O-sulfate esters using solvolytic conditions, and finally purified by reverse-phase HPLC to afford the title compounds. PMID:23180905

  19. High-throughput pharmacokinetics screen of VLA-4 antagonists by LC/MS/MS coupled with automated solid-phase extraction sample preparation.

    PubMed

    Tong, Xinchun S; Wang, Junying; Zheng, Song; Pivnichny, James V

    2004-06-29

    Automation of plasma sample preparation for pharmacokinetic studies on VLA-4 antagonists has been achieved by using 96-well format solid-phase extraction operated by Beckman Coulter Biomek 2000 liquid handling system. A Biomek 2000 robot is used to perform fully automated plasma sample preparation tasks that include serial dilution of standard solutions, pipetting plasma samples, addition of standard and internal standard solutions, performing solid-phase extraction (SPE) on Waters OASIS 96-well plates. This automated sample preparation process takes less than 2 h for a typical pharmacokinetic study, including 51 samples, 24 standards, 9 quality controls, and 3-6 dose checks with minimal manual intervention. Extensive validation has been made to ensure the accuracy and reliability of this method. A two-stage vacuum pressure controller has been incorporated in the program to improve SPE efficiency. This automated SPE sample preparation approach combined with liquid chromatography coupled with the high sensitivity and selectivity of tandem mass spectrometry (LC/MS)/MS has been successfully applied on both individual and cassette dosing for pharmacokinetic screening of a large number of VLA-4 antagonists with a limit of quantitation in the range of 1-5 ng/ml. Consequently, a significant throughput increase has been achieved along with an elimination of tedious labor and its consequential tendency to produce errors.

  20. 96-Well Polycarbonate-Based Microfluidic Titer Plate for High-Throughput Purification of DNA and RNA

    PubMed Central

    Witek, Małgorzata A.; Hupert, Mateusz L.; Park, Daniel S.-W.; Fears, Kirby; Murphy, Michael C.; Soper, Steven A.

    2008-01-01

    We report a simple and effective method for the high-throughput purification of a variety of nucleic acids (NAs) from whole cell lysates or whole blood using a photactivated polycarbonate solid-phase reversible immobilization (PPC-SPRI) microfluidic chip. High-throughput operation was achieved by placing 96 purification beds, each containing an array of 3800 20 µm diameter posts, on a single 3″ × 5″ polycarbonate (PC) wafer fabricated by hot embossing. All beds were interconnected through a common microfluidic network that permitted parallel access through the use of a vacuum and syringe pump for delivery of immobilization buffer (IB) and effluent. The PPC-SPRI purification was accomplished by condensation of NAs onto a UV-modified PC surface in the presence of the IB comprised of polyethylene glycol, NaCl, and ethanol with a composition dependent on the length of the NAs to be isolated and the identity of the sample matrix. The performance of the device was validated by quantification of the recovered material following PCR (for DNA) or RT-PCR (for RNA). The extraction bed load capacity of NAs was 206 ± 93 ng for gDNA and 165 ± 81 ng for TRNA from Escherichia coli. Plate-to-plate variability was found to be 35 ± 10%. The purification process was fast (>30 min) and easy to automate, and the low cost of wafer fabrication makes it appropriate for single-use applications. PMID:18355091

  1. Fuel spill identification using solid-phase extraction and solid-phase microextraction. 1. Aviation turbine fuels.

    PubMed

    Lavine, B K; Brzozowski, D M; Ritter, J; Moores, A J; Mayfield, H T

    2001-12-01

    The water-soluble fraction of aviation jet fuels is examined using solid-phase extraction and solid-phase microextraction. Gas chromatographic profiles of solid-phase extracts and solid-phase microextracts of the water-soluble fraction of kerosene- and nonkerosene-based jet fuels reveal that each jet fuel possesses a unique profile. Pattern recognition analysis reveals fingerprint patterns within the data characteristic of fuel type. By using a novel genetic algorithm (GA) that emulates human pattern recognition through machine learning, it is possible to identify features characteristic of the chromatographic profile of each fuel class. The pattern recognition GA identifies a set of features that optimize the separation of the fuel classes in a plot of the two largest principal components of the data. Because principal components maximize variance, the bulk of the information encoded by the selected features is primarily about the differences between the fuel classes.

  2. Solid-Phase S-Alkylation Promoted by Molecular Sieves.

    PubMed

    Calce, Enrica; Leone, Marilisa; Mercurio, Flavia Anna; Monfregola, Luca; De Luca, Stefania

    2015-11-20

    A solid-phase S-alkylation procedure to introduce chemical modification on the cysteine sulfhydryl group of a peptidyl resin is reported. The reaction is promoted by activated molecular sieves and consists of a solid-solid process, since both the catalyst and the substrate are in a solid state. The procedure was revealed to be efficient and versatile, particularly when used in combination with the solution S-alkylation approach, allowing for the introduction of different molecular diversities on the same peptide molecule.

  3. CO2 in the mantle: Melting and solid-solid phase boundaries

    NASA Astrophysics Data System (ADS)

    Teweldeberhan, A. M.; Boates, B.; Bonev, S. A.

    2013-07-01

    The high temperature phase boundaries of CO2 in the proximity of the Earth's adiabat are determined using first-principles molecular dynamics simulations based on density functional theory. The melting curve, predicted here up to 71 GPa, and the molecular to polymeric solid phase transition are computed through a phase coexistence approach from free energy calculations. The resulting CO2 phase IV-phase V-liquid triple point is at 31.8 GPa and 1636 K, in excellent agreement with the available experimental data. The Earth's geotherm crosses into the non-molecular phase V near 40 GPa and 2160 K, indicating that free deposits of carbon dioxide in the lower mantle would exist as a polymeric solid. We have also examined the thermodynamic stability of phase V and find no indication of transformations into a dissociated diamond and oxygen phase at mantle conditions.

  4. Solid-phase products of bacterial oxidation of arsenical pyrite.

    PubMed

    Carlson, L; Lindström, E B; Hallberg, K B; Tuovinen, O H

    1992-03-01

    Bacterial leaching of an As-containing pyrite concentrate produced acidic (pH < 1) leachates. During the leaching, the bacteria solubilized both As and Fe, and these two elements were distributed in solution-phase and solid-phase products. Jarosite and scorodite were the exclusive crystalline products in precipitate samples from the bacterial leaching of the sulfide concentrate.

  5. Diagnostic immunoassay by solid phase separation for digoxin

    SciTech Connect

    Grenier, F.C.; Pry, T.A.; Kolaczkowski, L.

    1988-11-29

    A method is described for conducting a diagnostic immunoassay for digoxin, comprising: (a) forming a reaction mixture of a test sample with a molar excess of labeled anti-digoxin antibodies whereby the labeled antibodies are capable of forming complex with digoxin present in the sample; (b) contacting the reaction mixture with a solid phase material having immobilized thereon a compound; (c) separating the solid phase material from the reaction mixture; and (d) determining the presence of digoxin in the test sample by measuring the amount of complex present in the liquid phase.

  6. Anisotropic kinetics of solid phase transition from first principles: alpha-omega phase transformation of Zr.

    PubMed

    Guan, Shu-Hui; Liu, Zhi-Pan

    2016-02-14

    Structural inhomogeneity is ubiquitous in solid crystals and plays critical roles in phase nucleation and propagation. Here, we develop a heterogeneous solid-solid phase transition theory for predicting the prevailing heterophase junctions, the metastable states governing microstructure evolution in solids. Using this theory and first-principles pathway sampling simulation, we determine two types of heterophase junctions pertaining to metal α-ω phase transition at different pressures and predict the reversibility of transformation only at low pressures, i.e. below 7 GPa. The low-pressure transformation is dominated by displacive Martensitic mechanism, while the high-pressure one is controlled by the reconstructive mechanism. The mechanism of α-ω phase transition is thus highly pressure-sensitive, for which the traditional homogeneous model fails to explain the experimental observations. The results provide the first atomic-level evidence on the coexistence of two different solid phase transition mechanisms in one system.

  7. Simplified method for determination of clarithromycin in human plasma using protein precipitation in a 96-well format and liquid chromatography-tandem mass spectrometry.

    PubMed

    Shin, Jaekyu; Pauly, Daniel F; Johnson, Julie A; Frye, Reginald F

    2008-08-01

    A simplified method to determine clarithromycin concentrations in human plasma using protein precipitation in a 96-well plate and liquid chromatography-tandem mass spectrometry was developed and validated. Plasma proteins were precipitated with acetonitrile and roxithromycin was used as the internal standard. After vortex mixing and centrifugation, the supernatants were directly injected onto a Phenomenex Luna Phenyl-Hexyl column (50 mm x 2.0 mm ID, 3 microm). The mobile phase consisted of water and methanol (30:70, v/v) containing 0.1% formic acid and 5mM ammonium acetate. The flow rate was 0.22 mL/min and the total run time (injection to injection) was less than 3 min. Detection of the analytes was achieved using positive ion electrospray tandem mass spectrometry in selected reaction monitoring (SRM) mode. The linear standard curve ranged from 100 to 5000 ng/mL and the precision and accuracy (inter- and intra-run) were within 7.9% and 4.9%, respectively. The method was successfully used to determine clarithromycin concentrations in human plasma samples obtained from healthy subjects who were given clarithromycin 500 mg for 3 days. The method is rapid, simple, precise and directly applicable to clarithromycin pharmacokinetic studies.

  8. A rapid solid-phase extraction fluorometric method for thiamine and riboflavin in salmonid eggs

    USGS Publications Warehouse

    Zajicek, James L.; Tillitt, Donald E.; Brown, Scott B.; Brown, Lisa R.; Honeyfield, Dale C.; Fitzsimons, John D.

    2005-01-01

    A new method has been developed and successfully applied to the selective measurement of thiamine (nonphosphorylated), total thiamine (sum of thiamine, thiamine monophosphate [TMP], thiamine diphosphate [TDP], and thiamine triphosphate [TTP]), and potentially interfering riboflavin in acidic (2% trichloroacetic acid) extracts of selected salmonid and walleye egg samples. Acidic extracts of eggs were applied directly to end-capped C18, reversed-phase solid-phase extraction (SPE) columns and separated into three fractions by elution with mixtures of PO4 buffer (pH 2), methanol (10%), and acetonitrile (20%). All thiamine compounds recovered in the first two fractions were oxidized to their corresponding thiochromes with alkaline potassium hexacyanoferrate, and we measured the thiochrome fluorescence (excitation at 360 nm, emission at 460 nm) in a 96-well microplate reader. Riboflavin, recovered in third fraction (eluted with pH 2, 20% acetonitrile), was analyzed directly by measuring the fluorescence of this fraction (excitation at 450 nm, emission at 530 nm). Significant portions of the phosphate esters of thiamine (TMP, TDP, and presumably TTP), when present at low concentrations (< 10 nmol of total -thiamine per gram of egg), were not retained by the 100-mg SPE column, and were collected directly during sample loading and in a subsequent phosphoric acid rinse as fraction 1. Free thiamine (nonphosphorylated) and remaining portions of the TDP and TMP were then eluted in the second fraction with 10% methanol/PO4 buffer, whereas the un-ionized, relatively nonpolar riboflavin was eluted in the third fraction with 20% acetonitrile. This new method uses a traditional sample homogenization of egg tissue to extract thiamine compounds into 2% trichlororacetic acid solution; an inexpensive, commercially available SPE column; small amounts of sample (0.5-1 g); microliter volumes of solvents per sample; a traditional, relatively nonhazardous, oxidation of thiamine compounds to

  9. Further optimization of detritylation in solid-phase oligodeoxyribonucleotide synthesis.

    PubMed

    Tram, Kha; Sanghvi, Yogesh S; Yan, Hongbin

    2011-01-01

    Various conditions for optimum detritylation (i.e., the removal of 5'-O-trityl protecting groups) during solid-phase synthesis of oligodeoxyribonucleotides were investigated. Di- and tri-chloroacetic acids of variable concentrations were used to study the removal of the 4,4'-dimethoxytrityl (DMTr) group. It was found that the DMTr group could be completely removed under much milder acidic conditions than what are currently used for automated solid-phase synthesis. The 2,7-dimethylpixyl (DMPx) is proposed as an alternative and more readily removable group for the protection of the 5'-OH functions both in solid- and solution-phase synthesis. The improved detritylation conditions are expected to minimize the waste and offer a protocol for incorporation of acid sensitive building-blocks in oligonucleotides.

  10. Solid state photomultiplier for astronomy, phase 2

    NASA Technical Reports Server (NTRS)

    Besser, P. J.; Hays, K. M.; Laviolette, R. A.

    1989-01-01

    Epitaxial layers with varying donor concentration profiles were grown on silicon substrate wafers using chemical vapor deposition (CVD) techniques, and solid state photomultiplier (SSPM) devices were fabricated from the wafers. Representative detectors were tested in a low background photon flux, low temperature environment to determine the device characteristics for comparison to NASA goals for astronomical applications. The SSPM temperatures varied between 6 and 11 K with background fluxes in the range from less than 5 x 10 to the 6th power to 10 to the 13th power photons/square cm per second at wavelengths of 3.2 and 20 cm. Measured parameters included quantum efficiency, dark count rate and bias current. Temperature for optimal performance is 10 K, the highest ever obtained for SSPMs. The devices exhibit a combination of the lowest dark current and highest quantum efficiency yet achieved. Experimental data were reduced, analyzed and used to generate recommendations for future studies. The background and present status of the microscopic theory of SSPM operation were reviewed and summarized. Present emphasis is on modeling of the avalanche process which is the basis for SSPM operation. Approaches to the solution of the Boltzmann transport equation are described and the treatment of electron scattering mechanisms is presented. The microscopic single-electron transport theory is ready to be implemented for large-scale computations.

  11. Recent developments in matrix solid-phase dispersion extraction.

    PubMed

    Capriotti, Anna Laura; Cavaliere, Chiara; Giansanti, Piero; Gubbiotti, Riccardo; Samperi, Roberto; Laganà, Aldo

    2010-04-16

    Matrix solid-phase dispersion is a sample preparation strategy widely applied to solid, semisolid or viscous samples, including animal tissues and foods with a high lipidic content. The process consists in blending the matrix onto a solid support, allowing the matrix cell disruption and the subsequent extraction of target analytes by means of a suitable elution solvent. First introduced in 1989, MSPD employment and developments are still growing because of the feasibility and versatility of the process, as evidenced by the several reviews that have been published since nineties. Therefore, the aim of the present review is to provide a general overview and an update of the last developments of MSPD.

  12. A 96-well single-pot liquid-liquid extraction, hydrophilic interaction liquid chromatography-mass spectrometry method for the determination of muraglitazar in human plasma.

    PubMed

    Xue, Y-J; Liu, Jane; Unger, Steve

    2006-06-07

    A single-pot liquid-liquid extraction (LLE) with hydrophilic interaction liquid chromatography/tandem mass spectrometry (HILIC/MS/MS) method has been developed and validated for the determination of muraglitazar, a hydrophobic diabetes drug, in human plasma. To 0.050 ml of each plasma sample in a 96-well plate, the internal standard solution in acetonitrile and toluene were added to extract the compound of interest. The plate was vortexed, followed by centrifugation. The organic layer was then directly injected into an LC/MS/MS system. Chromatographic separation was achieved isocratically on a Thermohypersil_Keystone, Hypersil silica column (3 mmx50 mm, 3 microm). The mobile phase contained 85% of methyl t-butyl ether and 15% of 90/10 (v/v) acetonitrile/water with 0.3% trifluoroacetic acid. Post-column mobile phase of 50/50 (v/v) acetonitrile/water containing 0.1% formic acid was added. Detection was by positive ion electrospray tandem mass spectrometry on a Sciex API 4000. The standard curve, ranged from 1 to 1000 ng/ml, was fitted to a 1/x weighted quadratic regression model. This single-pot LLE approach effectively eliminated time-consuming organic layer transfer, dry-down, and sample reconstitution steps, which are essential for a conventional liquid-liquid extraction procedure. The modified mobile phase was more compatible with the direct injection of the commonly used extraction solvents in LLE. Furthermore, the modified mobile phase improved the retention of muraglitazar, a hydrophobic compound, on the normal phase silica column. The validation results demonstrated that this method was rugged and suitable for analyzing muraglitazar in human plasma. In comparison with a revised-phase LC/MS/MS method, this single-pot LLE, HILIC/MS/MS method improved the detection sensitivity by more than four-fold based upon the LLOQ signal to noise ratio. This approach may be applied to other hydrophobic compounds with proper modification of the mobile phase compositions.

  13. Theoretical phase diagrams for solid H{sub 2}

    SciTech Connect

    Surh, M.P.; Runge, K.J.

    1993-07-01

    Possible phase diagrams for solid molecular para-hydrogen in the 0-200 GPa pressure regime are constructed on the basis of ab initio calculations. Structures for the broken symmetry phase (BSP) and H-A phase have recently been proposed under the assumption that the molecules are centered on sites of a hexagonal close-packed lattice with the ideal c/a ratio, i.e., only molecular orientational and electronic changes are allowed. Symmetry considerations then dictate the simplest phase diagrams consistent with experimental observations, although the possibility of additional transitions cannot be ruled out. A simple model is introduced to describe the BSP and H-A transitions.

  14. Influence of impurities on the solid-solid phase transitions in zirconium

    SciTech Connect

    Rigg, Paulo A; Greeff, Carl W; Gray, George T., III; Knudson, Marcus D

    2009-08-04

    In an effort to better understand the influence of impurities on the solid-solid phase transitions in Group IVb metals, experiments have been carried out on polycrystalline zirconium samples using plate impact and isentropic loading techniques. Samples with three levels of impurities were shock-loaded using both gas and powder-driven guns and isentropically loaded using magnetic drive (Sandia's Z-Machine) to determine the properties and characteristics of both the {alpha} {yields} {omega} and {omega} {yields} {beta} transitions.

  15. All solid-state SBS phase conjugate mirror

    DOEpatents

    Dane, Clifford B.; Hackel, Lloyd A.

    1999-01-01

    A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases.

  16. All solid-state SBS phase conjugate mirror

    DOEpatents

    Dane, C.B.; Hackel, L.A.

    1999-03-09

    A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases. 8 figs.

  17. Solid–solid phase transitions via melting in metals

    PubMed Central

    Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Uggowitzer, P. J.; Löffler, J. F.

    2016-01-01

    Observing solid–solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid–solid transition via the formation of a metastable liquid in a ‘real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory. PMID:27103085

  18. Solid Phase Characterization of Tank 241-C-105 Grab Samples

    SciTech Connect

    Ely, T. M.; LaMothe, M. E.; Lachut, J. S.

    2016-01-11

    The solid phase characterization (SPC) of three grab samples from single-shell Tank 241-C-105 (C-105) that were received at the laboratory the week of October 26, 2015, has been completed. The three samples were received and broken down in the 11A hot cells.

  19. Recent Approaches Toward Solid Phase Synthesis of β-Lactams

    NASA Astrophysics Data System (ADS)

    Mandal, Bablee; Ghosh, Pranab; Basu, Basudeb

    Since the discovery of penicillin in 1929, β-lactam antibiotics have been recognized as potentially chemotherapeutic drugs of incomparable effectiveness, conjugating a broad spectrum of activity with very low toxicity. The primary motif azetidin-2-one ring (β-lactam) has been considered as specific pharmacophores and scaffolds. With the advent of combinatorial chemistry and automated parallel synthesis coupled with ample interests from the pharmaceutical industries, recent trends have been driven mostly by adopting solid phase techniques and polymer-supported synthesis of β-lactams. The present survey will present an overview of the developments on the polymer-supported and solid phase techniques for the preparation of β-lactam ring or β-lactam containing antibiotics published over the last decade. Both unsubstituted and substitutions with different functional groups at various positions of β-lactams have been synthesized using solid phase technology. However, Wang resin and application of Staudinger [2+2] cycloaddition reaction have remained hitherto the major choice. It may be expected that other solid phase approaches involving different resins would be developed in the coming years.

  20. Solid-phase-supported synthesis of morpholinoglycine oligonucleotide mimics

    PubMed Central

    Belov, Sergey S; Tarasenko, Yulia V; Silnikov, Vladimir N

    2014-01-01

    Summary An efficient solid-phase-supported peptide synthesis (SPPS) of morpholinoglycine oligonucleotide (MorGly) mimics has been developed. The proposed strategy includes a novel specially designed labile linker group containing the oxalyl residue and the 2-aminomethylmorpholino nucleoside analogues as first subunits. PMID:24991266

  1. Kinetics of Microbial Reduction of Solid Phase U(VI)

    SciTech Connect

    Liu, Chongxuan; Jeon, Byong Hun; Zachara, John M.; Wang, Zheming; Dohnalkova, Alice; Fredrickson, Jim K.

    2006-10-01

    Sodium boltwoodite (NaUO2SiO3OH ?1.5H2O) was used to assess the kinetics of microbial reduction of solid phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Batch experiments were performed in a non-growth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solid phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intraparticle uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated the intimate coupling of biological, chemical, and physical processes in microbial reduction of solid phase U(VI).

  2. A method of solid-solid phase equilibrium calculation by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Karavaev, A. V.; Dremov, V. V.

    2016-12-01

    A method for evaluation of solid-solid phase equilibrium curves in molecular dynamics simulation for a given model of interatomic interaction is proposed. The method allows to calculate entropies of crystal phases and provides an accuracy comparable with that of the thermodynamic integration method by Frenkel and Ladd while it is much simpler in realization and less intense computationally. The accuracy of the proposed method was demonstrated in MD calculations of entropies for EAM potential for iron and for MEAM potential for beryllium. The bcc-hcp equilibrium curves for iron calculated for the EAM potential by the thermodynamic integration method and by the proposed one agree quite well.

  3. Solid phases of spatially nanoconfined oxygen: A neutron scattering study

    SciTech Connect

    Kojda, Danny; Wallacher, Dirk; Hofmann, Tommy; Baudoin, Simon; Hansen, Thomas; Huber, Patrick

    2014-01-14

    We present a comprehensive neutron scattering study on solid oxygen spatially confined in 12 nm wide alumina nanochannels. Elastic scattering experiments reveal a structural phase sequence known from bulk oxygen. With decreasing temperature cubic γ-, orthorhombic β- and monoclinic α-phases are unambiguously identified in confinement. Weak antiferromagnetic ordering is observed in the confined monoclinic α-phase. Rocking scans reveal that oxygen nanocrystals inside the tubular channels do not form an isotropic powder. Rather, they exhibit preferred orientations depending on thermal history and the very mechanisms, which guide the structural transitions.

  4. Phase field modeling of flexoelectricity in solid dielectrics

    NASA Astrophysics Data System (ADS)

    Chen, H. T.; Zhang, S. D.; Soh, A. K.; Yin, W. Y.

    2015-07-01

    A phase field model is developed to study the flexoelectricity in nanoscale solid dielectrics, which exhibit both structural and elastic inhomogeneity. The model is established for an elastic homogeneous system by taking into consideration all the important non-local interactions, such as electrostatic, elastic, polarization gradient, as well as flexoelectric terms. The model is then extended to simulate a two-phase system with strong elastic inhomogeneity. Both the microscopic domain structures and the macroscopic effective piezoelectricity are thoroughly studied using the proposed model. The results obtained show that the largest flexoelectric induced polarization exists at the interface between the matrix and the inclusion. The effective piezoelectricity is greatly influenced by the inclusion size, volume fraction, elastic stiffness, and the applied stress. The established model in the present study can provide a fundamental framework for computational study of flexoelectricity in nanoscale solid dielectrics, since various boundary conditions can be easily incorporated into the phase field model.

  5. Distribution of Dechlorinating Bacteria between the Aqueous and Solid Phases

    NASA Astrophysics Data System (ADS)

    Cápiro, N. L.; Hatt, J. K.; Wang, Y.; Loeffler, F. E.; Pennell, K. D.

    2010-12-01

    Microbial monitoring of aquifers relies on nucleic acid biomarker analysis, which is typically performed with biomass recovered from groundwater samples; however, it is unclear what fraction of the target population(s) is associated with groundwater (i.e., planktonic cells) or is attached to solid phases (i.e., biofilms). Understanding how the titer of target organism(s) in groundwater correlates with the true cell titers of the target organism in the aquifer (i.e., planktonic plus attached cells) is critical for a meaningful interpretation of the data, the prediction of bioremediation performance, and the implementation of site management strategies. To evaluate the distribution of active cells between resident solid phase and the aqueous phase, one-dimensional columns were packed under water-saturated conditions with Bio-Dechlor INOCULUM, a PCE-to ethene-dechlorinating bacterial consortium containing both multiple Dehalococcoides (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ). The columns were packed with two distinct solid matrices: a low organic content sandy Federal Fine Ottawa soil or Appling soil with higher organic matter content. Influent reduced mineral salts medium supplied at a groundwater pore-water velocity of 0.3 m/day contained both 10 mM lactate as electron donor and 0.33 mM PCE as electron acceptor. Routine collection of biomass from column side ports and effluent samples measured the titers of target cells in the aqueous phase and determined when steady state conditions had been reached. A second set of column experiments evaluated delivery and filtration effects by the solid matrix (i.e., Federal Fine Ottawa sand versus Appling soil) under the same conditions except that electron donor or acceptor were omitted (no growth conditions). Quantitative real-time PCR (qPCR) analysis using Dhc and GeoSZ 16S rRNA gene-targeted primer and probe sets determined the planktonic cell counts, and destructive sampling of the columns allowed measurement

  6. The solid phase of ginkgolide K: Structure and physicochemical properties

    NASA Astrophysics Data System (ADS)

    Zhang, Yiwen; Zhang, Guoshun; Wang, Zhenzhong; Lv, Yang; Xiao, Wei

    2016-05-01

    Four solvates of ginkgolide K with dimethyl sulfoxide(I), water molecule(II), acetone-isopropyl alcohol(III), methanol-ethanol(IV) and one solvate-free (V) have been described in this work. And the solid-state techniques such as X-ray diffraction, thermal analysis and Fourier transform infrared spectroscopy were used for characterization of the solid phases. The single crystal structures of ginkgolide K solvates (I-IV) have been determined. Ginkgolide K shows strong inflexibility and solvents being incorporated in the crystal structure results in it forming polymorphs via the diverse hydrogen bond interactions.

  7. High-throughput and sensitive quantitation of plasma catecholamines by ultraperformance liquid chromatography-tandem mass spectrometry using a solid phase microwell extraction plate.

    PubMed

    Dunand, Marielle; Gubian, Danilo; Stauffer, Maxime; Abid, Karim; Grouzmann, Eric

    2013-04-02

    Plasma catecholamines provide a reliable biomarker of sympathetic activity. The low circulating concentrations of catecholamines and analytical interferences require tedious sample preparation and long chromatographic runs to ensure their accurate quantification by HPLC with electrochemical detection. Published or commercially available methods relying on solid phase extraction technology lack sensitivity or require derivatization of catecholamine by hazardous reagents prior to tandem mass spectrometry (MS) analysis. Here, we manufactured a novel 96-well microplate device specifically designed to extract plasma catecholamines prior to their quantification by a new and highly sensitive ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. Processing time, which included sample purification on activated aluminum oxide and elution, is less than 1 h per 96-well microplate. The UPLC-MS/MS analysis run time is 2.0 min per sample. This UPLC-MS/MS method does not require a derivatization step, reduces the turnaround time by 10-fold compared to conventional methods used for routine application, and allows catecholamine quantification in reduced plasma sample volumes (50-250 μL, e.g., from children and mice).

  8. Phenomena of solid state grain boundaries phase transition in technology

    SciTech Connect

    Minaev, Y. A.

    2015-03-30

    The results of study the phenomenon, discovered by author (1971), of the phase transition of grain boundary by the formation of two-dimensional liquid or quasi-liquid films have been done. The described phenomena of the first order phase transition (two-dimensional melting) at temperatures 0.6 – 0.9 T{sub S0} (of the solid state melting point) is a fundamental property of solid crystalline materials, which has allowed to revise radically scientific representations about a solid state of substance. Using the mathematical tools of the film thermodynamics it has been obtained the generalized equation of Clausius - Clapeyron type for two-dimensional phase transition. The generalized equation has been used for calculating grain boundary phase transition temperature T{sub Sf} of any metal, which value lies in the range of (0.55…0.86) T{sub S0}. Based on these works conclusions the develop strategies for effective forming of coatings (by thermo-chemical processing) on surface layers of functional alloys and hard metals have been made. The short overview of the results of some graded alloys characterization has been done.

  9. Direct Sampling and Analysis from Solid Phase Extraction Cards using an Automated Liquid Extraction Surface Analysis Nanoelectrospray Mass Spectrometry System

    SciTech Connect

    Walworth, Matthew J; ElNaggar, Mariam S; Stankovich, Joseph J; WitkowskiII, Charles E.; Norris, Jeremy L; Van Berkel, Gary J

    2011-01-01

    Direct liquid extraction based surface sampling, a technique previously demonstrated with continuous flow and autonomous pipette liquid microjunction surface sampling probes, has recently been implemented as the Liquid Extraction Surface Analysis (LESA) mode on the commercially available Advion NanoMate chip-based infusion nanoelectrospray ionization system. In the present paper, the LESA mode was applied to the analysis of 96-well format custom solid phase extraction (SPE) cards, with each well consisting of either a 1 or 2 mm diameter monolithic hydrophobic stationary phase. These substrate wells were conditioned, loaded with either single or multi-component aqueous mixtures, and read out using the LESA mode of a TriVersa NanoMate or a Nanomate 100 coupled to an ABI/Sciex 4000QTRAPTM hybrid triple quadrupole/linear ion trap mass spectrometer and a Thermo LTQ XL linear ion trap mass spectrometer. Extraction conditions, including extraction/nanoESI solvent composition, volume, and dwell times, were optimized in the analysis of targeted compounds. Limit of detection and quantitation as well as analysis reproducibility figures of merit were measured. Calibration data was obtained for propranolol using a deuterated internal standard which demonstrated linearity and reproducibility. A 10x increase in signal and cleanup of micromolar Angiotensin II from a concentrated salt solution was demonstrated. Additionally, a multicomponent herbicide mixture at ppb concentration levels was analyzed using MS3 spectra for compound identification in the presence of isobaric interferences.

  10. Allantoin as a solid phase adsorbent for removing endotoxins.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

    2013-10-04

    In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance.

  11. Studies in Solid Phase Peptide Synthesis: A Personal Perspective

    SciTech Connect

    Mitchell, A R

    2007-06-01

    By the early 1970s it had became apparent that the solid phase synthesis of ribonuclease A could not be generalized. Consequently, virtually every aspect of solid phase peptide synthesis (SPPS) was reexamined and improved during the decade of the 1970s. The sensitive detection and elimination of possible side reactions (amino acid insertion, N{sup {alpha}}-trifluoroacetylation, N{sup {alpha}{var_epsilon}}-alkylation) was examined. The quantitation of coupling efficiency in SPPS as a function of chain length was studied. A new and improved support for SPPS, the 'PAM-resin', was prepared and evaluated. These and many other studies from the Merrifield laboratory and elsewhere increased the general acceptance of SPPS leading to the 1984 Nobel Prize in Chemistry for Bruce Merrifield.

  12. Solid-phase total synthesis of daptomycin and analogs.

    PubMed

    Lohani, Chuda Raj; Taylor, Robert; Palmer, Michael; Taylor, Scott D

    2015-02-06

    An entirely solid-phase synthesis of daptomycin, a cyclic lipodepsipeptide antibiotic currently in clinical use, was achieved using a combination of α-azido and Fmoc amino acids. This methodology was applied to the synthesis of several daptomycin analogs, one of which did not contain kynurenine or the synthetically challenging amino acid (2S,3R)-methylglutamate yet exhibited an MIC approaching that of daptomycin.

  13. Chromatography, solid-phase extraction, and capillary electrochromatography with MIPs.

    PubMed

    Tóth, Blanka; Horvai, George

    2012-01-01

    Most analytical applications of molecularly imprinted polymers are based on their selective adsorption properties towards the template or its analogs. In chromatography, solid phase extraction and electrochromatography this adsorption is a dynamic process. The dynamic process combined with the nonlinear adsorption isotherm of the polymers and other factors results in complications which have limited the success of imprinted polymers. This chapter explains these problems and shows many examples of successful applications overcoming or avoiding the problems.

  14. New Phase Transition of Solid Bromine under High Pressure

    SciTech Connect

    San-Miguel, A.; Libotte, H.; Gaspard, J.-P.; Gauthier, M.; Aquilanti, G.; Pascarelli, S.

    2007-07-06

    Solid bromine has been studied by x-ray absorption spectroscopy experiments up to a maximum pressure of 75 GPa. The data analysis of the extended fine structure reveals that the intramolecular distance first increases, reaching its maximum value at 25{+-}5 GPa. From this value the intramolecular distance abruptly begins to decrease evidencing a nonpreviously observed phase transformation taking place at 25{+-}5 GPa. A maximum variation of 0.08 A ring is observed at 65{+-}5 GPa where again a phase transition occurs. This last transformation could correspond with the recently observed change to an incommensurate modulated phase. We discuss the possible generalization of the observed new phase transition at 25{+-}5 GPa to the case of the other halogens.

  15. Oscillatory burning of solid propellants including gas phase time lag.

    NASA Technical Reports Server (NTRS)

    T'Ien, J. S.

    1972-01-01

    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  16. Clinically relevant interpretation of solid phase assays for HLA antibody

    PubMed Central

    Bettinotti, Maria P.; Zachary, Andrea A.; Leffell, Mary S.

    2016-01-01

    Purpose of review Accurate and timely detection and characterization of human leukocyte antigen (HLA) antibodies are critical for pre-transplant and post-transplant immunological risk assessment. Solid phase immunoassays have provided increased sensitivity and specificity, but test interpretation is not always straightforward. This review will discuss the result interpretation considering technical limitations; assessment of relative antibody strength; and the integration of data for risk stratification from complementary testing and the patient's immunological history. Recent findings Laboratory and clinical studies have provided insight into causes of test failures – false positive reactions because of antibodies to denatured HLA antigens and false negative reactions resulting from test interference and/or loss of native epitopes. Test modifications permit detection of complement-binding antibodies and determination of the IgG subclasses. The high degree of specificity of single antigen solid phase immunoassays has revealed the complexity and clinical relevance of antibodies to HLA-C, HLA-DQ, and HLA-DP antigens. Determination of antibody specificity for HLA epitopes enables identification of incompatible antigens not included in test kits. Summary Detection and characterization of HLA antibodies with solid phase immunoassays has led to increased understanding of the role of those antibodies in graft rejection, improved treatment of antibody-mediated rejection, and increased opportunities for transplantation. However, realization of these benefits requires careful and accurate interpretation of test results. PMID:27200498

  17. Nuclear Ordered Phases of Solid 3He in Silver Sinters

    NASA Astrophysics Data System (ADS)

    Schuberth, Erwin A.; Kath, Matthias; Bago, Simone

    2006-09-01

    To determine the exact spin structure of the nuclear magnetic ordered phases of solid 3He, the U2D2 low field and the high field phases above 0.4 T, a European Research and Training Network for neutron scattering from the ordered solid was established which consisted of a collaboration with the Hahn Meitner Institute, Berlin, and other European and US groups. For this experiment it is crucial to grow a single crystal within the sinter needed for cooling the solid to temperatures of the order of 500 μK and to keep it cold long enough to measure a magnetic neutron diffraction. The sinter is also necessary to absorb the major part (> 90%) of the heat generated by the neutron capture and decay reaction of the 3He nucleus. In this work we studied the growth of crystals in Ag sinters of different pore sizes and with different growth speeds to find an optimal way to obtain single crystalline samples, or at least samples with only a few grains. We used SQUID magnetometry and NMR to measure the magnetization in the ordered phases. They were indicated by the known drop of the intensity, both in the NMR signal and in the dc magnetization, for the U2D2 phase, and by an increase of about 30% for the high field phase. The best results for cooling were obtained with sinters made from 700 Å "Japanese powder" with a packing fraction of 50% which were annealed at 130 °C after sintering and then had a calculated particle size of about 4200 Å. In the dc magnetization we found a paramagnetic surface contribution from a few monolayers of 3He down to 500 μK in addition to the bulk magnetization.

  18. Collective Atomic Displacements during Complex Phase Boundary Migration in Solid-Solid Phase Transformations.

    PubMed

    Duncan, Juliana; Harjunmaa, Ari; Terrell, Rye; Drautz, Ralf; Henkelman, Graeme; Rogal, Jutta

    2016-01-22

    The A15 to bcc phase transition is simulated at the atomic scale based on an interatomic potential for molybdenum. The migration of the phase boundary proceeds via long-range collective displacements of entire groups of atoms across the interface. To capture the kinetics of these complex atomic rearrangements over extended time scales we use the adaptive kinetic Monte Carlo approach. An effective barrier of 0.5 eV is determined for the formation of each new bcc layer. This barrier is not associated with any particular atomistic process that governs the dynamics of the phase boundary migration. Instead, the effective layer transformation barrier represents a collective property of the complex potential energy surface.

  19. One-phase crystal disorder in pharmaceutical solids and its implication for solid-state stability.

    PubMed

    Clawson, Jacalyn S; Kennedy-Gabb, Sonya; Lee, Alfred Y; Copley, Royston C B

    2011-10-01

    Solid-state disorders of active pharmaceutical ingredients have been characterized by means of X-ray diffraction techniques and solid-state nuclear magnetic resonance spectroscopy. The results determined that the pleuromutilin-derivative, I, displays a unique continuous conformational disorder while retaining its long-range crystalline structure. The propionic acid (PA) version of this compound displayed partial crystalline order and site disorder of PA, depending on the quantity of PA incorporated in the structure. Thus, I is a unique example of one-phase crystalline-amorphous model. Physical and chemical stability data was acquired on these disordered systems and discussed in relation with the characterized disorder present in the crystal systems. Analysis of the results showed that in contrast to phase-separated amorphous, restrained disorders do not influence the stability.

  20. Mechanism of phase transition, from vapor to solid: Transient liquid phase is between the two

    NASA Astrophysics Data System (ADS)

    Mahapatra, A. K.; Wang, Junyong; Zhang, Hongwei; Han, Min

    2016-08-01

    The mechanism of phase transition, from vapor to solid, is studied by producing non-stoichiometric ZnO and CdS nanoclusters (NCs) by low-energy cluster beam deposition technique, and examining their morphological and compositional evolution over a long span of time. It is concluded that the transition of vapor to solid goes through a transient liquid phase: coagulation of a large number of atomic clusters first forms liquid NCs which then solidify. The nature of the material and the experimental conditions determine crystallinity and shape of the NCs during the solidification process.

  1. Phase transformation considerations during process development and manufacture of solid oral dosage forms.

    PubMed

    Zhang, Geoff G Z; Law, Devalina; Schmitt, Eric A; Qiu, Yihong

    2004-02-23

    The quality and performance of a solid oral dosage form depends on the choice of the solid phase, the formulation design, and the manufacturing process. The potential for process-induced solid phase transformations must be evaluated during design and development of formulations and manufacturing processes. This article briefly reviews the basic principles of polymorphism, defines the classes of phase transformation and the underlying transformation mechanisms, and discusses respective kinetic factors. The potential phase transformations associated with common unit operations employed in manufacturing solid oral dosage forms are highlighted. Specific examples are given to illustrate the importance of solid phases, and process-induced phase transitions in formulation and process development.

  2. Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

    DTIC Science & Technology

    2008-06-01

    LABORATORY STUDY REPORT Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant...Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility 5a. CONTRACT NUMBER 5b...PDMS poly dimethylsiloxane SPME Solid phase microextraction TOC Total organic carbon     1 1. LABORATORY DEMONSTRATION GOALS The

  3. Solid State NMR Studies of the Aluminum Hydride Phases

    NASA Technical Reports Server (NTRS)

    Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

    2006-01-01

    Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

  4. A device for automated direct sampling and quantitation from solid-phase sorbent extraction cards by electrospray tandem mass spectrometry.

    PubMed

    Wachs, Timothy; Henion, Jack

    2003-04-01

    A new solid-phase extraction (SPE) device in the 96-well format (SPE Card) has been employed for automated off-line sample preparation of low-volume urine samples. On-line automated analyte elution via SPE and direct quantitation by micro ion spray mass spectrometry is reported. This sample preparation device has the format of a microtiter plate and is molded in a plastic frame which houses 96 separate sandwiched 3M Empore sorbents (0.5-mm-thickness, 8-microm particles) covered on both sides by a microfiber support material. Ninety-six discrete SPE zones, each 7 mm in diameter, are imbedded into the sheet in the conventional 9-mm pitch (spacing) of a 96-well microtiter plate. In this study one-quarter of an SPE Card (24 individual zones) was used merely as a convenience. After automated off-line interference elution of applied human urine from 24 samples, a section of SPE Card is mounted vertically on a computer-controlled X, Y, Z positioner in front of a micro ion spray direct sampling tube equipped with a beveled tip. The beveled tip of this needle robotically penetrates each SPE elution zone (sorbent disk) or stationary phase in a serial fashion. The eluted analytes are sequentially transferred directly to a microelectrosprayer to obtain tandem mass spectrometric (MS/MS) analysis. This strategy precludes any HPLC separation and the associated method development. The quantitative determination of Ritalin (methylphenidate) from fortified human urine samples is demonstrated. A trideuterated internal standard of methylphenidate was used to obtain ion current response ratios between the parent drug and the internal standard. Human control urine samples fortified from 6.6 to 3300 ng/mL (normal therapeutic levels have been determined in other studies to be between 50 and 100 ng/mL urine) were analyzed and a linear calibration curve was obtained with a correlation coefficient of 0.9999, where the precision of the quality control (QC) samples ranged from 9.6% at the 24

  5. Progress of solid-phase microextraction coatings and coating techniques.

    PubMed

    Jiang, Guibin; Huang, Minjia; Cai, Yaqi; Lv, Jianxia; Zhao, Zongshan

    2006-07-01

    Solid-phase microextraction (SPME) has been popular as an environmentally friendly sample pretreatment technique to extract a very wide range of analytes. This is partly owing to the development of SPME coatings. One of the key factors affecting the extraction performances, such as the sensitivity, selectivity, and reproducibility, is the properties of the coatings on SPME fibers. This paper classifies the materials used as SPME coatings and introduces some common preparation techniques of SPME coating in detail, such as sol-gel technique, electrochemical polymerization technique, particle direct pasting technique, restricted access matrix SPME technique, and molecularly imprinted SPME technique.

  6. Advances in solid-phase extraction disks for environmental chemistry

    USGS Publications Warehouse

    Thurman, E.M.; Snavely, K.

    2000-01-01

    The development of solid-phase extraction (SPE) for environmental chemistry has progressed significantly over the last decade to include a number of new sorbents and new approaches to SPE. One SPE approach in particular, the SPE disk, has greatly reduced or eliminated the use of chlorinated solvents for the analysis of trace organic compounds. This article discusses the use and applicability of various SPE disks, including micro-sized disks, prior to gas chromatography-mass spectrometry for the analysis of trace organic compounds in water. Copyright (C) 2000 Elsevier Science B.V.

  7. Kinetics of solid-solid phase transitions in metals using proton radiography (u)

    SciTech Connect

    Schwartz, Cynthia L; Rigg, Paulo A; Hixson, Rob S; Jensen, Brian J

    2011-01-25

    When a compressed material changes phase it doesn't do so instantly. Instead it transitions through a mixed phase as it transforms to the end state phase for a given pressure, volume and temperature. Common phase diagrams show the phase boundaries as sharp lines when compression has been slowly applied and held for an infinite amount of time. When the compression is applied with high strain rate, however, the phase boundaries are no longer crisp as the kinetic effects of the crystal reorientation delay the transitions, resulting in regions of mixed phase. This opens up the possibility that some degree of metastability exists for such transition in dynamic compression. The compression path can go past the equilibrium phase boundary and the transition happen from a metastable state because of the very short timescale of the compression process. Molecular dynamics (MD) simulations recently have been used to examine shock-induced phase transitions in single crystal materials illustrating an orientation dependence of the transition stress, mechanisms, kinetics, and Hugoniot response. For example, the [100] orientation of iron had a simulated transition stress higher than the experimentally determined polycrystalline value of 13 GPa by 2 GPa. Previously, dynamic experiments on iron have observed a non-zero transition time and width in the solid-solid {alpha}-{var_epsilon} phase transition. Using Proton Radiography at the Los Alamos Neutron Science Center, we have performed plate impact experiments on iron to further study the {alpha}-{var_epsilon} phase transition which occurs at 13 GPa. A 40mm bore powder gun was coupled to a proton radiography beam line and imaging system and synchronized to the impact of the projectile on the target sample with the proton beam pattern. A typical experimental configuration for the iron study, as shown below in 3 color-enhanced radiographs, is a 40mm diameter aluminum sabot impacting a 40mm diameter sample of polycrystalline ARMCO iron

  8. Electrostatic levitation studies of supercooled liquids and metastable solid phases

    NASA Astrophysics Data System (ADS)

    Rustan, Gustav Errol

    been carried out to study the metastable phase formation in an Fe83B17 near eutectic alloy. Initial supercooling measurements using the ISU-ESL identified the formation of three metastable phases: a precipitate phase that shows stable coexistence with the deeply supercooled liquid, and two distinct bulk solidification phases. To identify the structure of the metastable phases, the Washington University Beamline ESL (WU-BESL) has been used to perform in-situ high energy x-ray diffraction measurements of the metastable phases. Based on the x-ray results, the precipitate phase has been identified as bcc-Fe, and the more commonly occurring bulk solidification product has been found to be a two-phase mixture of Fe23B6 plus fcc-Fe, which appears, upon cooling, to transform into a three phase mixture of Fe23B6, bcc-Fe, and an as-yet unidentified phase, with the transformation occurring at approximately the expected fcc-to-bcc transformation temperature of pure Fe. To further characterize the multi-phase metastable alloy, the ISU-ESL has been used to perform measurements of volume thermal expansion via the videographic technique, as well as RF susceptibility via the TDO technique. The results of the thermal expansion and susceptibility data have been found to be sensitive indicators of additional structural changes that may be occurring in the metastable solid at temperatures below 1000 K, and the susceptibility data has revealed that three distinct ferromagnetic phase transitions take place within the multi-phase mixture. Based on these results, it has been hypothesized that there may be an additional transformation taking place that leads to the formation of either bct- or o-Fe3B in addition to the Fe23B6 phase, although further work is required to test this hypothesis.

  9. Nucleation of the diamond phase in aluminium-solid solutions

    NASA Technical Reports Server (NTRS)

    Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.

    1993-01-01

    Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

  10. Two-phase flows in solid rocket motors

    NASA Astrophysics Data System (ADS)

    Murakami, Takuji; Shimada, Toru

    Axisymmetric gas-particle two-phase flows in solid-rocket-motor combustion chambers and nozzles with small throat radius of curvature and with submerged configuration are investigated numerically by utilizing a second-order finite-volume method with van Leer's flux-vector splitting in conjunction with a technique of body-fitted cell system. Effects of the particle radius and the particle mass fraction on the two-phase flow, especially on the particle density distribution, the particle-free zone, and the rate of deceleration of the gas are studied. The scheme can capture the particle-free zone with a relatively coarse cell system without numerical oscillation, being benefited by internal dissipative effect which this high-resolution upwind method involves. The validity of the present numerical simulation is thus confirmed.

  11. Powder metallurgy: Solid and liquid phase sintering of copper

    NASA Technical Reports Server (NTRS)

    Sheldon, Rex; Weiser, Martin W.

    1993-01-01

    Basic powder metallurgy (P/M) principles and techniques are presented in this laboratory experiment. A copper based system is used since it is relatively easy to work with and is commercially important. In addition to standard solid state sintering, small quantities of low melting metals such as tin, zinc, lead, and aluminum can be added to demonstrate liquid phase sintering and alloy formation. The Taguchi Method of experimental design was used to study the effect of particle size, pressing force, sintering temperature, and sintering time. These parameters can be easily changed to incorporate liquid phase sintering effects and some guidelines for such substitutions are presented. The experiment is typically carried out over a period of three weeks.

  12. SOLID-LIQUID PHASE EQUILIBRIUM IN BINARY SYSTEMS OF TRIPHENYL ANTIMONY WITH BIPHENYL, NAPHTHALENE, AND BENZOIC ACID.

    DTIC Science & Technology

    PHASE STUDIES, *ORGANOMETALLIC COMPOUNDS, SEMICONDUCTORS, SOLID STATE PHYSICS, ANTIMONY COMPOUNDS, EUTECTICS , ZONE MELTING, HALIDES, BISMUTH, ARSENIC, ELECTRONS, NAPHTHALENES , PHASE DIAGRAMS, SOLIDS.

  13. Selective Stationary Phase for Solid-Phase Microextraction Analysis of Sarin (GB)

    SciTech Connect

    Harvey, Scott; Nelson, D. A.; Wright, Bob W.; Gates, J. W.

    2002-03-02

    A number of critical field applications require monitoring air samples for trace levels of chemical warfare agents. Solid-phase microextraction (SPME) is a convenient format to conduct these analyses. Measurements could be significantly improved if a SPME phase selective for nerve agents were substituted for nonselective polymers typically used (e.g., polydimethylsiloxane). This paper evaluates a novel stationary phase, previously developed for methylphosphonate sensor applications, for use with SPME sampling. The phenol-based polymer, BSP3, was found to offer far higher selectivity toward sarin (GB) than polydimethylsiloxane due to a pronounced affinity toward the target analyte and a lower affinity toward hydrocarbons.

  14. Selective Stationary Phase for Solid-Phase Microextraction Analysis of Sarin (GB)

    SciTech Connect

    Harvey, Scott D.; Nelson, David A.; Wright, Bob W.; Grate, Jay W.

    2002-04-19

    A number of critical field applications require monitoring air samples for trace levels of chemical warfare agents. Solid-phase microextraction (SPME) is a convenient format to conduct these analyses. Measurements could be significantly improved if a SPME phase selective for nerve agents were substituted for nonselective polymers typically used (e.g.,polydimethylsiloxane). This paper evaluates a novel stationary phase, previously developed for methylphosphonate sensor applications, for use with SPME sampling. The phenol-based polymer, BSP3, was found to offer far higher selectivity toward sarin (GB) than polydimethylsiloxane due to a pronounced affinity toward the target analyte and a lower affinity toward hydrocarbons.

  15. Kinetics of β→δ Solid-Solid Phase Transition of HMX

    SciTech Connect

    Weese, Randall K.

    2000-09-01

    In order to calculate the kinetic parameters from DSC data, we have used the generally accepted methods of Bershtein [13]. We have calculated the rate constants for 4 temperatures and the activation energy based on the shift in the transition temperature, β→δ for HMX. The values of Ea from this work is 402 kJ/mol compared to previous results by Brill [9] of 204 kJ/mol. Brill and associates measured the phase transition of HMX using FTIR, sodium chloride plates and silicon oil. Given the differences in technique between FTIR and DSC the results found in this work are reasonable. In this investigation a large sample set (16) proved to be statistically valid for the determinations of k. Linear regressions were performed, observed and good fits were obtained, for each temperature. The enthalpy determination of ΔHo, for the β→δ phase transition was reproducible with in 3 parts in 100 over the range of this experiment. Thus, the data derived from this experiment k, Ea, and ΔHo are valid parameters for the solid-solid phase transition. Obtaining pure β phase HMX was very important for this investigation. Related to the phase change is the particle size distribution and is presented in Figure 3. Compared to previous work on HMX, this study utilized very pure β phase material. In addition, the particle size was controlled more rigorously at about 160 μm, giving a more consistent result for α. Thus, these kinetic results should have less scatter than results with less control of HMX purity and particle size. The kinetic basis of the polymorphic conversion is due to the cohesive forces in the HMX crystal lattice [21]. The energy required to bring about change from chair to chair-chair conformation has been reported by Brill [21] as ring torsion and is essentially a normal mode of the molecule that requires about 4 kJ mol-1. For the purpose of this investigation the energy of activation found in this work

  16. Solid Phase Characterization of Tank 241-C-108 Residual Waste Solids Samples

    SciTech Connect

    Cooke, Gary A.; Pestovich, John A.; Huber, Heinz J.

    2013-05-29

    This report presents the results for solid phase characterization (SPC) of solid samples removed from tank 241-C-108 (C-108) on August 12-13,2012, using the off-riser sampler. Samples were received at the 222-S Laboratory on August 13 and were described and photographed. The SPC analyses that were performed include scanning electron microscopy (SEM) using the ASPEX(R)l scanning electron microscope, X-ray diffraction (XRD) using the Rigaku(R) 2 MiniFlex X-ray diffractometer, and polarized light microscopy (PLM) using the Nikon(R) 3 Eclipse Pol optical microscope. The SEM is equipped with an energy dispersive X-ray spectrometer (EDS) to provide chemical information. Gary A. Cooke conducted the SEM analysis, John A. Pestovich performed the XRD analysis, and Dr. Heinz J. Huber performed the PLM examination. The results of these analyses are presented here.

  17. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy

    PubMed Central

    Zhou, Shengqiang; Liu, Fang; Prucnal, S.; Gao, Kun; Khalid, M.; Baehtz, C.; Posselt, M.; Skorupa, W.; Helm, M.

    2015-01-01

    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability. PMID:25660096

  18. Effects of sample homogenization on solid phase sediment toxicity

    SciTech Connect

    Anderson, B.S.; Hunt, J.W.; Newman, J.W.; Tjeerdema, R.S.; Fairey, W.R.; Stephenson, M.D.; Puckett, H.M.; Taberski, K.M.

    1995-12-31

    Sediment toxicity is typically assessed using homogenized surficial sediment samples. It has been recognized that homogenization alters sediment integrity and may result in changes in chemical bioavailability through oxidation-reduction or other chemical processes. In this study, intact (unhomogenized) sediment cores were taken from a Van Veen grab sampler and tested concurrently with sediment homogenate from the same sample in order to investigate the effect of homogenization on toxicity. Two different solid-phase toxicity test protocols were used for these comparisons. Results of amphipod exposures to samples from San Francisco Bay indicated minimal difference between intact and homogenized samples. Mean amphipod survival in intact cores relative to homogenates was similar at two contaminated sites. Mean survival was 34 and 33% in intact and homogenized samples, respectively, at Castro Cove. Mean survival was 41% and 57%, respectively, in intact and homogenized samples from Islais Creek. Studies using the sea urchin development protocol, modified for testing at the sediment/water interface, indicated considerably more toxicity in intact samples relative to homogenized samples from San Diego Bay. Measures of metal flux into the overlying water demonstrated greater flux of metals from the intact samples. Zinc flux was five times greater, and copper flux was twice as great in some intact samples relative to homogenates. Future experiments will compare flux of metals and organic compounds in intact and homogenized sediments to further evaluate the efficacy of using intact cores for solid phase toxicity assessment.

  19. Solid-Phase Purification of Synthetic DNA Sequences.

    PubMed

    Grajkowski, Andrzej; Cieslak, Jacek; Beaucage, Serge L

    2016-08-05

    Although high-throughput methods for solid-phase synthesis of DNA sequences are currently available for synthetic biology applications and technologies for large-scale production of nucleic acid-based drugs have been exploited for various therapeutic indications, little has been done to develop high-throughput procedures for the purification of synthetic nucleic acid sequences. An efficient process for purification of phosphorothioate and native DNA sequences is described herein. This process consists of functionalizing commercial aminopropylated silica gel with aminooxyalkyl functions to enable capture of DNA sequences carrying a 5'-siloxyl ether linker with a "keto" function through an oximation reaction. Deoxyribonucleoside phosphoramidites functionalized with the 5'-siloxyl ether linker were prepared in yields of 75-83% and incorporated last into the solid-phase assembly of DNA sequences. Capture of nucleobase- and phosphate-deprotected DNA sequences released from the synthesis support is demonstrated to proceed near quantitatively. After shorter than full-length DNA sequences were washed from the capture support, the purified DNA sequences were released from this support upon treatment with tetra-n-butylammonium fluoride in dry DMSO. The purity of released DNA sequences exceeds 98%. The scalability and high-throughput features of the purification process are demonstrated without sacrificing purity of the DNA sequences.

  20. Enhanced solid-phase recombinase polymerase amplification and electrochemical detection.

    PubMed

    Del Río, Jonathan Sabaté; Lobato, Ivan Magriñà; Mayboroda, Olena; Katakis, Ioanis; O'Sullivan, Ciara K

    2017-03-02

    Recombinase polymerase amplification (RPA) is an elegant method for the rapid, isothermal amplification of nucleic acids. Here, we elucidate the optimal surface chemistry for rapid and efficient solid-phase RPA, which was fine-tuned in order to obtain a maximum signal-to-noise ratio, defining the optimal DNA probe density, probe-to-lateral spacer ratio (1:0, 1:1, 1:10 and 1:100) and length of a vertical spacer of the probe as well as investigating the effect of different types of lateral spacers. The use of different labelling strategies was also examined in order to reduce the number of steps required for the analysis, using biotin or horseradish peroxidase-labelled reverse primers. Optimisation of the amplification temperature used and the use of surface blocking agents were also pursued. The combination of these changes facilitated a significantly more rapid amplification and detection protocol, with a lowered limit of detection (LOD) of 1 · 10(-15) M. The optimised protocol was applied to the detection of Francisella tularensis in real samples from hares and a clear correlation with PCR and qPCR results observed and the solid-phase RPA demonstrated to be capable of detecting 500 fM target DNA in real samples. Graphical abstract Relative size of thiolated lateral spacers tested versus the primer and the uvsx recombinase protein.

  1. Municipal solid waste development phases: Evidence from EU27.

    PubMed

    Vujić, Goran; Gonzalez-Roof, Alvaro; Stanisavljević, Nemanja; Ragossnig, Arne M

    2015-12-01

    Many countries in the European Union (EU) have very developed waste management systems. Some of its members have managed to reduce their landfilled waste to values close to zero during the last decade. Thus, European Union legislation is very stringent regarding waste management for their members and candidate countries, too. This raises the following questions: Is it possible for developing and developed countries to comply with the European Union waste legislation, and under what conditions? How did waste management develop in relation to the economic development in the countries of the European Union? The correlation between waste management practices and economic development was analysed for 27 of the European Union Member States for the time period between 1995 and 2007. In addition, a regression analysis was performed to estimate landfilling of waste in relation to gross domestic product for every country. The results showed a strong correlation between the waste management variables and the gross domestic product of the EU27 members. The definition of the municipal solid waste management development phases followed a closer analysis of the relation between gross domestic product and landfilled waste. The municipal solid waste management phases are characterised by high landfilling rates at low gross domestic product levels, and landfilling rates near zero at high gross domestic product levels. Hence the results emphasize the importance of wider understanding of what is required for developing countries to comply with the European Union initiatives, and highlight the importance of allowing developing countries to make their own paths of waste management development.

  2. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy.

    PubMed

    Zhou, Shengqiang; Liu, Fang; Prucnal, S; Gao, Kun; Khalid, M; Baehtz, C; Posselt, M; Skorupa, W; Helm, M

    2015-02-09

    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability.

  3. Studies of phase transitions in the aripiprazole solid dosage form.

    PubMed

    Łaszcz, Marta; Witkowska, Anna

    2016-01-05

    Studies of the phase transitions in an active substance contained in a solid dosage form are very complicated but essential, especially if an active substance is classified as a BCS Class IV drug. The purpose of this work was the development of sensitive methods for the detection of the phase transitions in the aripiprazole tablets containing initially its form III. Aripiprazole exhibits polymorphism and pseudopolymorphism. Powder diffraction, Raman spectroscopy and differential scanning calorimetry methods were developed for the detection of the polymorphic transition between forms III and I as well as the phase transition of form III into aripiprazole monohydrate in tablets. The study involved the initial 10 mg and 30 mg tablets, as well as those stored in Al/Al blisters, a triplex blister pack and HDPE bottles (with and without desiccant) under accelerated and long term conditions. The polymorphic transition was not observed in the initial and stored tablets but it was visible on the DSC curve of the Abilify(®) 10 mg reference tablets. The formation of the monohydrate was observed in the diffractograms and Raman spectra in the tablets stored under accelerated conditions. The monohydrate phase was not detected in the tablets stored in the Al/Al blisters under long term conditions. The results showed that the Al/Al blisters can be recommended as the packaging of the aripiprazole tablets containing form III.

  4. The role of solid-solid phase transitions in mantle convection

    NASA Astrophysics Data System (ADS)

    Faccenda, Manuele; Dal Zilio, Luca

    2017-01-01

    With changing pressure and temperature conditions, downwelling and upwelling crustal and mantle rocks experience several solid-solid phase transitions that affect the mineral physical properties owing to structural changes in the crystal lattice and to the absorption or release of latent heat. Variations in density, together with phase boundary deflections related to the non-null reaction slope, generate important buoyancy forces that add to those induced by thermal perturbations. These buoyancy forces are proportional to the density contrast between reactant and product phases, their volume fraction, the slope and the sharpness of the reaction, and affect the style of mantle convection depending on the system composition. In a homogeneous pyrolitic mantle there is little tendency for layered convection, with slabs that may stagnate in the transition zone because of the positive buoyancy caused by post-spinel and post-ilmenite reactions, and hot plumes that are accelerated by phase transformations in the 600-800 km depth range. By adding chemical and mineralogical heterogeneities as on Earth, phase transitions introduce bulk rock and volatiles filtering effects that generate a compositional gradient throughout the entire mantle, with levels that are enriched or depleted in one or more of these components. Phase transitions often lead to mechanical softening or hardening that can be related to a different intrinsic mechanical behaviour and volatile solubility of the product phases, the heating or cooling associated with latent heat, and the transient grain size reduction in downwelling cold material. Strong variations in viscosity would enhance layered mantle convection, causing slab stagnation and plume ponding. At low temperatures and relatively dry conditions, reactions are delayed due to the sluggish kinetics, so that non-equilibrium phase aggregates can persist metastably beyond the equilibrium phase boundary. Survival of low-density metastable olivine

  5. Modified phase-field-crystal model for solid-liquid phase transitions

    NASA Astrophysics Data System (ADS)

    Guo, Can; Wang, Jincheng; Wang, Zhijun; Li, Junjie; Guo, Yaolin; Tang, Sai

    2015-07-01

    A modified phase-field-crystal (PFC) model is proposed to describe solid-liquid phase transitions by reconstructing the correlation function. The effects of fitting parameters of our modified PFC model on the bcc-liquid phase diagram, numerical stability, and solid-liquid interface properties during planar interface growth are examined carefully. The results indicate that the increase of the correlation function peak width at k =km will enhance the stability of the ordered phase, while the increase of peak height at k =0 will narrow the two-phase coexistence region. The third-order term in the free-energy function and the short wave-length of the correlation function have significant influences on the numerical stability of the PFC model. During planar interface growth, the increase of peak width at k =km will decrease the interface width and the velocity coefficient C , but increase the anisotropy of C and the interface free energy. Finally, the feasibility of the modified phase-field-crystal model is demonstrated with a numerical example of three-dimensional dendritic growth of a body-centered-cubic structure.

  6. Modified phase-field-crystal model for solid-liquid phase transitions.

    PubMed

    Guo, Can; Wang, Jincheng; Wang, Zhijun; Li, Junjie; Guo, Yaolin; Tang, Sai

    2015-07-01

    A modified phase-field-crystal (PFC) model is proposed to describe solid-liquid phase transitions by reconstructing the correlation function. The effects of fitting parameters of our modified PFC model on the bcc-liquid phase diagram, numerical stability, and solid-liquid interface properties during planar interface growth are examined carefully. The results indicate that the increase of the correlation function peak width at k=k(m) will enhance the stability of the ordered phase, while the increase of peak height at k=0 will narrow the two-phase coexistence region. The third-order term in the free-energy function and the short wave-length of the correlation function have significant influences on the numerical stability of the PFC model. During planar interface growth, the increase of peak width at k=k(m) will decrease the interface width and the velocity coefficient C, but increase the anisotropy of C and the interface free energy. Finally, the feasibility of the modified phase-field-crystal model is demonstrated with a numerical example of three-dimensional dendritic growth of a body-centered-cubic structure.

  7. Determination of nitrate esters in water samples Comparison of efficiency of solid-phase extraction and solid-phase microextraction.

    PubMed

    Jezová, Vera; Skládal, Jan; Eisner, Ales; Bajerová, Petra; Ventura, Karel

    2007-12-07

    This paper deals with comparison of efficiency of extraction techniques (solid-phase extraction, SPE and solid-phase microextraction, SPME) used for extraction of nitrate esters (ethyleneglycoldinitrate, EGDN and nitroglycerin, NG), representing the first step of the method of quantitative determination of trace concentrations of nitrate esters in water samples. EGDN and NG are subsequently determined by means of high-performance liquid chromatography with ultraviolet detection (HPLC-UV). Optimization of SPE and SPME conditions was carried out using model water samples. Seven SPE cartridges were tested and the conditions were optimized (type of sorbent, type and volume of solvent to be used as eluent). For both nitrate esters the limit of detection (LOD) and the limit of quantification (LOQ) obtained using SPE/HPLC-UV were 0.23 microg mL(-1) and 0.70 microg mL(-1), respectively. Optimization of SPME conditions: type of SPME fibre (four fibres were tested), type and time of sorption/desorption, temperature of sorption. PDMS/DVB (polydimethylsiloxane/divinylbenzene) fibre coating proved to be suitable for extraction of EGDN and NG. For this fibre the LOD and the LOQ for both nitrate esters were 0.16 microg mL(-1) and 0.50 microg mL(-1), respectively. Optimized methods SPE/HPLC-UV and SPME/HPLC-UV were then used for quantitative determination of nitrate esters content in real water samples from the production of EGDN and NG.

  8. System for exchange of hydrogen between liquid and solid phases

    DOEpatents

    Reilly, J.J.; Grohse, E.W.; Johnson, J.R.; Winsche, W.E.

    1985-02-22

    The reversible reaction M + x/2 H/sub 2/ reversible MH/sub x/, wherein M is a reversible metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the actual H/sub 2/ pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

  9. Ferrofluid-based dispersive solid phase extraction of palladium.

    PubMed

    Farahani, Malihe Davudabadi; Shemirani, Farzaneh; Gharehbaghi, Maysam

    2013-05-15

    A new mode of dispersive solid phase extraction based on ferrofluid has been developed. In this method, an appropriate amount of ferrofluid is injected rapidly into the aqueous sample by a syringe. Since the sorbent is highly dispersed in the aqueous phase, extraction can be achieved within a few seconds. The ferrofluid can be attracted by a magnet and no centrifugation step is needed for phase separation. Palladium was used as a model compound in the development and evaluation of the extraction procedure in combination with flame atomic absorption spectrometry. The experimental parameters (pH, DDTC concentration, type and concentration of eluent, the amount of adsorbent, extraction time, and the effect of interfering ions) were investigated in detail. Under the optimized conditions, the calibration graph was linear over the range of 1-100 μg L(-1) and relative standard deviation of 3.3% at 0.1 μg mL(-1) was obtained (n=7). The limit of detection and enrichment factor (EF) was obtained to be 0.35 μg L(-1) and 267, respectively. The maximum adsorption capacity of the adsorbent at optimum conditions was found to be 24.6 mg g(-1) for Pd(II). The method was validated using certified reference material, and has been applied for the determination of trace Pd(II) in actual samples with satisfactory results.

  10. Density functional theory study of phase IV of solid hydrogen

    NASA Astrophysics Data System (ADS)

    Pickard, Chris J.; Martinez-Canales, Miguel; Needs, Richard J.

    2012-06-01

    We have studied solid hydrogen up to pressures of 300 GPa and temperatures of 350 K using density functional theory methods and have found “mixed structures” that are more stable than those predicted earlier. Mixed structures consist of alternate layers of strongly bonded molecules and weakly bonded graphene-like sheets. Quasiharmonic vibrational calculations show that mixed structures are the most stable at room temperature over the pressure range 250-295 GPa. These structures are stabilized with respect to strongly bonded molecular phases at room temperature by the presence of lower frequency vibrational modes arising from the graphene-like sheets. Our results for the mixed structures are consistent with the experimental Raman data [M. I. Eremets and I. A. Troyan, Nat. Mater.1476-112210.1038/nmat3175 10, 927 (2011) and R. T. Howie , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.108.125501 108, 125501 (2012)]. We find that mixed phases are reasonable structural models for phase IV of hydrogen.

  11. System for exchange of hydrogen between liquid and solid phases

    DOEpatents

    Reilly, James J.; Grohse, Edward W.; Johnson, John R.; Winsche, deceased, Warren E.

    1988-01-01

    The reversible reaction M+x/2 H.sub.2 .rarw..fwdarw.MH.sub.x, wherein M is a reversible metal hydride former that forms a hydride MH.sub.x in the presence of H.sub.2, generally used to store and recall H.sub.2, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H.sub.2, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H.sub.2 through the liquid is dependent upon the H.sub.2 pressure in the gas phase at a given temperature. When the actual H.sub.2 pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particles. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

  12. Time-lapse 3-D measurements of a glucose biosensor in multicellular spheroids by light sheet fluorescence microscopy in commercial 96-well plates

    PubMed Central

    Maioli, Vincent; Chennell, George; Sparks, Hugh; Lana, Tobia; Kumar, Sunil; Carling, David; Sardini, Alessandro; Dunsby, Chris

    2016-01-01

    Light sheet fluorescence microscopy has previously been demonstrated on a commercially available inverted fluorescence microscope frame using the method of oblique plane microscopy (OPM). In this paper, OPM is adapted to allow time-lapse 3-D imaging of 3-D biological cultures in commercially available glass-bottomed 96-well plates using a stage-scanning OPM approach (ssOPM). Time-lapse 3-D imaging of multicellular spheroids expressing a glucose Förster resonance energy transfer (FRET) biosensor is demonstrated in 16 fields of view with image acquisition at 10 minute intervals. As a proof-of-principle, the ssOPM system is also used to acquire a dose response curve with the concentration of glucose in the culture medium being varied across 42 wells of a 96-well plate with the whole acquisition taking 9 min. The 3-D image data enable the FRET ratio to be measured as a function of distance from the surface of the spheroid. Overall, the results demonstrate the capability of the OPM system to measure spatio-temporal changes in FRET ratio in 3-D in multicellular spheroids over time in a multi-well plate format. PMID:27886235

  13. Time-lapse 3-D measurements of a glucose biosensor in multicellular spheroids by light sheet fluorescence microscopy in commercial 96-well plates

    NASA Astrophysics Data System (ADS)

    Maioli, Vincent; Chennell, George; Sparks, Hugh; Lana, Tobia; Kumar, Sunil; Carling, David; Sardini, Alessandro; Dunsby, Chris

    2016-11-01

    Light sheet fluorescence microscopy has previously been demonstrated on a commercially available inverted fluorescence microscope frame using the method of oblique plane microscopy (OPM). In this paper, OPM is adapted to allow time-lapse 3-D imaging of 3-D biological cultures in commercially available glass-bottomed 96-well plates using a stage-scanning OPM approach (ssOPM). Time-lapse 3-D imaging of multicellular spheroids expressing a glucose Förster resonance energy transfer (FRET) biosensor is demonstrated in 16 fields of view with image acquisition at 10 minute intervals. As a proof-of-principle, the ssOPM system is also used to acquire a dose response curve with the concentration of glucose in the culture medium being varied across 42 wells of a 96-well plate with the whole acquisition taking 9 min. The 3-D image data enable the FRET ratio to be measured as a function of distance from the surface of the spheroid. Overall, the results demonstrate the capability of the OPM system to measure spatio-temporal changes in FRET ratio in 3-D in multicellular spheroids over time in a multi-well plate format.

  14. Higher throughput bioanalysis by automation of a protein precipitation assay using a 96-well format with detection by LC-MS/MS.

    PubMed

    Watt, A P; Morrison, D; Locker, K L; Evans, D C

    2000-03-01

    Generic methodology for the automated preparation and analysis of drug levels in plasma samples within a drug discovery environment was achieved through the redesign of a protein precipitation assay to a microtiter (96-well) plate format and the application of robotic liquid handling for performance of all transfer and pipetting steps. Validation studies revealed that the application of robotics to sample preparation, in general, maintained the analytical accuracy and precision compared with preparing samples manually. The use of rapid gradient LC-MS/MS for analysis coupled with flow diversion of the solvent front allowed the introduction of protein-precipitated samples into the mass spectrometer without the necessity for source cleaning. The problem inherent in automatically pipetting plasma, caused by fibrinogen clots, was overcome by storing samples at -80 degrees C and thus precluding clot formation. The resulting methodology allowed sample preparation for a 96-well plate designed to accommodate 54 unknowns, duplicate 12-point calibration curves, and 6 sets of quality controls at three levels in approximately 2 h. This approach allowed an increase in throughput of sample preparation and analysis to >400 samples per day per LC-MS/MS instrument with minimal manual intervention. Overall, substantial time savings were realized, demonstrating that automation is an increasingly essential tool in a drug discovery bioanalytical environment.

  15. Time-lapse 3-D measurements of a glucose biosensor in multicellular spheroids by light sheet fluorescence microscopy in commercial 96-well plates.

    PubMed

    Maioli, Vincent; Chennell, George; Sparks, Hugh; Lana, Tobia; Kumar, Sunil; Carling, David; Sardini, Alessandro; Dunsby, Chris

    2016-11-25

    Light sheet fluorescence microscopy has previously been demonstrated on a commercially available inverted fluorescence microscope frame using the method of oblique plane microscopy (OPM). In this paper, OPM is adapted to allow time-lapse 3-D imaging of 3-D biological cultures in commercially available glass-bottomed 96-well plates using a stage-scanning OPM approach (ssOPM). Time-lapse 3-D imaging of multicellular spheroids expressing a glucose Förster resonance energy transfer (FRET) biosensor is demonstrated in 16 fields of view with image acquisition at 10 minute intervals. As a proof-of-principle, the ssOPM system is also used to acquire a dose response curve with the concentration of glucose in the culture medium being varied across 42 wells of a 96-well plate with the whole acquisition taking 9 min. The 3-D image data enable the FRET ratio to be measured as a function of distance from the surface of the spheroid. Overall, the results demonstrate the capability of the OPM system to measure spatio-temporal changes in FRET ratio in 3-D in multicellular spheroids over time in a multi-well plate format.

  16. Volume phase holographic gratings for astronomy based on solid photopolymers

    NASA Astrophysics Data System (ADS)

    Zanutta, Alessio; Bianco, Andrea; Insausti, Maider; Garzón, Francisco

    2014-07-01

    Volume Phase Holographic Gratings (VPHG) are gaining more and more interest as optical dispersing elements in new astronomical spectrographs at low and medium resolution. A key point is the development of new photosensitive materials suitable to produce VPHGs that match the stringent requirements of the astronomical environment. Here we report on the performances of VPHG based on Bayfol®HX solid photopolymer films developed by Bayer MaterialScience AG. Parameters affecting the grating efficiency (e. g. photopolymer film thickness and refractive index modulation) are measured and linked to the performances of VPHG working in the VIS-NIR region. Moreover, the behavior at low temperature and the aging properties of such materials/gratings are reported. Substantial efficiency gains on a new VPHG installed at the Asiago's spectrograph are shown and proven on the observation of a standard star (hr5501).

  17. Porous protective solid phase micro-extractor sheath

    DOEpatents

    Andresen, Brian D.; Randich, Erik

    2005-03-29

    A porous protective sheath for active extraction media used in solid phase microextraction (SPME). The sheath permits exposure of the media to the environment without the necessity of extending a fragile coated fiber from a protective tube or needle. Subsequently, the sheath can pierce and seal with GC-MS septums, allowing direct injection of samples into inlet ports of analytical equipment. Use of the porous protective sheath, within which the active extraction media is contained, mitigates the problems of: 1) fiber breakage while the fiber is extended during sampling, 2) active media coating loss caused by physical contact of the bare fiber with the sampling environment; and 3) coating slough-off during fiber extension and retraction operations caused by rubbing action between the fiber and protective needle or tube.

  18. Microscale solid-phase extraction system for explosives.

    PubMed

    Smith, Matthew; Collins, Greg E; Wang, Joseph

    2003-04-04

    A simple, semi-automated, microcolumn solid-phase extraction (SPE) system is optimized for the extraction, preconcentration and HPLC analysis of seven different explosives and explosive derivatives contaminating seawater, river water and well water samples. The microcolumns were constructed from 1/16 in. O.D. PTFE tubing (1 in.=2.54 cm) packed with 0.5-1.5 mg of SPE material. LiChrolut EN or Porapak R. The extraction system consisted of two syringe pumps and several solenoid valves. Optimal detection limits were realized when the sample water flow-rate was maximally increased within the limits of the pump, 5-10 ml/min (despite exceeding the breakthrough threshold of the SPE microcolumn), and when the eluate volume collected from the column was minimized, <5 microl (despite very low recovery percentages).

  19. Solid phase epitaxial regrowth of (001) anatase titanium dioxide

    SciTech Connect

    Barlaz, David Eitan; Seebauer, Edmund G.

    2016-03-15

    The growing interest in metal oxide based semiconductor technologies has driven the need to produce high quality epitaxial films of one metal oxide upon another. Largely unrecognized in synthetic efforts is that some metal oxides offer strongly polar surfaces and interfaces that require electrostatic stabilization to avoid a physically implausible divergence in the potential. The present work examines these issues for epitaxial growth of anatase TiO{sub 2} on strontium titanate (001). Solid phase epitaxial regrowth yields only the (001) facet, while direct crystalline growth by atomic layer deposition yields both the (112) and (001). The presence of amorphous TiO{sub 2} during regrowth may provide preferential stabilization for formation of the (001) facet.

  20. Solid-phase genotoxicity assay for organic compounds in soil

    SciTech Connect

    Alexander, R.R.; Chung, N.; Alexander, M.

    1999-03-01

    A genotoxicity assay was developed for samples from environments in which toxic organic compounds are largely sorbed. The assay entails measurement of the rate of mutation of a strain of Pseudomonas putida to rifampicin resistance. The ratio of induced to spontaneous mutants was a function of the concentration of a test mutagen in soil. In studies of the utility of the assay in samples amended with 2-aminofluorene as a test mutagen, the ratio of induced to spontaneous mutants declined with time. The decline paralleled the disappearance of extractable 2-aminofluorene from the soil. The ratio of induced to spontaneous mutants also feel in four other soils with dissimilar properties. The authors suggest that this solid-phase assay is more appropriate for the estimation of genotoxicants sorbed in soil than assays involving extractants or suspensions of soil or sediment samples.

  1. Method for preparing a solid phase microextraction device using aerogel

    DOEpatents

    Miller, Fred S.; Andresen, Brian D.

    2006-10-24

    A sample collection substrate of aerogel and/or xerogel materials bound to a support structure is used as a solid phase microextraction (SPME) device. The xerogels and aerogels may be organic or inorganic and doped with metals or other compounds to target specific chemical analytes. The support structure is typically formed of a glass fiber or a metal wire (stainless steel or kovar). The devices are made by applying gel solution to the support structures and drying the solution to form aerogel or xerogel. Aerogel particles may be attached to the wet layer before drying to increase sample collection surface area. These devices are robust, stable in fields of high radiation, and highly effective at collecting gas and liquid samples while maintaining superior mechanical and thermal stability during routine use. Aerogel SPME devices are advantageous for use in GC/MS analyses due to their lack of interfering background and tolerance of GC thermal cycling.

  2. Bench-scale solid phase biotreatment: Benfield Industries Superfund site

    SciTech Connect

    Marlowe, M.W.; Harper, T.R.; Semenak, R.K.

    1995-12-31

    The Benfield Industries, Inc. Superfund site located in Hazelwood, North Carolina has been found to have approximately 15,000 cubic yards of polycyclic aromatic hydrocarbon (PAH) contaminated soil. Risk based clean up goals were specified at the site for eight target PAH compounds including benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, chrysene, indeno(1,2,3-cd)pyrene, naphthalene, and pentachlorophenol. Treatability studies were performed to evaluate solid phase bioremediation, which includes ex-situ and in-situ land treatment processes, for treatment of the site soil. All treatments were conducted using only indigenous microorganisms maintained under aerobic conditions. Two soil samples with different levels of PAH contamination were collected from the site for use in the treatability evaluations. The two soil samples were contaminated with total PAHs at concentrations of approximately 30 milligrams per kilogram (mg/kg) and 6,000 mg/kg, respectively. Three solid phase bioremediation studies were conducted over a one and one half year period using starting concentrations of total PAHs of approximately 30; 600; and 6,000 mg/kg. The objectives of the studies included determining (1) if clean up goals could be achieved, (2) the approximate biodegradation rate of PAHs in the site soils, and (3) the optimum environmental conditions for biodegradation of the PAHs. Some of the environmental parameters which were varied during the testing included moisture levels, soil conditioners, nutrients and pH. The results of the testing indicated that total and target PAHs can be reduced by up to 90 percent in less than 50 days, depending on environmental conditions maintained in the reactors. Clean up goals for all of the target compounds were achieved at some point during the study.

  3. ACTIVATION OF HAGEMAN FACTOR IN SOLID AND FLUID PHASES

    PubMed Central

    Cochrane, C. G.; Revak, S. D.; Wuepper, K. D.

    1973-01-01

    The activation of Hageman factor in solid and fluid phase has been analyzed. Activation of highly purified Hageman factor occurred after it interacted with and became bound to a negatively charged surface. Activation was observed in the absence of enzymes that are inhibitable with diisopropylfluorophosphate, phenyl methyl sulfonyl fluoride and ε-amino-n-caproic acid. The binding of [125I]Hageman factor to the negatively charged surface was markedly inhibited by plasma or purified plasma proteins. Activation of Hageman factor in solution (fluid phase) was obtained with kallikrein, plasmin, and Factor XI (plasma thromboplastin antecedent). Kallikrein was greater than 10 times more active in its ability to activate Hageman factor than plasmin and Factor XI. The data offer a plausible explanation for the finding that highly purified kallikrein promotes clotting of normal plasma. In addition, the combined results of this and previously reported data from this laboratory indicate that the reciprocal activation of Hageman factor by kallikrein in fluid phase is essential for normal rate of activation of the intrinsic-clotting, kinin-forming, and fibrinolytic systems. Activation of Hageman factor was associated with three different structural changes in the molecule: (a) Purified Hageman factor, activated on negatively charged surfaces retained its native mol wt of 80–90,000. Presumably a conformational change accompanied activation. (b) In fluid phase, activation with kallikrein and plasmin did not result in cleavage of large fragments of rabbit Hageman factor, although the activation required hydrolytic capacity of the enzymes. (c) Activation of human Hageman factor with kallikrein or plasmin was associated with cleavage of the molecule to 52,000, 40,000, and 28,000 mol wt fragments. Activation of rabbit Hageman factor with trypsin resulted in cleavage of the molecule into three fragments, each of 30,000 mol wt as noted previously. This major cleavage occurred

  4. New methods and materials for solid phase extraction and high performance liquid chromatography

    SciTech Connect

    Dumont, Philip John

    1996-04-23

    This paper describes methods for solid phase extraction and high performance liquid chromatography (HPLC). The following are described: Effects of Resin Sulfonation on the Retention of Polar Organic Compounds in Solid Phase Extraction; Ion-Chromatographic Separation of Alkali Metals In Non-Aqueous Solvents; Cation-Exchange Chromatography in Non-Aqueous Solvents; and Silicalite As a Stationary Phase For HPLC.

  5. Development of novel solid-phase protein formulations

    NASA Astrophysics Data System (ADS)

    Montalvo Ortiz, Brenda Liz

    Proteins are the next-generation drugs for the treatment of several diseases. However, the number of protein drugs is still limited due to the physical or chemical instability of proteins during processing, formulation, storage, and delivery. The formulation of proteins at the solid state has advantages over liquid state, such as improved stability during long-term storage and delivery and decreases transportation costs. In this dissertation, we developed new solid-phase protein formulations in which the integrity of the protein was not compromised. The long term goal of this research was to use these protein formulations to improve protein stability in drug delivery devices, such as poly(lactic-co-glycolic) acid (PLGA). The first solid-phase protein formulation developed in this investigation was named "glassification". We proposed glassification as an alternative protein dehydration technique to the common used one, lyophilization, because this last method involves a series of steps which are detrimental to protein structure and stability. The glassification method consisted on protein dehydration by the use of organic solvents. As a result of the glassification process a small (micrometer size range) protein solid bead was obtained. The proteins used to study the glassification process were lysozyme (LYS), alpha-chymotrypsin (CHYMO) and horseradish peroxidase (HRP). These studies revealed that the glassification process itself did not alter protein structure and the activity was preserved. Ethyl acetate was the most effective organic solvent for protein glassification because it led to the highest protein residual activity, no insoluble aggregate formation and is a relatively non-toxic solvent, which allow the incorporation of these protein microparticles in PLGA microspheres. The incorporation of spherical HRP microparticles into PLGA microspheres resulted in superior properties when compared with encapsulated lyophilized HRP powder, such as improved release

  6. Solid-solid phase transformations induced through cation exchange and strain in 2D heterostructured copper sulfide nanocrystals.

    PubMed

    Ha, Don-Hyung; Caldwell, Andrew H; Ward, Matthew J; Honrao, Shreyas; Mathew, Kiran; Hovden, Robert; Koker, Margaret K A; Muller, David A; Hennig, Richard G; Robinson, Richard D

    2014-12-10

    We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (<1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu1.81S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu1.94S)/low chalcocite (Cu2S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼ 5 nm thick. To minimize this strain energy, a second phase transformation occurs back to the roxbyite phase, which shares a similar sulfur sublattice to wurtzite ZnS. The observation of a solid-solid phase transformation in our unique heterostructured NCs provides a new pathway to control desired phases and an insight into the influence of cation exchange on nanoscale phase transitions in heterostructured materials.

  7. Alternative solvents for elevated-temperature solid-phase parallel synthesis. Application to thionation of amides.

    PubMed

    Coats, Steven J; Link, Jeffrey S; Hlasta, Dennis J

    2003-03-06

    A new class of higher-boiling solvents was investigated for elevated-temperature solid-phase parallel synthesis. Extremely low vapor pressures at high temperature and a broader range of solvent effect tuning make this new class of solvents an ideal choice for high-temperature parallel solid-phase synthesis. Benzyl benzoate is identified as a superior high-boiling solvent for parallel solid-phase Lawesson's thionation reactions.

  8. Demonstration of entanglement-enhanced phase estimation in solid

    PubMed Central

    Liu, Gang-Qin; Zhang, Yu-Ran; Chang, Yan-Chun; Yue, Jie-Dong; Fan, Heng; Pan, Xin-Yu

    2015-01-01

    Precise parameter estimation plays a central role in science and technology. The statistical error in estimation can be decreased by repeating measurement, leading to that the resultant uncertainty of the estimated parameter is proportional to the square root of the number of repetitions in accordance with the central limit theorem. Quantum parameter estimation, an emerging field of quantum technology, aims to use quantum resources to yield higher statistical precision than classical approaches. Here we report the first room-temperature implementation of entanglement-enhanced phase estimation in a solid-state system: the nitrogen-vacancy centre in pure diamond. We demonstrate a super-resolving phase measurement with two entangled qubits of different physical realizations: an nitrogen-vacancy centre electron spin and a proximal 13C nuclear spin. The experimental data shows clearly the uncertainty reduction when entanglement resource is used, confirming the theoretical expectation. Our results represent an elemental demonstration of enhancement of quantum metrology against classical procedure. PMID:25832364

  9. Size Dependence of a Temperature-Induced Solid-Solid Phase Transition in Copper(I) Sulfide

    SciTech Connect

    Rivest, Jessy B; Fong, Lam-Kiu; Jain, Prashant K; Toney, Michael F; Alivisatos, A Paul

    2011-07-24

    Determination of the phase diagrams for the nanocrystalline forms of materials is crucial for our understanding of nanostructures and the design of functional materials using nanoscale building blocks. The ability to study such transformations in nanomaterials with controlled shape offers further insight into transition mechanisms and the influence of particular facets. Here we present an investigation of the size-dependent, temperature-induced solid-solid phase transition in copper sulfide nanorods from low- to high-chalcocite. We find the transition temperature to be substantially reduced, with the high chalcocite phase appearing in the smallest nanocrystals at temperatures so low that they are typical of photovoltaic operation. Size dependence in phase trans- formations suggests the possibility of accessing morphologies that are not found in bulk solids at ambient conditions. These other- wise-inaccessible crystal phases could enable higher-performing materials in a range of applications, including sensing, switching, lighting, and photovoltaics.

  10. A simple 96-well liquid-liquid extraction with a mixture of acetonitrile and methyl t-butyl ether for the determination of a drug in human plasma by high-performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Xue, Y-J; Pursley, Janice; Arnold, Mark E

    2004-02-04

    A simple 96-well plate liquid-liquid extraction (LLE), liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated for the determination of a basic drug candidate in human plasma. Against the wisdom of conventional approaches, an aqueous/organic miscible solvent, acetonitrile, was used for liquid-liquid extraction along with methyl t-butyl ether. The use of acetonitrile effectively eliminated the formation of the irregular emulsion between aqueous/organic interfaces and modulated the polarity of the extraction solvents to achieve the desired recovery. This approach, which solved the emulsion problem, permitted the method to be automated using standard 96-well plate technology. A practical application was demonstrated through the use of this technique in the measurement of a novel drug in human plasma samples by LC/MS/MS. Chromatographic separation was achieved isocratically on a Phenomenox C18(2) Luna column (2 mm x 50 mm, 5 microm). The mobile phase contained 60% of 0.1% formic acid and 40% acetonitrile. Detection was by positive ion electrospray tandem mass spectrometry. The standard curve, which ranged from 1.22 to 979ng/ml, was fitted to a 1/x2 weighted quadratic regression model. The validation results show that this method was very rugged and had excellent precision and accuracy. The actual sample analysis results further demonstrated that this extraction procedure is well suited for real life applications. It is expected that with some modifications, this approach can be applied for the extraction of similar compounds from various biological fluids.

  11. A 96-well single-pot protein precipitation, liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the determination of muraglitazar, a novel diabetes drug, in human plasma.

    PubMed

    Xue, Y-J; Liu, Jane; Pursley, Janice; Unger, Steve

    2006-02-02

    A 96-well single-pot protein precipitation, liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated for the determination of muraglitazar, a PPAR alpha/gamma dual agonist, in human plasma. The internal standard, a chemical analogue, was dissolved in acetonitrile containing 0.1% formic acid. The solvent system was also served as a protein precipitation reagent. Human plasma samples (0.1 mL) and the internal standard solution (0.3 mL) were added to a 96-well plate. The plate was vortexed for 1 min and centrifuged for 5 min. Then the supernatant layers were directly injected into the LC/MS/MS system. The chromatographic separation was achieved isocratically on a Phenomenox C18(2) Luna column (2 mm x 50 mm, 5 microm). The mobile phase contained 20/80 (v/v) of water and acetonitrile containing 0.1% formic acid. Detection was by positive ion electrospray tandem mass spectrometry on a Sciex API 3000. The standard curve, which ranged from 1 to 1000 ng/mL, was fitted to a 1/x weighted quadratic regression model. This single-pot approach effectively eliminated three time consuming sample preparation steps: sample transfer, dry-down, and reconstitution before the injection, while it preserved all the benefits of the traditional protein precipitation. By properly adjusting the autosampler needle offset level, only the supernatant was injected, without disturbing the precipitated proteins in the bottom. As a result, the quality of chromatography and column life were not compromised. After more than 600 injections, there was only slightly increase of column back-pressure. The validation results demonstrated that this method was rugged and provide satisfactory precision and accuracy. The method has been successfully applied to analyze human plasma samples in support of a first-in-man study. This method has also been validated in monkey and mouse plasma for the determination of muraglitazar.

  12. High-throughput sample preparation for the quantitation of acephate, methamidophos, omethoate, dimethoate, ethylenethiourea, and propylenethiourea in human urine using 96-well-plate automated extraction and high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Jayatilaka, Nayana K; Angela Montesano, M; Whitehead, Ralph D; Schloth, Sara J; Needham, Larry L; Barr, Dana Boyd

    2011-07-01

    Acephate, methamidophos, o-methoate, and dimethoate are organophosphorus pesticides, and ethylenethiouria and propylenethiourea are two metabolites from the bisdithiocarbamate fungicide family. They are some of the most widely used pesticides and fungicides in agriculture both domestically and abroad. The existing high-performance liquid chromatography (HPLC)-tandem mass spectrometry (MS/MS) method for the measurement of these compounds in human urine was improved by using a 96-well plate format sample preparation; the use of HPLC-MS/MS was comparable with a concentration range of 0.125 to 50 ng/ml. Deuterium-labeled acephate, ethylenethiouria, and methamidophos were used as internal standards. The sample preparation procedure, in the 96-well format with a 0.8-ml urine sample size, uses lyophilization of samples, followed by extraction with dichloromethane. The analytes were chromatographed on a Zorbax SB-C3 (4.6 × 150 mm, 5.0-μm) column with gradient elution by using 0.1% formic acid in aqueous solution (solvent A) and 0.1% formic acid in methanol (solvent B) mobile phase at a flow rate of 1 ml/min. Quantitative analysis was performed by atmospheric pressure chemical ionization source in positive ion mode using multiple-reaction monitoring of the precursor-to-product ion pairs for the analytes on a TSQ Quantum Ultra HPLC-MS/MS. Repeated analyses of urine samples spiked with high (15 ng/ml), medium (5 ng/ml), and low (1 ng/ml) concentrations of the analytes gave relative SDs of <13%. The limits of detection were in the range of 0.004-0.01 ng/ml. The method also has high accuracy, high precision, and excellent extraction recovery. Furthermore, the improved sample preparation method decreased the cost and labor required while effectively doubling the analytic throughput with minimal matrix effect.

  13. Development of cystic embryoid bodies with visceral yolk-sac-like structures from mouse embryonic stem cells using low-adherence 96-well plate.

    PubMed

    Yasuda, Emiko; Seki, Yuji; Higuchi, Takatoshi; Nakashima, Fumio; Noda, Tomozumi; Kurosawa, Hiroshi

    2009-04-01

    Cystic embryoid bodies with visceral yolk-sac-like structure (cystic EB-Vs) are used as a model for the study of early extraembryonic tissue formation containing visceral endoderm-like derivatives. In this study, we optimized the cell density of embryonic stem (ES) cells for developing cystic EB-Vs in a low-adherence 96-well plate. When ES cells were seeded at a density of 4000 cells/well, the cystic EB-Vs were most efficiently developed from ES cells via forming multicellular spherical aggregates called embryoid bodies (EBs). The suspension culture in the low-adherence plate was preferable for developing EBs into cystic EB-Vs rather than the attachment culture in the plate coated with 0.1% gelatin. The seeding cell density of 4000 cells/well was always superior to 1000 cells/well in the efficiency of cystic EB-V development. Because the high-cell density culture generally raises the limitation of oxygen and nutrient supplies, we investigated the effects of low-oxygen and low-nutrient conditions on the development of cystic EB-Vs. It was found that low oxygen tension was not a factor for promoting the development of cystic EB-Vs. It was suggested that a low-nutrient medium is preferred for developing cystic EB-Vs rather than a sufficient-nutrient medium. In conclusion, the suspension culture in the low-adherence 96-well plate seeded with 4000 ES cells/well was optimum for developing cystic EB-Vs. The low-nutrient condition may be one of the factors for promoting the development of cystic EB-Vs.

  14. Phase field modeling of grain growth in porous polycrystalline solids

    NASA Astrophysics Data System (ADS)

    Ahmed, Karim E.

    The concurrent evolution of grain size and porosity in porous polycrystalline solids is a technically important problem. All the physical properties of such materials depend strongly on pore fraction and pore and grain sizes and distributions. Theoretical models for the pore-grain boundary interactions during grain growth usually employ restrictive, unrealistic assumptions on the pore and grain shapes and motions to render the problem tractable. However, these assumptions limit the models to be only of qualitative nature and hence cannot be used for predictions. This has motivated us to develop a novel phase field model to investigate the process of grain growth in porous polycrystalline solids. Based on a dynamical system of coupled Cahn-Hilliard and All en-Cahn equations, the model couples the curvature-driven grain boundary motion and the migration of pores via surface diffusion. As such, the model accounts for all possible interactions between the pore and grain boundary, which highly influence the grain growth kinetics. Through a formal asymptotic analysis, the current work demonstrates that the phase field model recovers the corresponding sharp-interface dynamics of the co-evolution of grain boundaries and pores; this analysis also fixes the model kinetic parameters in terms of real materials properties. The model was used to investigate the effect of porosity on the kinetics of grain growth in UO2 and CeO2 in 2D and 3D. It is shown that the model captures the phenomenon of pore breakaway often observed in experiments. Pores on three- and four- grain junctions were found to transform to edge pores (pores on two-grain junction) before complete separation. The simulations demonstrated that inhomogeneous distribution of pores and pore breakaway lead to abnormal grain growth. The simulations also showed that grain growth kinetics in these materials changes from boundary-controlled to pore-controlled as the amount of porosity increases. The kinetic growth

  15. Modeling the solid-liquid phase transition in saturated triglycerides

    NASA Astrophysics Data System (ADS)

    Pink, David A.; Hanna, Charles B.; Sandt, Christophe; MacDonald, Adam J.; MacEachern, Ronald; Corkery, Robert; Rousseau, Dérick

    2010-02-01

    We investigated theoretically two competing published scenarios for the melting transition of the triglyceride trilaurin (TL): those of (1) Corkery et al. [Langmuir 23, 7241 (2007)], in which the average state of each TL molecule in the liquid phase is a discotic "Y" conformer whose three chains are dynamically twisted, with an average angle of ˜120° between them, and those of (2) Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid-state conformation of the TL molecule in the liquid phase is a nematic h∗-conformer whose three chains are in a modified "chair" conformation. We developed two competing models for the two scenarios, in which TL molecules are in a nematic compact-chair (or "h") conformation, with extended, possibly all-trans, chains at low-temperatures, and in either a Y conformation or an h∗ conformation in the liquid state at temperatures higher than the phase-transition temperature, T∗=319 K. We defined an h-Y model as a realization of the proposal of Corkery et al. [Langmuir 23, 7241 (2007)], and explored its predictions by mapping it onto an Ising model in a temperature-dependent field, performing a mean-field approximation, and calculating the transition enthalpy ΔH. We found that the most plausible realization of the h-Y model, as applied to the solid-liquid phase transition in TL, and likely to all saturated triglycerides, gave a value of ΔH in reasonable agreement with the experiment. We then defined an alternative h-h∗ model as a realization of the proposal of Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid phase exhibits an average symmetry breaking similar to an h conformation, but with twisted chains, to see whether it could describe the TL phase transition. The h-h∗ model gave a value of ΔH that was too small by a factor of ˜3-4. We also predicted the temperature dependence of the 1132 cm-1 Raman band for both models, and performed measurements of the ratios of three TL Raman

  16. Solid Phase Microextraction for the Analysis of Nuclear Weapons

    SciTech Connect

    Chambers, D M

    2001-06-01

    This document is a compendium of answers to commonly asked questions about solid phase microextraction as it relates to the analysis of nuclear weapons. We have also included a glossary of terms associated with this analytical method as well as pertinent weapons engineering terminology. Microextraction is a new collection technique being developed to nonintrusively sample chemicals from weapon headspace gases for subsequent analysis. The chemicals that are being targeted outgas from the high explosives and other organic materials used in the weapon assembly. This technique is therefore a valuable tool to: (1) remotely detect and assess the aging of Lawrence Livermore National Laboratory (LLNL) and, in some cases, Sandia National Laboratory (SNL) organic materials; and (2) identify potential compatibility issues (i.e., materials interactions) that should be more carefully monitored during surveillance tear-downs. Microextraction is particularly attractive because of the practical constraints inherent to the weapon surveillance procedure. To remain transparent to other core surveillance activities and fall within nuclear safety guidelines, headspace analysis of the weapons requires a procedure that: (1) maintains ambient temperature conditions; (2) allows practical collection times of less than 20 min; (3) maintains the integrity of the weapon gas volume; (4) provides reproducible and quantitative results; and (5) can identify all possible targets.

  17. Monitoring solid phase synthesis reactions with electrochemical impedance spectroscopy (EIS).

    PubMed

    Hutton, Roger S; Adams, Joseph P; Trivedi, Harish S

    2003-01-01

    This work describes the use of electrochemical impedance spectroscopy (EIS) as a means to monitor solid phase synthesis on resin beads. EIS was used to track changes during the swelling of beads in various solvents, during three typical reactions and throughout cleavage of the final product from the bead. The impedance response was investigated in a chemical reactor and was found to be faintly sensitive to the resin swelling and solvent flow. The position of the electrode within the reactor was found to be critical as polystyrene based beads float or sink dependent upon the solvent used. However, by choosing electrode position it was possible to monitor reaction progress on beads or within the bulk reactant/product mixture. Of the three typical chemical reactions studied impedance spectroscopy successfully followed two. Fitting of the impedance data to an equivalent electrical circuit provided an estimate as to the relative contribution of capacitive and resistive components to the overall response. Kinetic data from two reactions were also modelled, in both cases complex kinetics was observed, in close agreement with other studies.

  18. Molecularly imprinted solid phase extraction of fluconazole from pharmaceutical formulations.

    PubMed

    Manzoor, S; Buffon, R; Rossi, A V

    2015-03-01

    This work encompasses a direct and coherent strategy to synthesise a molecularly imprinted polymer (MIP) capable of extracting fluconazole from its sample. The MIP was successfully prepared from methacrylic acid (functional monomer), ethyleneglycoldimethacrylate (crosslinker) and acetonitrile (porogenic solvent) in the presence of fluconazole as the template molecule through a non-covalent approach. The non-imprinted polymer (NIP) was prepared following the same synthetic scheme, but in the absence of the template. The data obtained from scanning electronic microscopy, infrared spectroscopy, thermogravimetric and nitrogen Brunauer-Emmett-Teller plot helped to elucidate the structural as well as the morphological characteristics of the MIP and NIP. The application of MIP as a sorbent was demonstrated by packing it in solid phase extraction cartridges to extract fluconazole from commercial capsule samples through an offline analytical procedure. The quantification of fluconazole was accomplished through UPLC-MS, which resulted in LOD≤1.63×10(-10) mM. Furthermore, a high percentage recovery of 91±10% (n=9) was obtained. The ability of the MIP for selective recognition of fluconazole was evaluated by comparison with the structural analogues, miconazole, tioconazole and secnidazole, resulting in percentage recoveries of 51, 35 and 32%, respectively.

  19. Immobilization of microorganisms for detection by solid-phase immunoassays.

    PubMed Central

    Ibrahim, G F; Lyons, M J; Walker, R A; Fleet, G H

    1985-01-01

    Several cultures of gram-negative and gram-positive bacteria were successfully immobilized with titanous hydroxide. The immobilization efficiency for the microorganisms investigated in saline and broth media ranged from 80.2 to 99.9%. The immobilization of salmonellae was effective over a wide pH range. The presence of buffers, particularly phosphate buffer, drastically reduced the immobilization rate. However, buffers may be added to immunoassay systems after immobilization of microorganisms. The immobilization process involved only one step, i.e., shaking 100 microliter of culture with 50 microliter of titanous hydroxide suspension in polystyrene tubes for only 10 min. The immobilized cells were so tenaciously bound that vigorous agitation for 24 h did not result in cell dissociation. The nonspecific binding of 125I-labeled antibody from rabbits and 125I-labeled protein A by titanous hydroxide was inhibited in the presence of 2% gelatin and amounted to only 5.6 and 3.9%, respectively. We conclude that this immobilization procedure is a potentially powerful tool which could be utilized in solid-phase immunoassays concerned with the diagnosis of microorganisms. PMID:3900128

  20. ON-SITE SOLID-PHASE EXTRACTION AND LABORATORY ...

    EPA Pesticide Factsheets

    Fragrance materials such as synthetic musks in aqueous samples, are normally determined by gas chromatography/mass spectrometry in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of I -L samples. Full-scan mass spectra are required to verify that a target analyte has been found by comparison with the mass spectra of fragrance compounds in the NIST mass spectral library. A I -L sample usually provides insufficient analyte for full scan data acquisition. This paper describes an on-site extraction method developed at the U.S. Environmental Protection Agency (USEPA)- Las Vegas Nevada - for synthetic musks from 60 L of wastewater effluent. Such a large sample volume permits high-quality, full-scan mass spectra to be obtained for a wide array of synthetic musks. Quantification of these compounds was achieved from the full-scan data directly, without the need to acquire SIM data. The detection limits obtained with this method are an order of magnitude lower than those obtained from liquid-liquid and other solid phase extraction methods. This method is highly reproducible, and recoveries ranged from 80 to 97% in spiked sewage treatment plant effluent. The high rate of sorbent-sample mass transfer eliminated the need for a methanolic activation step, which reduced extraction time, labor, and solvent use, More samples could be extracted in the field at lower cost. After swnple extraction, the light- weight cartridges ar

  1. Characterizing solid phase ammonia toxicity in marine sediments

    SciTech Connect

    Ho, K.T.; Burgess, R.M.; Kuhn, A.

    1994-12-31

    The presence and toxicity of ammonia in sediments represents an interesting scientific and regulatory concern. From a scientific perspective, ammonia toxicity is largely pH dependent and easily detected under special exposure conditions. Regulating the concentration of ammonia is difficult because ammonia concentrations may be elevated by naturally occurring anaerobic sediment bacteria; however, these bacteria may be enhanced by excessive carbon inputs into a system. This presentation will demonstrate progress toward characterizing ammonia toxicity.in solid phase exposure. Toxicity tests were conducted using the mysid (Mysidopsis bahia) and the amphipod (Ampelisca abdita). Results from ammonia spiked and ammonia induced whole marine sediments demonstrate pH dependent toxicity under a graduated pH (7, 8 and 9) testing regime. Several metals (Cd, Cu, Ni, Pb and Zn) tested under the graduated pH testing regime showed varying toxicity patterns also as a function of pH. Other compounds, the toxicity of which are pH dependent will be discussed. In addition the results of testing with complex environmental sediments containing high ammonia concentrations and other contaminants will be reported.

  2. Monolithic graphene fibers for solid-phase microextraction.

    PubMed

    Fan, Jing; Dong, Zelin; Qi, Meiling; Fu, Ruonong; Qu, Liangti

    2013-12-13

    Monolithic graphene fibers for solid-phase microextraction (SPME) were fabricated through a dimensionally confined hydrothermal strategy and their extraction performance was evaluated. For the fiber fabrication, a glass pipeline was innovatively used as a hydrothermal reactor instead of a Teflon-lined autoclave. Compared with conventional methods for SPME fibers, the proposed strategy can fabricate a uniform graphene fiber as long as several meters or more at a time. Coupled to capillary gas chromatography (GC), the monolithic graphene fibers in a direct-immersion (DI) mode achieved higher extraction efficiencies for aromatics than those for n-alkanes, especially for polycyclic aromatic hydrocarbons (PAHs), thanks to π-π stacking interaction and hydrophobic effect. Additionally, the fibers exhibited excellent durability and can be repetitively used more than 160 times without significant loss of extraction performance. As a result, an optimum extraction condition of 40°C for 50min with 20% NaCl (w/w) was finally used for SPME of PAHs in aqueous samples. For the determination of PAHs in water samples, the proposed DI-SPME-GC method exhibited linear range of 0.05-200μg/L, limits of detection (LOD) of 4.0-50ng/L, relative standard deviation (RSD) less than 9.4% and 12.1% for one fiber and different fibers, respectively, and recoveries of 78.9-115.9%. The proposed method can be used for analysis of PAHs in environmental water samples.

  3. Ionic liquids in solid-phase microextraction: a review.

    PubMed

    Ho, Tien D; Canestraro, Anthony J; Anderson, Jared L

    2011-06-10

    Solid-phase microextraction (SPME) has undergone a surge in popularity within the field of analytical chemistry in the past two decades since its introduction. Owing to its nature of extraction, SPME has become widely known as a quick and cost-effective sample preparation technique. Although SPME has demonstrated extraordinary versatility in sampling capabilities, the technique continues to experience a tremendous growth in innovation. Presently, increasing efforts have been directed towards the engineering of novel sorbent material in order to expand the applicability of SPME for a wider range of analytes and matrices. This review highlights the application of ionic liquids (ILs) and polymeric ionic liquids (PILs) as innovative sorbent materials for SPME. Characterized by their unique physico-chemical properties, these compounds can be structurally-designed to selectively extract target analytes based on unique molecular interactions. To examine the advantages of IL and PIL-based sorbent coatings in SPME, the field is reviewed by gathering available experimental data and exploring the sensitivity, linear calibration range, as well as detection limits for a variety of target analytes in the methods that have been developed.

  4. IN SITU SOLID-PHASE EXTRACTION AND ANALYSIS OF ...

    EPA Pesticide Factsheets

    Fragrance materials, such as synthetic musks in aqueous samples, are normally analyzed by GC/MS in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of 1-L samples. A 1-L sample, however, usually provides too little analyte for full-scan data acquisition.We have developed an on-site extraction method for extracting synthetic musks from 60 L of wastewater effluent. Such a large sample volume permits high-quality, full-scan mass spectra to be obtained for various synthetic musk compounds. Quantification of these compounds was conveniently achieved from the full-scan data directly, without preparing SIM descriptors for each compound to acquire SIM data. The research focused on in the subtasks is the development and application of state-of the-art technologies to meet the needs of the public, Office of Water, and ORD in the area of Water Quality. Located In the subtasks are the various research projects being performed in support of this Task and more in-depth coverage of each project. Briefly, each project's objective is stated below.Subtask 1: To integrate state-of-the-art technologies (polar organic chemical integrative samplers, advanced solid-phase extraction methodologies with liquid chromatography/electrospray/mass spectrometry) and apply them to studying the sources and fate of a select list of PPCPs. Application and improvement of analytical methodologies that can detect non-volatile, polar, water-s

  5. Spherical clay conglomerates:  a novel stationary phase for solid-phase extraction and "reversed-phase" liquid chromatography.

    PubMed

    Bucheli, T D; Müller, S R; Reichmuth, P; Haderlein, S B; Schwarzenbach, R P

    1999-06-01

    A new solid phase is presented to be used for the solid-phase extraction (SPE) of organic compounds from aqueous solutions and as a stationary phase for the separation of organic compounds in "reversed-phase" HPLC. The material consists of spherical clay conglomerates (SCCs) in the size ranges of 2-5, 5-10, and 10-20 μm. SCCs are especially well suited for the extraction and separation of aromatic compounds with electron-withdrawing substituents, because of the formation of specific electron donor-acceptor (EDA) complexes of such compounds with natural clay minerals. A series of nitroaromatic compounds (NACs), e.g., nitrophenols, and nitrotoluenes, served as probe substances for the characterization of the SPE with SCCs online coupled to a C18-HPLC-DAD system. Breakthrough volumes were > 1 L and method detection limits (MDLs) < 100 ng/L for compounds with moderate to high affinity towards clay minerals. The performance of the material is hardly affected by matrix effects and because of its excellent physical properties, i.e., regenerability and pressure-resistance, it meets the requirements for fully automated routine trace analysis of several primary pollutants, such as 6-methyl-2,4-dinitrophenol (DNOC) or 2,4,6-trinitrotoluene (TNT), in various natural waters. Offline SPE with SCCs was superior or equivalent to commercial SPE products for analysis of such compounds. Finally, SCCs are shown to be well suited as a stationary phase in reversed-phase HPLC. This opens a wide range of applications, e.g., as an easy and fast separation technique that is orthogonal to C18 reversed-phase HPLC.

  6. Determining the solid phases hosting arsenic in Mekong Delta sediments

    NASA Astrophysics Data System (ADS)

    Wucher, M.; Stuckey, J. W.; McCurdy, S.; Fendorf, S.

    2011-12-01

    The major river systems originating from the Himalaya deposit arsenic bearing sediment into the deltas of South and Southeast Asia. High rates of sediment and organic carbon deposition combined with frequent flooding leads to anaerobic processes that release arsenic into the pore-water. Arsenic concentrations in the groundwater of these sedimentary basins are often above the World Health Organization drinking water standard of 10 μg As L-1. As a result, 150 million people are at risk of chronic arsenic poisoning through water and rice consumption. The composition of the iron bearing phases hosting the arsenic in these deltaic sediments is poorly understood. Here we implemented a suite of selective chemical extractions to help constrain the types of arsenic bearing solid phases, which were complimented with synchrotron-based X-ray absorption spectroscopy and X-ray diffraction analyses to define the arsenic and iron mineralogy of the system. Sediment cores were collected in triplicate from a seasonally-inundated wetland in Cambodia at depths of 10, 50, 100, and 150 centimeters. We hypothesize that (i) arsenic will be predominantly associated with iron oxides, and (ii) the ratio of crystalline to amorphous iron oxides will increase with sediment depth (and age). We performed four selective extractions in parallel to quantify the various pools of arsenic. First, 1 M MgCl2 was used to extract electrostatically-bound arsenic (labile forms) from the sediment. Second, 1 M NaH2PO4 targeted strongly adsorbed arsenic. Third, 1 M HCl was used to liberated arsenic coprecipitated with amorphous Fe/Mn oxides, carbonates, and acid-volatile sulfides. Finally, a dithionite extraction was used to account for arsenic associated with reducible Fe/Mn oxides. Through this work, we identified the composition of the phases hosting arsenic at various depths through the soil profile, improving our understanding of how arsenic persists in the aquifer. In addition, defining the arsenic and

  7. The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

    ERIC Educational Resources Information Center

    Long, Gary J.; Leighly, H. P., Jr.

    1982-01-01

    Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

  8. Rapid synthesis of oligodeoxyribonucleotides. IV. Improved solid phase synthesis of oligodeoxyribonucleotides through phosphotriester intermediates.

    PubMed Central

    Gait, M J; Singh, M; Sheppard, R C; Edge, M D; Greene, A R; Heathcliffe, G R; Atkinson, T C; Newton, C R; Markham, A F

    1980-01-01

    A phosphotriester solid phase method on a polyamide support has been used to prepare oligodeoxyribonucleotides up to 12 units long. Compared to solid phase phosphodiester synthesis the new methodology is quicker, more flexible and gives 10-60-fold better overall yields. PMID:7443540

  9. Estimating production and consumption of solid reactive Fe phases in marine sediments from concentration profiles

    EPA Science Inventory

    1D diffusion models may be used to estimate rates of production and consumption of dissolved metabolites in marine sediments, but are applied less often to the solid phase. Here we used a numerical inverse method to estimate solid phase Fe(III) and Fe(II) consumption and product...

  10. Manual Solid-Phase Peptide Synthesis of Metallocene-Peptide Bioconjugates

    ERIC Educational Resources Information Center

    Kirin, Srecko I.; Noor, Fozia; Metzler-Nolte, Nils; Mier, Walter

    2007-01-01

    A simple and relatively inexpensive procedure for preparing a biologically active peptide using solid phase peptide synthesis (SPPS) is described. Fourth-year undergraduate students have gained firsthand experience from the solid-phase synthesis techniques and they have become familiar with modern analytical techniques based on the particular…

  11. Novel materials and methods for solid-phase extraction and liquid chromatography

    SciTech Connect

    Ambrose, Diana

    1997-06-24

    This report contains a general introduction which discusses solid-phase extraction and solid-phase micro-extraction as sample preparation techniques for high-performance liquid chromatography, which is also evaluated in the study. This report also contains the Conclusions section. Four sections have been removed and processed separately: silicalite as a sorbent for solid-phase extraction; a new, high-capacity carboxylic acid functionalized resin for solid-phase extraction; semi-micro solid-phase extraction of organic compounds from aqueous and biological samples; and the high-performance liquid chromatographic determination of drugs and metabolites in human serum and urine using direct injection and a unique molecular sieve.

  12. Inhibition of a solid phase reaction among excipients that accelerates drug release from a solid dispersion with aging.

    PubMed

    Mizuno, Masayasu; Hirakura, Yutaka; Yamane, Ikuro; Miyanishi, Hideo; Yokota, Shoji; Hattori, Munetaka; Kajiyama, Atsushi

    2005-11-23

    Hydrophobic drug substances can be formulated as a solid dispersion or solution using macromolecular matrices with high glass transition temperatures to attain satisfactory dissolution. However, very few marketed products have previously relied on solid dispersion technology due to physical and chemical instability problems, and processing difficulties. In the present study, a modified release product of a therapeutic drug for hypertension, Barnidipine hydrochloride, was developed. The drug product consisted of solid dispersion based on a matrix of carboxymethylethylcellulose (CMEC), which was produced using the spray-coating method. An enteric coat layer was sprayed on the surface of the solid dispersion to control drug release. Interestingly, the release rate accelerated as the drug product aged, while there were no indications of deceleration of the release rate which was due to crystallization of the drug substance. To prevent changes in the dissolution kinetics during storage periods, a variety of processing conditions were tried. It was found that not only use of non-aqueous solvents but also a reduction in coating temperatures consistently resulted in stable solid dispersions. The molecular bases of dissolution of the drug substance from those matrices were investigated. The molecular weight of CMEC was found to be a dominant factor that determined dissolution kinetics, which followed zero-order release, suggesting an involvement of an osmotic pumping mechanism. While dissolution was faster using a higher molecular weight CMEC, the molecular weight of CMEC in the drug product slowly increased with aging (solid phase reaction) depending on the processing conditions, causing the time-induced elevation of dissolution. While no crystalline components were found in the solid dispersion, the amorphous structure maintained a degree of non-equilibrium by nature. Plasticization by water in the coating solution relaxed the amorphous system and facilitated phase

  13. Development and application of a high-throughput sample cleanup process based on 96-well plate for simultaneous determination of 16 steroids in biological matrices using liquid chromatography-triple quadrupole mass spectrometry.

    PubMed

    Luo, Guanzhong; Li, Youxin; Bao, James J

    2016-02-01

    A novel high-throughput sample pretreatment system was developed by the integration of protein precipitation (PP), phospholipid removal (PPR), and hollow fiber liquid-phase microextraction (HF-LPME) into two simple 96-well plates and a matching 96-grid lid. With this system, 16 steroids were separated from biological matrices of plasma, milk, and urine and analyzed by liquid chromatography-triple quadrupole mass spectrometry. In the tandem sample cleanup process, the prepositive PP and PPR step preliminarily removed some of the interferences from the biological matrices. The following HF-LPME step kept the residual interference out of the hollow fiber and enriched the steroids in the hollow fiber to achieve high sensitivity. By a series of method optimizations, acetonitrile was chosen as the crash solvent for PP and PPR. A mixture of octanol and toluene (1:1 v/v) was used as the acceptor phase for HF-LPME. The extraction was conducted at 80 rpm for 50 min in a donor phase containing 1 mL 20% sodium chloride at 25 °C. Under these conditions, the limits of detection for the 16 steroids were 3.6-300.0 pg(.)mL(-1) in plasma, 3.0-270.0 pg·mL(-1) in milk, and 2.2-210.0 pg(.)mL(-1) in urine. The recoveries of the 16 steroids were 81.9-97.9% in plasma (relative standard deviation 1.0-8.0%), 80.6-97.7% in milk (relative standard deviation 0.8-5.4%), and 87.3-98.7% in urine (relative standard deviation 1.0-4.9%). Further, the integrated 96-well platform of PP, PPR, and HF-LPME enabled us to run this assay in an automatic and high-throughput fashion. The reliability of the method was further corroborated by evaluation of its applicability in plasma and urine samples from volunteers and fresh bovine milk from local dairy enterprises.

  14. Rapid and Specific Approach for Direct Measurement of Glimepiride in Human Plasma by LC–ESI-MS–MS Employing Automated 96 Well Format: Application to a Bioequivalence Study

    PubMed Central

    Kundlik, M.L.; Zaware, B.H.; Kuchekar, S.R.

    2012-01-01

    A rapid liquid chromatographic method with electrospray ionization tandem mass spectrometric (LC–MS–MS) detection is developed and validated for quantification of glimepiride in heparinized human plasma. Plasma samples, without a drying and reconstitution step, are extracted by solid-phase extraction (SPE) and eluted with 0.9 mL of acetonitrile–methanol (1:1, v/v) containing 0.05% formic acid. The analyte and glimepiride d8 (internal standard, IS) are chromatographed on a C18 column; the mobile phase is acetonitrile–2 mm ammonium formate (88:12, v/v), with the pH adjusted to 3.5 with formic acid, at a flow rate of 0.5 mL/min. The retention times of glimepiride and the IS are 0.93 min, and the runtime is 1.6 min per sample. Selected reaction monitoring of MH+ at m/z 491.20 and 499.26 result in stable fragment ions with m/z 351.80 and 359.96 for glimepiride and the IS, respectively. The response was a linear function of the concentration in the range of 2.0–650.0 ng/mL, with r ≥ 0.9994. The recovery of glimepiride and the IS ranged from 81.91 to 83.36%. The assay has excellent characteristics and has been successfully used for the analysis of glimepiride in healthy human subjects in a bioequivalence study. It was well suited to clinical studies of the drug involving large numbers of samples. PMID:22291058

  15. Ultrarapid mutation detection by multiplex, solid-phase chemical cleavage

    SciTech Connect

    Rowley, G.; Saad, S.; Giannelli, F.; Green, P.M.

    1995-12-10

    The chemical cleavage of mismatches in heteroduplexes formed by probe and test DNA detects and locates any sequence change in long DNA segments ({approximately}1.8 kb), and its efficiency has been well tested in the analysis of both average (e.g., coagulation factor IX) and large, complex genes (e.g., coagulation factor VIII and dystrophin). In the latter application RT/PCR products allow the examination of all essential sequences of the gene in a minimum number of reactions. We use two specific chemical reactants (hydroxylamine and osmium tetroxide) and piperidine cleavage of the above procedure to develop a very fast mutation screening method. This is based on: (1) 5{prime} or internal fluorescent labeling to allow concurrent screening of three to four DNA fragments and (2) solid-phase chemistry to use a microliter format and reduce the time required for the procedure, from amplification of sequence to gel loading inclusive, to one person-working-day. We test the two variations of the method, one entailing 5{prime} labeling of probe DNA and the other uniform labeling of both probe and target DNA, by detecting 114 known hemophilia B (coagulation factor IX) mutations and by analyzing 129 new patients. Uniform labeling of both probe and target DNA prior to formation of the heteroduplexes leads to almost twofold redundancy in the ability to detect mutations. Alternatively, the latter procedure may offer very efficient though less than 100% screening for sequence changes with only hydroxylamine. The full method with two chemical reactions (hydroxylamine and osmium tetroxide) should allow one person to screen with virtually 100% accuracy more than 300 kb of sequence in three ABI 373 gels in 1 day. 26 refs., 7 figs., 1 tab.

  16. Solid phase epitaxial regrowth of (100)GaAs

    SciTech Connect

    Almonte, Marlene Isabel

    1996-02-01

    This thesis showed that low temperature (250°C) SPE of stoichiometrically balanced ion implanted GaAs layers can yield good epitaxial recovery for doses near the amorphization threshold. For 250°C anneals, most of the regrowth occurred in the first 10 min. HRTEM revealed much lower stacking fault density in the co-implanted sample than in the As-only and Ga-only samples with comparable doses. After low temp annealing, the nonstoichiometric samples had a large number of residual defects. For higher dose implants, very high temperatures (700°C) were needed to remove residual defects for all samples. The stoichiometrically balanced layer did not regrow better than the Ga-only and As-only samples. The co-implanted sample exhibited a thinner amorphous layer and a room temperature (RT) annealing effect. The amorphous layer regrew about 5 nm, suggesting that stoichiometrically balanced amorphous layers can regrow even at RT. Mechanisms for solid phase crystallization in (100)GasAs is discussed: nucleation and growth of randomly oriented crystallites and SPE. These two mechanisms compete in compound semiconductors at much lower temperatures than in Si. For the low dose As-only and Ga-only samples with low-temp anneals, both mechanisms are active. For this amorphization threshold dose, crystallites remain in the amorphous layer for all as-implants. 250°C annealing showed recrystallization from the surface and bulk for these samples; for the co-implant, the mechanism is not evident.

  17. Porous, High Capacity Coatings for Solid Phase Microextraction by Sputtering.

    PubMed

    Diwan, Anubhav; Singh, Bhupinder; Roychowdhury, Tuhin; Yan, DanDan; Tedone, Laura; Nesterenko, Pavel N; Paull, Brett; Sevy, Eric T; Shellie, Robert A; Kaykhaii, Massoud; Linford, Matthew R

    2016-02-02

    We describe a new process for preparing porous solid phase microextraction (SPME) coatings by the sputtering of silicon onto silica fibers. The microstructure of these coatings is a function of the substrate geometry and mean free path of the silicon atoms, and the coating thickness is controlled by the sputtering time. Sputtered silicon structures on silica fibers were treated with piranha solution (a mixture of concd H2SO4 and 30% H2O2) to increase the concentration of silanol groups on their surfaces, and the nanostructures were silanized with octadecyldimethylmethoxysilane in the gas phase. The attachment of this hydrophobic ligand was confirmed by X-ray photoelectron spectroscopy and contact angle goniometry on model, planar silicon substrates. Sputtered silicon coatings adhered strongly to their surfaces, as they were able to pass the Scotch tape adhesion test. The extraction time and temperature for headspace extraction of mixtures of alkanes and alcohols on the sputtered fibers were optimized (5 min and 40 °C), and the extraction performances of SPME fibers with 1.0 or 2.0 μm of sputtered silicon were compared to those from a commercial 7 μm poly(dimethylsiloxane) (PDMS) fiber. For mixtures of alcohols, aldehydes, amines, and esters, the 2.0 μm sputtered silicon fiber yielded signals that were 3-9, 3-5, 2.5-4.5, and 1.5-2 times higher, respectively, than those of the commercial fiber. For the heavier alkanes (undecane-hexadecane), the 2.0 μm sputtered fiber yielded signals that were approximately 1.0-1.5 times higher than the commercial fiber. The sputtered fibers extracted low molecular weight analytes that were not detectable with the commercial fiber. The selectivity of the sputtered fibers appears to favor analytes that have both a hydrophobic component and hydrogen-bonding capabilities. No detectable carryover between runs was noted for the sputtered fibers. The repeatability (RSD%) for a fiber (n = 3) was less than 10% for all analytes tested

  18. Solid rocket motor fire tests: Phases 1 and 2

    NASA Astrophysics Data System (ADS)

    Chang, Yale; Hunter, Lawrence W.; Han, David K.; Thomas, Michael E.; Cain, Russell P.; Lennon, Andrew M.

    2002-01-01

    JHU/APL conducted a series of open-air burns of small blocks (3 to 10 kg) of solid rocket motor (SRM) propellant at the Thiokol Elkton MD facility to elucidate the thermal environment under burning propellant. The propellant was TP-H-3340A for the STAR 48 motor, with a weight ratio of 71/18/11 for the ammonium perchlorate, aluminum, and HTPB binder. Combustion inhibitor applied on the blocks allowed burning on the bottom and/or sides only. Burns were conducted on sand and concrete to simulate near-launch pad surfaces, and on graphite to simulate a low-recession surface. Unique test fixturing allowed propellant self-levitation while constraining lateral motion. Optics instrumentation consisted of a longwave infrared imaging pyrometer, a midwave spectroradiometer, and a UV/visible spectroradiometer. In-situ instrumentation consisted of rod calorimeters, Gardon gauges, elevated thermocouples, flush thermocouples, a two-color pyrometer, and Knudsen cells. Witness materials consisted of yttria, ceria, alumina, tungsten, iridium, and platinum/rhodium. Objectives of the tests were to determine propellant burn characteristics such as burn rate and self-levitation, to determine heat fluxes and temperatures, and to carry out materials analyses. A summary of qualitative results: alumina coated almost all surfaces, the concrete spalled, sand moisture content matters, the propellant self-levitated, the test fixtures worked as designed, and bottom-burning propellant does not self-extinguish. A summary of quantitative results: burn rate averaged 1.15 mm/s, thermocouples peaked at 2070 C, pyrometer readings matched MWIR data at about 2400 C, the volume-averaged plume temperatures were 2300-2400 C with peaks of 2400-2600 C, and the heat fluxes peaked at 125 W/cm2. These results are higher than other researchers' measurements of top-burning propellant in chimneys, and will be used, along with Phase 3 test results, to analyze hardware response to these environments, including General

  19. A Quantitative High-Throughput 96-well plate Fluorescence Assay for Mechanism-Based Inactivators of Cytochromes P450 Exemplified using CYP2B6

    PubMed Central

    Kenaan, Cesar; Zhang, Haoming; Hollenberg, Paul F.

    2010-01-01

    Mechanism-based inactivators such as bergamottin are useful chemical tools for identifying the roles of specific active-site amino acid residues in the reactions catalyzed by the cytochromes P450 (CYPs or P450s) that are responsible for the metabolism of a wide variety of drugs and endogenous substrates. In clinical settings mechanism-based inactivation of P450s involved in xenobiotic metabolism has the potential to lead to adverse drug-drug interactions and assays to identify and characterize drug candidates as P450 inactivators are important in drug discovery and development. Here we present a quantitative high-throughput protocol for investigating cytochrome P450 mechanism-based inactivators using the example of CYP2B6 and bergamottin to illustrate the finer points of this protocol. This protocol details the adaptation of a 7-ethoxytrifluoromethyl coumarin (7-EFC) O-deethylation fluorescence activity assay to a 96-well microtiter plate format and uses a plate-reader to detect the fluorescence of the product. Compared to previous methods, this protocol requires less P450 and takes significantly less time while greatly increasing throughput. The protocol as written takes approximately two hours to complete. The principles and procedures outlined in this protocol can be easily adapted to other inactivators, P450 isoforms, substrates and plate-readers. PMID:20885377

  20. A semi-automated 96-well protein precipitation method for the determination of montelukast in human plasma using high performance liquid chromatography/fluorescence detection.

    PubMed

    Kitchen, Chester J; Wang, Amy Q; Musson, Donald G; Yang, Amy Y; Fisher, Alison L

    2003-03-26

    A simple, semi-automated, protein precipitation assay for the determination of montelukast (SINGULAIR, MK-0476) in human plasma has been developed. Montelukast is a potent and selective antagonist of the cysteinyl leukotriene receptor used for the treatment of asthma. A Packard MultiPROBE II EX is used to transfer 300 microl of plasma from sample, standard, and QC sample tubes to a microtiter plate (96-well). After addition of the internal standard by a repeating pipettor, a Tomtec QUADRA 96 adds 400 microl of acetonitrile to all plasma sample wells, simultaneously, in the microtiter plate. The Tomtec is also used to transfer the acetonitrile supernatant from the plasma protein precipitation step, batchwise, to another microtiter plate for analysis by HPLC with fluorescence detection. This assay has been validated and implemented for a clinical study of over 1300 plasma samples and is comparable to manual assays in the LLOQ (lower limit of quantitation, 3 ng/ml) and in stability. This is the first semi-automated protein precipitation assay published for the analysis of montelukast in human plasma and it results in significant time savings over the manual methods, both in sample preparation and in HPLC run time.

  1. Induction of apoptosis by intracellular potassium ion depletion: using the fluorescent dye PBFI in a 96-well plate method in cultured lung cancer cells.

    PubMed

    Andersson, B; Janson, V; Behnam-Motlagh, P; Henriksson, R; Grankvist, K

    2006-09-01

    Depletion of intracellular potassium ions (K+) is necessary for cells to shrink, activate caspases and induce DNA fragmentation, events which are features of apoptosis. Here we describe a 96-well plate method using the cell permeable form of K+ binding benzofuran isophtalate (PBFI-AM) to measure intracellular K+ content in relation to untreated control. Cultured human pulmonary mesothelioma cells (P31) and small-cell lung cancer cells (U1690) were treated with K+ flux modulators in order to deprive the cells of intracellular K+. The combination of K+ influx inhibition with 10 micromol/L bumetanide plus 10 micromol/L ouabain and K+ efflux stimulation with 3 mg/L amphotericin B or 5 micromol/L nigericin efficiently reduced the intracellular K+ content after 3 h. Manipulation of K+ fluxes with subsequent intracellular K+ depletion induced apoptosis of lung cancer cells, as detected by caspase-3 activity after 3 h K+ depletion followed by 24 h proliferation and TUNEL positive staining after 48 h proliferation. We concluded that the PBFI-AM assay was a useful tool to determine intracellular K+ content in relation to untreated control, and that intracellular K+ depletion of lung cancer cells by clinically used drugs of relevant concentrations induced apoptosis. These findings may lead to novel therapeutic strategies in the treatment of lung cancer.

  2. Soluble penicillin-binding protein 2a: beta-lactam binding and inhibition by non-beta-lactams using a 96-well format.

    PubMed

    Toney, J H; Hammond, G G; Leiting, B; Pryor, K D; Wu, J K; Cuca, G C; Pompliano, D L

    1998-01-01

    High level methicillin resistance in Staphylococcus aureus is dependent upon the acquisition of the mecA gene encoding penicillin-binding protein 2a (PBP2a). PBP2a is a member of a family of peptidoglycan biosynthetic enzymes involved in assembly of the cell wall in bacteria and is poorly inactivated by beta-lactam antibiotics. We describe a 96-well-filter binding assay using recombinant, soluble PBP2a which allows for kinetic measurement of penicillin binding. The deacylation rate constant for the PBP2a-penicillin G covalent complex was found to be 5.7 +/- 1.0 x 10(-5) s-1 at 30 degrees C (half-life of approximately 200 min). For the PBP2a acylation reaction, the value of K(m) (penicillin G) = 0.5 +/- 0.1 mM and kcat = 1 x 10(-3) s-1, which yields a second-order rate constant (kcat/K(m)) for inactivation of 2.0 M-1 s-1. Using this assay, several non-beta-lactam inhibitors including Cibacron blue have been found which exhibit IC50 values between 10 and 30 microM. The binding affinities of several carbapenems and beta-lactams correlated well between the filter binding assay described in this report and an electrophoretic assay for PBP2a using membranes prepared form methicillin-resistant S. aureus.

  3. Quantum dot immunoassays in renewable surface column and 96-well plate formats for the fluorescence detection of Botulinum neurotoxin using high-affinity antibodies

    SciTech Connect

    Warner, Marvin G.; Grate, Jay W.; Tyler, Abby J.; Ozanich, Richard M.; Miller, Keith D.; Lou, Jianlong; Marks, James D.; Bruckner-Lea, Cindy J.

    2009-09-01

    A fluorescence sandwich immunoassay using high affinity antibodies and quantum dot (QD) reporters has been developed for detection of botulinum toxin serotype A (BoNT/A). For the development of the assay, a nontoxic recombinant fragment of the holotoxin (BoNT/A-HC-fragment) has been used as a structurally valid simulant for the full toxin molecule. The antibodies used, AR4 and RAZ1, bind to nonoverlapping epitopes present on both the full toxin and on the recombinant fragment. In one format, the immunoassay is carried out in a 96-well plate with detection in a standard plate reader. Detection down to 31 pM of the BoNT/Hc-fragment was demonstrated with a total incubation time of 3 hours, using AR4 as the capture antibody and QD-coupled RAZ1 as the reporter. In a second format, the AR4 capture antibody was coupled to Sepharose beads, and the immunochemical reactions were carried out in microcentrifuge tubes with an incubation time of 1 hour. These beads were subsequently captured and concentrated in a rotating rod “renewable surface” flow cell as part of a sequential injection fluidic system. This flow cell was equipped with a fiber optic system for fluorescence measurements. In PBS buffer solution matrix, the BoNT/A-HC-fragment was detected to concentrations as low as 5 pM using the fluidic measurement approach.

  4. Observation of Solid-Solid Phase Transitions in Ramp-Compressed Aluminum

    NASA Astrophysics Data System (ADS)

    Polsin, D. N.; Boehly, T. R.; Delettrez, J. A.; Gregor, M. C.; McCoy, C. A.; Henderson, B.; Fratanduono, D. E.; Smith, R.; Kraus, R.; Eggert, J. H.; Collins, R.; Coppari, F.; Celliers, P. M.

    2016-10-01

    We present results of experiments using x-ray diffraction to study the crystalline structure of solid aluminum compressed up to 500 GPa. Aluminum is of interest because it is frequently used as a standard material in high-pressure compression experiments. At ambient pressure and temperature, Al is a face-centered cubic close-packed crystal and has been observed to transform to hexagonal close-packed (hcp) when compressed to 200GPa in a diamond anvil cell. It is predicted to transform from hcp to body-centered cubic when compressed to 315GPa. Laser-driven ramp waves will be used to compress Al to various constant-pressure states. The goal is to investigate the Al phase diagram along its isentrope, i.e., at temperatures 1000K and pressures ranging from 200 to 500 GPa. X-ray diffraction will be used to measure the crystalline structure of the compressed Al and observe the transformations that occur at various pressures. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  5. Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells.

    PubMed

    Hatke, A T; Liu, Yang; Magill, B A; Moon, B H; Engel, L W; Shayegan, M; Pfeiffer, L N; West, K W; Baldwin, K W

    2014-06-20

    In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.

  6. Materials research for passive solar systems: solid-state phase-change materials

    SciTech Connect

    Benson, D.K.; Webb, J.D.; Burrows, R.W.; McFadden, J.D.O.; Christensen, C.

    1985-03-01

    A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C/sub 5/H/sub 12/O/sub 4/), pentaglycerinve (C/sub 5/H/sub 12/O/sub 3/), and neopentyl glycol (C/sub 5/H/sub 12/O/sub 2/). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature betweeen 25/sup 0/C and 188/sup 0/C, and have latent heats of transformation between 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier. Nevertheless, a higher cost of the phase-change materials (approx. =$0.70 per pound) is likely to limit their applicability in passive solar systems unless their performance can be significantly improved through further research.

  7. A novel mixed-mode solid phase extraction coupled with LC-MS/MS for the re-evaluation of free 3-nitrotyrosine in human plasma as an oxidative stress biomarker.

    PubMed

    Li, Xiaoguang Sunny; Li, Shu; Kellermann, Gottfried

    2015-08-01

    3-Nitrotyrosine (3-NT) has been widely adopted as a biomarker of oxidative stress. However, an enormous range of reported concentrations of 3-NT in biological matrices indicated an underlying methodological problem. Consequently, our understanding of tyrosine nitration in vivo and its significance as a biomarker may have been confounded. Here we report a fast, specific and sensitive LC-MS/MS method to accurately quantify free 3-NT in human plasma. For the first time, a single-step solid phase extraction of 3-NT using mixed-mode sorbent in a 96-well plate was developed after significant optimization. Complete chromatographic separation of 3-NT from other tyrosine analogs was achieved on a PFPP column (150 mm, 2.1 mm, 3 μm) with a cycle time of 10 min. The developed method was validated in terms of linearity, sensitivity, specificity, precision, accuracy, matrix effect, carryover, analyte stability and reference interval. The lower limit of quantification of the method was 5 pg/ml for plasma 3-NT, which represents a significant sensitivity improvement over reported methods. No artifactual 3-NT formation was observed, and the assay was not affected by 40 likely interferences. The average intra- and inter-assay variances were 3.4% and 3.7%, respectively. Of note, the reference interval for a healthy population was established to be 2.0-40.1 pg/ml (8.8-177 pM) with a mean of 11.1 pg/ml (49 pM). The mean value is at least 13-fold lower than previously reported mean values. Furthermore, the method was applied to the investigation of biological variation (n=15) over a three week period and no statistical differences were found. The solid phase extraction in a 96-well format and a fast LC-MS/MS delivered a practical, precise and accurate tool well-suited to quantify free plasma 3-NT in a large number of biological samples.

  8. Characterization of interactions between soil solid phase and soil solution in the initial ecosystem development phase

    NASA Astrophysics Data System (ADS)

    Zimmermann, Claudia; Schaaf, Wolfgang

    2010-05-01

    In the initial phase of soil formation interactions between solid and liquid phases and processes like mineral weathering, formation of reactive surfaces and accumulation of organic matter play a decisive role in developing soil properties. As part of the Transregional Collaborative Research Centre (SFB/TRR 38) 'Patterns and processes of initial ecosystem development' in an artificial catchment, these interactions are studied at the catchment 'Chicken Creek' (Gerwin et al. 2009). To link the interactions between soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale, microcosm experiments under controlled laboratory conditions were carried out. Main objectives were to determine the transformation processes of C and N from litter decomposition within the gaseous, liquid and solid phase, the interaction with mineral surfaces and its role for the establishment of biogeochemical cycles. The microcosm experiments were established in a climate chamber at constant 10 ° C. In total 48 soil columns (diameter: 14.4 cm; height: 30 cm) were filled with two different quaternary substrates (sand and loamy sand) representing the textural variation within the catchment at a bulk density of 1.4-1.5 g*cm-3. The columns were automatically irrigated four times a day with 6.6 ml each (corresponding to 600 mm*yr-1). The gaseous phase in the headspace of the microcosms was analysed continuously for CO2 and N2O contents. C and N transformation processes were studied using 13C and 15N labelled litter of two different plant species occurring at the catchment (Lotus corniculatus, Calamagrostis epigejos) that was incorporated into the microcosm surface. All treatments including a control ran with four replicates over a period of 40 weeks. Two additional microcosms act as pure litter controls where substrate was replaced by glass pearls. Litter and substrate were analysed before and after the experiment. Percolate was continuously collected and

  9. Quarter-filled supersolid and solid phases in the extended Bose-Hubbard model.

    PubMed

    Ng, Kwai-Kong; Chen, Y C; Tzeng, Y C

    2010-05-12

    We numerically study the ground state phase diagram of the two-dimensional hard-core Bose-Hubbard model with nearest-(V(1)) and next-nearest-neighbour (V(2)) repulsions. In particular, we focus on the quarter-filled phases where one supersolid and two solid phases are observed. Using both canonical and grand canonical quantum Monte Carlo (QMC) methods and a mean-field calculation, we provide evidence for the existence of a commensurate supersolid. Despite the two possible diagonal long-range orderings for the solid phase, only one kind of supersolid phase is found to be energetically stable. The competition between the two solid phases manifests itself as a first-order phase transition around 2V(2) ∼ V(1). The change of order parameters as a function of the chemical potential is also presented.

  10. Microfluidic chips with reversed-phase monoliths for solid phase extraction and on-chip labeling.

    PubMed

    Nge, Pamela N; Pagaduan, Jayson V; Yu, Ming; Woolley, Adam T

    2012-10-26

    The integration of sample preparation methods into microfluidic devices provides automation necessary for achieving complete micro total analysis systems. We have developed a technique that combines on-chip sample enrichment with fluorescence labeling and purification. Polymer monoliths made from butyl methacrylate were fabricated in cyclic olefin copolymer microdevices and used for solid phase extraction. We studied the retention of fluorophores, amino acids and proteins on these columns. The retained samples were subsequently labeled with both Alexa Fluor 488 and Chromeo P503, and unreacted dye was rinsed off the column before sample elution. Additional purification was obtained from the differential retention of proteins and fluorescent labels. A linear relation between the eluted peak areas and concentrations of on-chip labeled heat shock protein 90 samples demonstrated the utility of this method for on-chip quantitation. Our fast and simple method of simultaneously concentrating and labeling samples on-chip is compatible with miniaturization and desirable for automated analysis.

  11. Plate-to-plate fluorous solid-phase extraction for solution-phase parallel synthesis.

    PubMed

    Zhang, Wei; Lu, Yimin; Nagashima, Tadamichi

    2005-01-01

    A commercially available Argonaut VacMaster-96 plate-to-plate solid-phase extraction (SPE) station equipped with 24 FluoroFlash cartridges is employed for parallel purification of fluorous reaction mixtures. Each cartridge charged with 3 g of fluorous silica gel has the capability to produce up to 100 mg of purified small molecules. The 24-well receiving plate has a standard footprint that can be directly concentrated in a Genevac vacuum centrifuge. Important issues such as sample loading, product cross-contamination, cartridge reuse, and reproducibility are investigated. The SPE system has been demonstrated in the purification of three small libraries that were produced involving amine scavenging reactions with fluorous isatoic anhydride, amide coupling reactions with 2-chloro-4,6-bis[(perfluorohexyl)propyloxy]-1,3,5-triazine (fluorous CDMT), and amide coupling reactions with a newly developed fluorous Mukaiyama condensation reagent.

  12. Crystallization and Phase Changes in Paracetamol from the Amorphous Solid to the Liquid Phase

    PubMed Central

    2014-01-01

    For the case of paracetamol, we show how terahertz time-domain spectroscopy can be used to characterize the solid and liquid phase dynamics. Heating of supercooled amorphous paracetamol from 295 K in a covered sample under vacuum leads to its crystallization at 330 K. First, form III is formed followed by the transformation of form III to form II at 375 K, to form I at 405 K, and finally melting is observed around 455 K. We discuss the difference between the featureless spectra of the supercooled liquid and its liquid melt. Lastly, we studied the onset of crystallization from the supercooled liquid in detail and quantified its kinetics based on the Avrami–Erofeev model. We determined an effective rate constant of k = 0.056 min–1 with a corresponding onset of crystallization at T = 329.5 K for a heating rate of 0.4 K min–1. PMID:24579729

  13. The Double Solid Reactant Method for modeling the release of trace elements from dissolving solid phases: I. Outline and limitations

    NASA Astrophysics Data System (ADS)

    Accornero, Marina; Marini, Luigi

    2008-10-01

    A Double Solid Reactant Method was elaborated from a suggestion of Marini (Geological sequestration of carbon dioxide: Thermodynamics, kinetics, and reaction path modeling. Developments in Geochemistry, Elsevier, Amsterdam, 2007) to simulate the release of trace elements during the progressive dissolution of solid phases. The method is based on the definition, for each dissolving solid, of both an entity whose thermodynamic and kinetic properties are known (either a pure mineral or a solid mixture) and a special reactant, that is, a material of known stoichiometry and unknown thermodynamic and kinetic properties. The special reactant is utilised to take into account the concentrations of trace elements in the dissolving solid phase. In this communication, the influence of several trace elements on the Δ G f o, Δ G r o and log K of the minerals considered by Lelli et al. (Environ Geol, 2007) and Accornero and Marini (Geobasi, 2007a; Proceedings of IMWA symposium, Cagliari, 27 31 May 2007b) was evaluated assuming ideal mixing in the solid state. These effects were found to be negligible for albite and the leucite latitic glass, limited for muscovites and chlorites, and slightly more important for apatites. These influences become progressively higher with increasing concentration of trace elements in these minerals. Based on these deviations in thermodynamic parameters, special reactants should not include oxide components with molar fractions higher than 0.003.

  14. Method development for the quantitation of ABT-578 in rabbit artery tissue by 96-well liquid-liquid extraction and liquid chromatography/tandem mass spectrometric detection.

    PubMed

    Ji, Qin C; Zhang, Jun; Rodila, Ramona; Watson, Pamela; El-Shourbagy, Tawakol

    2004-01-01

    Quantitative determination of drug concentrations in tissue samples can provide critical information for drug metabolism, kinetics, and toxicity evaluations. For analysis of tissue samples using liquid chromatography/tandem mass spectrometric (LC/MS/MS) detection, homogenization is a critical step in achieving good assay performance. Assay performance can be closely evaluated by spiking the drug directly into tissue samples prior to homogenization. It is especially important to include this assay evaluation for the analysis of artery tissue samples because artery tissue is very elastic, making it quite a challenge to develop an effective procedure for homogenization. An LC/MS/MS assay in 96-well format using liquid-liquid extraction was developed for analyzing ABT-578 in rabbit artery samples. Tissue quality control samples were prepared by spiking ABT-578 stock solutions directly into the tissue before homogenization. The usage of the tissue control samples gives a thorough evaluation of the sample preparation process that includes both homogenization and sample extraction. A 20% blood in saline solution was used as a homogenization solution. Calibration standards were made by spiking ABT-578 into rabbit whole blood. Blood quality control samples were also prepared by spiking ABT-578 into rabbit whole blood. These blood QC samples were used to confirm the validity of the calibration curve. A lower limit of quantitation of 0.050 ng/mL was achieved. The linear dynamic range of blood standards was from 0.050-30.3 ng/mL with the correlation coefficient (r) ranging from 0.9969-0.9996. Overall %CV was between 1.3 and 7.0%, and analytical recovery was between 98.2 and 105.8% for blood QC samples. The %CVs for tissue QC samples were between 6.7 and 13.0%, and analytical recovery after correction was between 93.5 and 114.3%.

  15. A high-throughput protein refolding screen in 96-well format combined with design of experiments to optimize the refolding conditions.

    PubMed

    Dechavanne, Vincent; Barrillat, Nicolas; Borlat, Frederic; Hermant, Aurélie; Magnenat, Laurent; Paquet, Mikael; Antonsson, Bruno; Chevalet, Laurent

    2011-02-01

    Production of correctly folded and biologically active proteins in Escherichiacoli can be a challenging process. Frequently, proteins are recovered as insoluble inclusion bodies and need to be denatured and refolded into the correct structure. To address this, a refolding screening process based on a 96-well assay format supported by design of experiments (DOE) was developed for identification of optimal refolding conditions. After a first generic screen of 96 different refolding conditions the parameters that produced the best yield were further explored in a focused DOE-based screen. The refolding efficiency and the quality of the refolded protein were analyzed by RP-HPLC and SDS-PAGE. The results were analyzed by the DOE software to identify the optimal concentrations of the critical additives. The optimal refolding conditions suggested by DOE were verified in medium-scale refolding tests, which confirmed the reliability of the predictions. Finally, the refolded protein was purified and its biological activity was tested in vitro. The screen was applied for the refolding of Interleukin 17F (IL-17F), stromal-cell-derived factor-1 (SDF-1α/CXCL12), B cell-attracting chemokine 1 (BCA-1/CXCL13), granulocyte macrophage colony stimulating factor (GM-CSF) and the complement factor C5a. This procedure identified refolding conditions for all the tested proteins. For the proteins where refolding conditions were already available, the optimized conditions identified in the screening process increased the yields between 50% and 100%. Thus, the method described herein is a useful tool to determine the feasibility of refolding and to identify high-yield scalable refolding conditions optimized for each individual protein.

  16. Solid-Phase Equilibria for Metal-Silicon-Oxygen Ternary Systems. II. Sc, Y, and La

    DTIC Science & Technology

    1991-02-28

    Organization: Regents of the University of California TECHNICAL REPORT No. 9 SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND La...34’ SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND 1a 13 0911OtiA AUTHORCS) Haojie Yuan and R. Stanley Williams lI" TV...0660te tCLhSSWI=) Solid phase equilibria for metal-silicon-oxygen ternary systems I1: Sc, Y and La Haojie Yuan and R. Stanley Williams Department of

  17. Solid-fluid and solid-solid equilibrium in hard sphere united atom models of n-alkanes: rotator phase stability.

    PubMed

    Cao, M; Monson, P A

    2009-10-22

    We present a study of the phase behavior for models of n-alkanes with chain lengths up to C(21) based on hard sphere united atom models of methyl and methylene groups, with fixed bond lengths and C-C-C bond angles. We extend earlier work on such models of shorter alkanes by allowing for gauche conformations in the chains. We focus particularly on the orientational order about the chain axes in the solid phase near the melting point, and our model shows how the loss of this orientational order leads to the formation of rotator phases. We have made extensive calculations of the thermodynamic properties of the models as well as order parameters for tracking the degree of orientational order around the chain axis. Depending on the chain length and whether the carbon number is even or odd, the model exhibits both a rotator phase and a more orientationally ordered solid phase in addition to the fluid phase. Our results indicate that the transition between the two solid phases is first-order with a small density change. The results are qualitatively similar to those seen experimentally and show that rotator phases can appear in models of alkanes without explicit treatment of attractive forces or explicit treatment of the hydrogen atoms in the chains.

  18. Anomalous bond length behavior and a new solid phase of bromine under pressure

    PubMed Central

    Wu, Min; Tse, John S.; Pan, Yuanming

    2016-01-01

    The behavior of diatomic molecular solids under pressure have attracted great interest and been extensively studied. Under ambient pressure, the structure of bromine is known to be a molecular phase (phase I). With increasing pressure, it transforms into an incommensurate phase (phase V) before eventually to a monoatomic phase (phase II). However, between phases I and V, the interatomic distance was found to first increase with pressure and then decreased abruptly. This anomalous bond length behavior is accompanied by the splitting of the Raman bands. These phenomena have not been resolved. Here we suggest a new solid phase that explains the Raman spectra. Furthermore, the anomalous bond length behavior is found to be the result of subtle second neighbor intermolecular interactions and is an intrinsic property of bromine in molecular phases. PMID:27156710

  19. Anomalous bond length behavior and a new solid phase of bromine under pressure

    NASA Astrophysics Data System (ADS)

    Wu, Min; Tse, John S.; Pan, Yuanming

    2016-05-01

    The behavior of diatomic molecular solids under pressure have attracted great interest and been extensively studied. Under ambient pressure, the structure of bromine is known to be a molecular phase (phase I). With increasing pressure, it transforms into an incommensurate phase (phase V) before eventually to a monoatomic phase (phase II). However, between phases I and V, the interatomic distance was found to first increase with pressure and then decreased abruptly. This anomalous bond length behavior is accompanied by the splitting of the Raman bands. These phenomena have not been resolved. Here we suggest a new solid phase that explains the Raman spectra. Furthermore, the anomalous bond length behavior is found to be the result of subtle second neighbor intermolecular interactions and is an intrinsic property of bromine in molecular phases.

  20. Automated liquid-liquid extraction based on 96-well plate format in conjunction with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for the quantitation of methoxsalen in human plasma.

    PubMed

    Yadav, Manish; Contractor, Pritesh; Upadhyay, Vivek; Gupta, Ajay; Guttikar, Swati; Singhal, Puran; Goswami, Sailendra; Shrivastav, Pranav S

    2008-09-01

    A sensitive, specific and high throughput bioanalytical method using automated sample processing via 96-well plate liquid-liquid extraction and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) has been developed for the determination of methoxsalen in human plasma. Plasma samples with ketoconazole as internal standard (IS) were prepared by employing 0.2 mL human plasma in ethyl acetate:dichloromethane (80:20, v/v). The chromatographic separation was achieved on a Waters Acquity UPLC BEH C18 column using isocratic mobile phase, consisting of 10 mM ammonium formate and acetonitrile (60:40, v/v), at a flow rate of 0.5 mL/min. The linear dynamic range was established over the concentration range 1.1-213.1 ng/mL for methoxsalen. The method was rugged and rapid with a total run time of 1.5 min. It was successfully applied to a pivotal bioequivalence study in 12 healthy human subjects after oral administration of 10 mg extended release methoxsalen formulation under fasting condition.

  1. Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility. ESTCP Cost and Performance Report

    DTIC Science & Technology

    2012-08-01

    Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility August 2012 Report Documentation Page Form...DATES COVERED - 4. TITLE AND SUBTITLE Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and...polyoxymethylene PRC performance reference compounds SERDP Strategic Environmental Research and Development Program SPME solid phase microextraction

  2. Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility (User’s Manual)

    DTIC Science & Technology

    2012-05-01

    GUIDANCE DOCUMENT Demonstration and Evaluation of Solid Phase Microextraction For the Assessment of Bioavailability and Contaminant Mobility...Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility ER-200624Danny R. Reible...in-situ measurement of sediment pore water concentrations with solid phase microextraction using polydimethyl siloxane as the extractant. The method

  3. Silica supported Fe(3)O(4) magnetic nanoparticles for magnetic solid-phase extraction and magnetic in-tube solid-phase microextraction: application to organophosphorous compounds.

    PubMed

    Moliner-Martinez, Y; Vitta, Yosmery; Prima-Garcia, Helena; González-Fuenzalida, R A; Ribera, Antonio; Campíns-Falcó, P; Coronado, Eugenio

    2014-03-01

    This work demonstrates the application of silica supported Fe3O4 nanoparticles as sorbent phase for magnetic solid-phase extraction (MSPE) and magnetic on-line in-tube solid-phase microextraction (Magnetic-IT-SPME) combined with capillary liquid chromatography-diode array detection (CapLC-DAD) to determine organophosphorous compounds (OPs) at trace level. In MSPE, magnetism is used as separation tool while in Magnetic-IT-SPME, the application of an external magnetic field gave rise to a significant improvement of the adsorption of OPs on the sorbent phase. Extraction efficiency, analysis time, reproducibility and sensitivity have been compared. This work showed that Magnetic-IT-SPME can be extended to OPs with successful results in terms of simplicity, speed, extraction efficiency and limit of detection. Finally, wastewater samples were analysed to determine OPs at nanograms per litre.

  4. Phase nucleation and evolution mechanisms in heterogeneous solids

    NASA Astrophysics Data System (ADS)

    Udupa, Anirudh

    Phase nucleation and evolution is a problem of critical importance in many applications. As the length scales are reduced, it becomes increasingly important to consider interfacial and micro-structural effects that can be safely ignored at larger length scales owing to randomness. The theory of phase nucleation has been addressed usually by the classical nucleation theory, which was originally derived for single component fluid systems, after making an assumption of equilibrium. The criterion has not been rigorously derived for solids, which are far from equilibrium due to dissipation by multiple physical drivers. In this thesis, a thermodynamically sound nucleation criterion is derived for systems with multiple interacting physical phenomena and multiple dissipating mechanisms. This is done, using the tools of continuum mechanics, by determining the change in free energy upon the introduction of a new nucleus into the system. The developed theory is demonstrated to be a generalization of the classical nucleation theory (CNT). The developed theory is then applied to the problem of electromigration driven void nucleation, a serious reliability concern for the microelectronics industry. The void grows and eventually severs the line making the chip nonfunctional. There are two classes of theories at present in the electromigration literature to address the problem of void nucleation, the vacancy supersaturation theory and the entropic dissipation theory, both of which are empirical and based on intuition developed from experimental observations. When the developed theory was applied to the problem of electromigration, it was found to be consistent with the vacancy supersaturation theory, but provided the correct energetic quantity, the chemical potential, which has contribution from both the vacancy concentration as well as the hydrostatic stress. An experiment, consisting of electromigration tests on serpentine lines, was developed to validate the developed

  5. EVALUATION OF SOLID PHASE MICROEXTRACTION FOR THE ANALYSIS OF HYDROPHILIC COMPOUNDS

    EPA Science Inventory

    Two commercially available solid phase microextractions (SPME) fibers, polyacrylate and carboxem/polydimethylsiloxane (PDMS), were evaluated for their ability to extract hydrophilic compounds from drinking water. Conditions, such as desorption time, desorption temperature, sample...

  6. DETERMINATION OF CHLOROETHENES IN ENVIRONMENTAL BIOLOGICAL SAMPLES USING GAS CHROMATOGRAPHY COUPLED WITH SOLID PHASE MICRO EXTRACTION

    EPA Science Inventory

    An analytical method has been developed to determine the chloroethene series, tetrachloroethene (PCE), trichloroethene (TCE),cisdichloroethene (cis-DCE) andtransdichloroethene (trans-DCE) in environmental biotreatment studies using gas chromatography coupled with a solid phase mi...

  7. Recent Application of Solid Phase Based Techniques for Extraction and Preconcentration of Cyanotoxins in Environmental Matrices.

    PubMed

    Mashile, Geaneth Pertunia; Nomngongo, Philiswa N

    2017-03-04

    Cyanotoxins are toxic and are found in eutrophic, municipal, and residential water supplies. For this reason, their occurrence in drinking water systems has become a global concern. Therefore, monitoring, control, risk assessment, and prevention of these contaminants in the environmental bodies are important subjects associated with public health. Thus, rapid, sensitive, selective, simple, and accurate analytical methods for the identification and determination of cyanotoxins are required. In this paper, the sampling methodologies and applications of solid phase-based sample preparation methods for the determination of cyanotoxins in environmental matrices are reviewed. The sample preparation techniques mainly include solid phase micro-extraction (SPME), solid phase extraction (SPE), and solid phase adsorption toxin tracking technology (SPATT). In addition, advantages and disadvantages and future prospects of these methods have been discussed.

  8. Effect of solids, caloric content on dual-phase gastric emptying

    SciTech Connect

    Van Den Maegdenbergh, V.; Urbain, J.L.; Siegel, J.A.; Mortelmans, L.; De Roo, M. Temple Univ. Hospital, Philadelphia, PA )

    1990-03-01

    The dual-phase gastric emptying technique is routinely employed to determine the differential emptying of solids and liquids in a wide spectrum of gastrointestinal diseases. Composition, acidity, volume, caloric density, physical form and viscosity of the test means have been shown to be important determinants for the quantitative evaluation of gastric emptying. In this study, the authors have evaluated the effect of increasing the caloric content of the solid portion of a physiologic test mean on both solid and liquid emptying kinetics in health male volunteers. They observed that increasing solid caloric content delayed emptying of both solids and liquids. For the solid phase, the delay was accounted for by a longer lag phase and decrease in emptying rate; for liquids a longer emptying rate was also obtained. They conclude that modification of the caloric content of the solid portion of a meal not only affects the emptying of the solid phase but also alters the emptying of the liquid component of the meal.

  9. Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

    PubMed

    Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio

    2016-04-21

    We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

  10. Solid Phase Equilibria in the Pi-Ga-As and Pt-Ga-Sb Systems

    DTIC Science & Technology

    1988-07-22

    OFFICE OF NAVAL RESEARCH Research Contract N00014-87-K-0014 R&T Code 413E026---01 AD-A 198 654 TECHNICAL REPORT No. 9 SOLID PHASE EQUILIBRIA IN THE...Classtcation) UNCLASSLFIED: Tech.Rept.#9 SOLID PHASE EQUILIBRIA IN T11: Pt-Ga-As AND Pt-Ga-Sb SYST’IS 12 PERSONAL AuTiOR(S) C.T. Tsai and R.S. Williats 13a TYPE

  11. Two-dimensional solid-phase extraction strategy for the selective enrichment of aminoglycosides in milk.

    PubMed

    Shen, Aijin; Wei, Jie; Yan, Jingyu; Jin, Gaowa; Ding, Junjie; Yang, Bingcheng; Guo, Zhimou; Zhang, Feifang; Liang, Xinmiao

    2016-12-19

    An orthogonal two-dimensional solid-phase extraction strategy was established for the selective enrichment of three aminoglycosides including spectinomycin, streptomycin, and dihydrostreptomycin in milk. A reversed-phase liquid chromatography material (C18 ) and a weak cation-exchange material (TGA) were integrated in a single solid-phase extraction cartridge. The feasibility of two-dimensional clean-up procedure that experienced two-step adsorption, two-step rinsing, and two-step elution was systematically investigated. Based on the orthogonality of reversed-phase and weak cation-exchange procedures, the two-dimensional solid-phase extraction strategy could minimize the interference from the hydrophobic matrix existing in traditional reversed-phase solid-phase extraction. In addition, high ionic strength in the extracts could be effectively removed before the second dimension of weak cation-exchange solid-phase extraction. Combined with liquid chromatography and tandem mass spectrometry, the optimized procedure was validated according to the European Union Commission directive 2002/657/EC. A good performance was achieved in terms of linearity, recovery, precision, decision limit, and detection capability in milk. Finally, the optimized two-dimensional clean-up procedure incorporated with liquid chromatography and tandem mass spectrometry was successfully applied to the rapid monitoring of aminoglycoside residues in milk.

  12. Analysis of the structure of synthetic and natural melanins by solid-phase

    SciTech Connect

    Duff, G.A.; Roberts, J.E.; Foster, N.

    1988-09-06

    The structures of one synthetic and two natural melanins are examined by solid-state NMR using cross polarization, magic angle sample spinning, and high-power proton decoupling. The structural features of synthetic dopa malanin are compared to those of melanin from malignant melanoma cells grown in culture and sepia melanin from squid ink. Natural abundance /sup 13/C and /sup 15/N spectra show resonances consistent with known pyrrolic and indolic structures within the heterogeneous biopolymer; /sup 13/C spectra indicate the presence of aliphatic residues in all three materials. These solid-phase experiments illustrate the promise of solid-phase NMR for elucidating structural from insoluble biomaterials.

  13. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    PubMed

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

    2014-11-26

    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

  14. Phase transition of solid bismuth under high pressure

    NASA Astrophysics Data System (ADS)

    Chen, Hai-Yan; Xiang, Shi-Kai; Yan, Xiao-Zhen; Zheng, Li-Rong; Zhang, Yi; Liu, Sheng-Gang; Bi, Yan

    2016-10-01

    As a widely used pressure calibrator, the structural phase transitions of bismuth from phase I, to phase II, to phase III, and then to phase V with increasing pressure at 300 K have been widely confirmed. However, there are different structural versions for phase III, most of which are determined by x-ray diffraction (XRD) technology. Using x-ray absorption fine structure (XAFS) measurements combined with ab initio calculations, we show that the proposed incommensurate composite structure of bismuth of the three configurations is the best option. An abnormal continuous increase of the nearest-neighbor distance of phase III with elevated pressure is also observed. The electronic structure transformation from semimetal to metal is responsible for the complex behavior of structure transformation. Project supported by the National Natural Science Foundation of China (Grant Nos. 10904133, 11304294, 11274281, 11404006, and U1230201), the Development Foundation of China Academy of Engineering Physics (Grant Nos. 2015B0101004, 2013B0401062, and 2012A0101001), the Research Foundation of the Laboratory of Shock Wave and Detonation, China (Grant No. 9140C670201140C67282).

  15. New insights in Microbial Fuel Cells: novel solid phase anolyte.

    PubMed

    Tommasi, Tonia; Salvador, Gian Paolo; Quaglio, Marzia

    2016-07-04

    For the development of long lasting portable microbial fuel cells (MFCs) new strategies are necessary to overcome critical issues such as hydraulic pump system and the biochemical substrate retrieval overtime to sustain bacteria metabolism. The present work proposes the use of a synthetic solid anolyte (SSA), constituted by agar, carbonaceous and nitrogen sources dissolved into diluted seawater. Results of a month-test showed the potential of the new SSA-MFC as a long lasting low energy consuming system.

  16. New insights in Microbial Fuel Cells: novel solid phase anolyte

    PubMed Central

    Tommasi, Tonia; Salvador, Gian Paolo; Quaglio, Marzia

    2016-01-01

    For the development of long lasting portable microbial fuel cells (MFCs) new strategies are necessary to overcome critical issues such as hydraulic pump system and the biochemical substrate retrieval overtime to sustain bacteria metabolism. The present work proposes the use of a synthetic solid anolyte (SSA), constituted by agar, carbonaceous and nitrogen sources dissolved into diluted seawater. Results of a month-test showed the potential of the new SSA-MFC as a long lasting low energy consuming system. PMID:27375205

  17. New insights in Microbial Fuel Cells: novel solid phase anolyte

    NASA Astrophysics Data System (ADS)

    Tommasi, Tonia; Salvador, Gian Paolo; Quaglio, Marzia

    2016-07-01

    For the development of long lasting portable microbial fuel cells (MFCs) new strategies are necessary to overcome critical issues such as hydraulic pump system and the biochemical substrate retrieval overtime to sustain bacteria metabolism. The present work proposes the use of a synthetic solid anolyte (SSA), constituted by agar, carbonaceous and nitrogen sources dissolved into diluted seawater. Results of a month-test showed the potential of the new SSA-MFC as a long lasting low energy consuming system.

  18. Phase relationships involving RDX and common solid propellant binders

    SciTech Connect

    Boyer, E.; Brown, P.W.; Kuo, K.K.

    1996-07-01

    The solubilities of the common propellant ingredients acetyl triethyl citrate (ATEC) and cellulose acetate butyrate (CAB) and their effects on RDX (cyclotrimethylenetrinitramine) unit cell dimensions were investigated. If there is appreciable solid solubility, solutions will form and will have enthalpies of fusion, melting temperatures, and other characteristics different from those of pure RDX. It is desirable to establish the properties of such mixtures when designing new propellant formulations. Samples were aged at an elevated temperature to speed the formation of solid solutions. A least-squares analysis of X-ray diffraction data was used to obtain the lattice parameters from which unit cell volume and solubility was deduced. Both ATEC and CAB caused an expansion of the unit cell, indicating the formation of a solid solution. The limit of solubility in the ATEC/RDX mixture appeared to be approximately 13 wt% ATEC, while the CAB/RDX limit is above 16 wt% CAB. In both mixes, the cell volume expanded linearly with increasing proportion of binder. The large amount of gas generated and high energy released during combustion make RDX very attractive for both rocket and gun propulsion applications. The absence of HCl in the combustion products makes RDX desirable on an environmental basis as well.

  19. Solid-matrix fluorescence and phosphorescence and solid-phase microextraction of polycyclic aromatic hydrocarbons with hydrophobic paper

    SciTech Connect

    Ackerman, A.H.; Hurtubise, R.J.

    1999-07-01

    Solid-matrix fluorescence (SMF) and solid-matrix phosphorescence (SMP) have been used in conjunction with solid-phase microextraction to characterize mixtures of polycyclic aromatic hydrocarbons (PAHs) isolated from water. Whatman 1PS paper was used to extract the PAH from water, and then the isolated PAHs were directly identified on the paper by obtaining SMF and SMP spectra. The SMF and SMP properties of 10 PAH were obtained, and the PAHs in a two-component mixture, a three-component mixture, and a four-component mixture were easily identified by a combination of SMF and SMP. No external heavy atom was needed to acquire the SMP data. Benzo[{ital e}]pyrene gave a limit of detection of 6.2 pg/mL with SMP, and with SMF benzo[{ital a}]pyrene gave a limit of detection of 19 pg/mL. {copyright} {ital 1999} {ital Society for Applied Spectroscopy}

  20. Application of nuclear techniques in two-phase liquid-solid particles hydrotransport investigations

    NASA Astrophysics Data System (ADS)

    Zych, Marcin; Hanus, Robert; Vlasak, Pavel; Petryka, Leszek; Jaszczur, Marek

    2016-03-01

    The paper presents gamma radiation application to two-phase flow investigation in a vertical pipeline, where the flow of solid particles transported by water was examined by use of both: radiotracers and gamma-absorption method. The simultaneous use of two methods allows analyzing of important parameters of solid particles hydrotransport. In the described experiments as solid phase the ceramic models representing natural polymetallic ocean nodules were used. Radiotracers allow to track the movements of selected models, representing specified grain size and the designation of its velocity. However gamma-absorption method enables measurement of average solid-phase velocity. For analysis of electrical signals obtained from scintillation detectors the cross-correlation method has been applied.

  1. Solid-liquid phase equilibria of the Gaussian core model fluid.

    PubMed

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J

    2009-11-14

    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision.

  2. Synthesis of gold-silica composite nanowires through solid-liquid-solid phase growth.

    PubMed

    Paulose, Maggie; Varghese, Oomman K; Grimes, Craig A

    2003-08-01

    Nanoscale wires of silicon oxide, and silicon oxide with embedded gold-silicide nanospheres, are synthesized by heating of a gold-coated silicon wafer at temperatures of 1000 degrees C or above, with the resulting wires having diameters ranging from 30 to 150 nm and lengths of approximately 1 mm. This simple fabrication process should make possible economical bulk production of nanowires. Studies indicate that the growth of these gold-silica composite nanowires occurs directly on the silicon wafer by a solid-liquid-solid mechanism.

  3. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... centrifugation and filtration through a 0.45 micron filter. The suspended particulate phase is the supernatant as obtained above prior to centrifugation and filtration. The solid phase includes all material settling to... interact with ocean water to form insoluble matter or new toxic compounds, or materials which may...

  4. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... centrifugation and filtration through a 0.45 micron filter. The suspended particulate phase is the supernatant as obtained above prior to centrifugation and filtration. The solid phase includes all material settling to... interact with ocean water to form insoluble matter or new toxic compounds, or materials which may...

  5. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... centrifugation and filtration through a 0.45 micron filter. The suspended particulate phase is the supernatant as obtained above prior to centrifugation and filtration. The solid phase includes all material settling to... interact with ocean water to form insoluble matter or new toxic compounds, or materials which may...

  6. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... centrifugation and filtration through a 0.45 micron filter. The suspended particulate phase is the supernatant as obtained above prior to centrifugation and filtration. The solid phase includes all material settling to... interact with ocean water to form insoluble matter or new toxic compounds, or materials which may...

  7. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... centrifugation and filtration through a 0.45 micron filter. The suspended particulate phase is the supernatant as obtained above prior to centrifugation and filtration. The solid phase includes all material settling to... interact with ocean water to form insoluble matter or new toxic compounds, or materials which may...

  8. Comparison of the solid-phase fragment condensation and phase-change approaches in the synthesis of salmon I calcitonin.

    PubMed

    Gatos, D; Tzavara, C

    2001-02-01

    Salmon I calcitonin was synthesized using both phase-change and conventional solid-phase fragment condensation (SPFC) approaches, utilizing the Rink amide linker (Fmoc-amido-2,4-dimethoxybenzyl-4-phenoxyacetic acid) combined with 2-chlorotrityl resin and the Fmoc/tBu(Trt)-based protection scheme. Phase-change synthesis, performed by the selective detachment of the fully protected C-terminal 22-mer peptide-linker from the resin and subsequent condensation in solution with the N-terminal 1-10 fragment, gave a product of slightly less purity (85 vs. 92%) than the corresponding synthesis on the solid-phase. In both cases salmon I calcitonin was easily obtained in high purity.

  9. Solid-State Phase Equilibria in the ZnS-CdS System

    DTIC Science & Technology

    1988-09-01

    OFFICE OF NAVAL RESEARCH !iTIB - K Contract N00014-87-K-0531 R&TCode 431a016 TECHNICAL REPORT NO. I Solid-State Phase Equilibria in the ZnS-CdS...PROGRAM PROJECT TASK VVORK j*JT ELEMENT NO NO NO % Q I rTi (Incluc e Security Classitication) Solid-State Phase Equilibria in the ZnS-CdS System 12 PERSONAL...are obsolete Accesslon For NTI& GRA&1 SOLD-STATE PHASE EQUILIBRIA IN THE ZnS-CdS SYSTEM DTIC TAB 3 W. W. Chen, J. M. Zhang, A. J. Ardell, and B. Dunn

  10. Use of a solid-state multihead gamma counter in a second-generation system for solid-phase immunoassay

    SciTech Connect

    Parsons, G.H. Jr.; Rogers, C.H.; Polsky-Cynkin, R.; Wood, A.M.; Miles, L.E.; Rogers, A.H.

    1983-09-01

    Simultaneous advances in detector technology and solid-phase separation systems, as well as the availability of powerful desktop computers, have made possible the development of ''second-generation'' solid-phase immunoassays. These retain the advantages of classical solid phase while significantly accelerating reaction kinetics. Hapten assays--such as for digoxin, thyroxin, and triiodothyronine uptake--in batches of 48 are processed in about 20 min from reagent introduction until hard-copy printout, with minimal operator involvement. The system also functions as a 48-detector gamma counter, capable of counting and reducing data for any /sup 125/I-based RIA that can be run in a 12 X 75 mm test tube. System control, data management, and computer screen displays of kinetic data are provided by an unmodified Hewlett Packard HP-87XM computer. User-friendly disc-based software facilitates the creation and storage of counting and data reduction protocols for as many as 30 RIAs from various manufacturers as well as up to 30 of our own assays.

  11. Theoretical calculations of phase transitions and optical properties of solid iodine under high pressures

    NASA Astrophysics Data System (ADS)

    San, Xiaojiao; Wang, Liancheng; Ma, Yanming; Liu, Zhiming; Cui, Tian; Liu, Bingbing; Zou, Guangtian

    2008-04-01

    The structural stability and optical properties of solid iodine under pressure have been studied using the ab initio pseudopotential plane-wave method. The dependence of lattice parameters on pressure indicates that the first structural phase transition from phase I to phase V occurs at about 20 GPa. From the pressure dependence of our elastic constants for solid iodine in phase I, it is found that the first structural transformation from molecular phase I to the intermediate phase V occurs at about 20 GPa due to the softening of the elastic constant C44, which is very close to the transition pressure of 20 GPa obtained by geometry optimizations and 23.2 GPa obtained by experimental measurements. The optimized structure for phase V is a face-centered orthorhombic (fco) phase with equal interatomic distances d1 = d2 = d3, but this fco structure is mechanically unstable, with shear elastic stiffness coefficient C44<0. To understand the modulated phase V, we use a periodic crystal structure to mimic the incommensurate phase V and obtain some quantitative information. In our calculation, the modulated phase is thermodynamically and mechanically stable. It is believed that phase V is not a monatomic phase but an intermediate state between a molecular and a monatomic state.

  12. Rapidly Activated Dynamic Phase Transitions in Nonlinear Solids

    DTIC Science & Technology

    1993-02-15

    I Form Approv# edAD -A263 601 AiENTA11ON PAGE- f____________18 1. AGENCY USE ONLY (Lea"e blaWk 12. REPORT DATE 13. REPORT TYPE AND OATES COVEREO Feb...phase transforming media during high energy impact. Conversion of mechanical energy to thermal ener- gy has been studied by means of an extended theory...and Phase Structures in General Media , R. Fosdick, E. Dunn & M. Slemrod eds., IMA volume series, Springer- Verlag. Song, J. and T. L. Pence (1992

  13. Two-phase anaerobic digestion of vegetable market waste fraction of municipal solid waste and development of improved technology for phase separation in two-phase reactor.

    PubMed

    Majhi, Bijoy Kumar; Jash, Tushar

    2016-12-01

    Biogas production from vegetable market waste (VMW) fraction of municipal solid waste (MSW) by two-phase anaerobic digestion system should be preferred over the single-stage reactors. This is because VMW undergoes rapid acidification leading to accumulation of volatile fatty acids and consequent low pH resulting in frequent failure of digesters. The weakest part in the two-phase anaerobic reactors was the techniques applied for solid-liquid phase separation of digestate in the first reactor where solubilization, hydrolysis and acidogenesis of solid organic waste occur. In this study, a two-phase reactor which consisted of a solid-phase reactor and a methane reactor was designed, built and operated with VMW fraction of Indian MSW. A robust type filter, which is unique in its implementation method, was developed and incorporated in the solid-phase reactor to separate the process liquid produced in the first reactor. Experiments were carried out to assess the long term performance of the two-phase reactor with respect to biogas production, volatile solids reduction, pH and number of occurrence of clogging in the filtering system or choking in the process liquid transfer line. The system performed well and was operated successfully without the occurrence of clogging or any other disruptions throughout. Biogas production of 0.86-0.889m(3)kg(-1)VS, at OLR of 1.11-1.585kgm(-3)d(-1), were obtained from vegetable market waste, which were higher than the results reported for similar substrates digested in two-phase reactors. The VS reduction was 82-86%. The two-phase anaerobic digestion system was demonstrated to be stable and suitable for the treatment of VMW fraction of MSW for energy generation.

  14. Solid phase stability of molybdenum under compression: Sound velocity measurements and first-principles calculations

    SciTech Connect

    Zhang, Xiulu; Liu, Zhongli; Jin, Ke; Xi, Feng; Yu, Yuying; Tan, Ye; Dai, Chengda; Cai, Lingcang

    2015-02-07

    The high-pressure solid phase stability of molybdenum (Mo) has been the center of a long-standing controversy on its high-pressure melting. In this work, experimental and theoretical researches have been conducted to check its solid phase stability under compression. First, we performed sound velocity measurements from 38 to 160 GPa using the two-stage light gas gun and explosive loading in backward- and forward-impact geometries, along with the high-precision velocity interferometry. From the sound velocities, we found no solid-solid phase transition in Mo before shock melting, which does not support the previous solid-solid phase transition conclusion inferred from the sharp drops of the longitudinal sound velocity [Hixson et al., Phys. Rev. Lett. 62, 637 (1989)]. Then, we searched its structures globally using the multi-algorithm collaborative crystal structure prediction technique combined with the density functional theory. By comparing the enthalpies of body centered cubic structure with those of the metastable structures, we found that bcc is the most stable structure in the range of 0–300 GPa. The present theoretical results together with previous ones greatly support our experimental conclusions.

  15. Phase separation in garnet solid solutions and its effect on optical properties.

    PubMed

    Kaveh, Shakiba; Tremblay, Clément P; Norhashim, Nurhakimah; Curry, Richard J; Cheetham, Anthony K

    2013-11-26

    Phase behavior is studied in erbium-doped Y3 Al5 O12 (YAG) garnets synthesized by solid-state reactions. High resolution synchrotron XRD and SEM-EDX studies reveal phase separation at an erbium content between 8 and 50 at%, depending upon the processing conditions. Similar results are found in closely-related garnet systems. The phase separation has a striking effect on the optical properties of YAG:Er(3+) .

  16. SANS study of phase separation in solid {sup 3}He-{sup 4}He

    SciTech Connect

    Koster, J.P.; Nagler, S.E.; Adams, E.D.; Wignall, G.D.

    1994-12-31

    Small angle neutron scattering has been used to study phase separation in a quantum alloy, solid {sup 3}He{sub x}-{sup 4}He{sub 1{minus}x}. The onset of phase separation is marked by a dramatic increase in the measured scattering. A simple interpretation of the results suggests that the late-stage phase separation kinetics are dominated by an increase in the concentration of {sup 3}He atoms in preexisting precipitate regions.

  17. Functional Ceramic Ferroelectromagnetic Materials in Single Phase Solid-Solutions

    DTIC Science & Technology

    2007-12-05

    materials of 99.9% purity ( Aldrich) ( Bi2O3 , La2O3, PbO, Fe2O3, TiO2) were weighed in a stochiometirc proportion and ball milled in acetone medium for...Aldrich) ( Bi2O3 , MgO, ZrO2, PbO, Fe2O3, TiO2) were weighed in a stochiometirc proportion and ball milled in acetone medium for 24 hours.The mixture...prepared using conventional solid- state reaction route. The raw materials of 99.9% purity ( Aldrich) ( Bi2O3 , La2O3, PbO, Fe2O3, TiO2) were weighed in a

  18. Determination of melamine in aquaculture feed samples based on molecularly imprinted solid-phase extraction.

    PubMed

    Lian, Ziru; Liang, Zhenlin; Wang, Jiangtao

    2015-10-01

    This research highlights the application of highly efficient molecularly imprinted solid-phase extraction for the preconcentration and analysis of melamine in aquaculture feed samples. Melamine-imprinted polymers were synthesized employing methacrylic acid and ethylene glycol dimethacrylate as functional monomer and cross-linker, respectively. The characteristics of obtained polymers were evaluated by scanning electron microscopy, Fourier transform infrared spectroscopy and binding experiments. The imprinted polymers showed an excellent adsorption ability for melamine and were applied as special solid-phase extraction sorbents for the selective cleanup of melamine. An off-line molecularly imprinted solid-phase extraction procedure was developed for the separation and enrichment of melamine from aquaculture feed samples prior to high-performance liquid chromatography analysis. Optimum molecularly imprinted solid-phase extraction conditions led to recoveries of the target in spiked feed samples in the range 84.6-96.6% and the relative standard deviation less than 3.38% (n = 3). The aquaculture feed sample was determined, and there was no melamine found. The results showed that the molecularly imprinted solid-phase extraction protocols permitted the sensitive, uncomplicated and inexpensive separation and pre-treatment of melamine in aquaculture feed samples.

  19. Online in situ analysis of selected semi-volatile organic compounds in water by automated microscale solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry.

    PubMed

    Li, Yongtao; George, John E; McCarty, Christina L

    2007-12-28

    A fully automated analytical method was developed for the online in situ analysis of selected semi-volatile organic compounds in water. The method used a large-volume injection/gas chromatography/mass spectrometry coupled with a fully automated microscale solid-phase extraction technique, which was based on x-y-z robotic techniques. Water samples were extracted by using a 96-well solid-phase extraction plate. For most analytes included in this study, the obtained linear calibrations ranged from 0.05 to 5.0 microg/L with correlation coefficients of 0.996-1.000, the method detection limits were less than 0.1 microg/L, and the relative recoveries were in the range of 70-120% with a relative standard deviation of less than 15% for fortified reagent water samples. The applications to chlorinated tap water, well water, and river water have been validated. The obtained results were similar to those resulting from fortified reagent water samples for all analytes except metribuzin, bromacil, aldrin, and methoxychlor. Matrix effects were observed for these analytes. In general, this fully automated analytical method was rugged, reliable, and easy to operate, and was capable of providing real-time data to water treatment and distribution systems as well as water reservation and protection systems. In addition, the method could reduce the analytical costs associated with sample collection, transportation, storage, and preparation.

  20. Solid phosphorus phase in aluminum- and iron-treated biosolids.

    PubMed

    Huang, Xiao-Lan; Chen, Yona; Shenker, Moshe

    2007-01-01

    Stabilization of phosphorus (P) in sewage sludge (biosolids) to reduce water-soluble P concentrations is essential for minimizing P loss from amended soils and maximizing the capacity of the soil to safely serve as an outlet for this waste material. The chemical form at which P is retained in biosolids stabilized by Al(2)(SO(4))(3) x 18H(2)O (alum) or FeSO(4) x 7H(2)O (FeSul) was investigated by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS) and by X-ray diffraction (XRD). Both treatments resulted in the formation of a Ca-P phase, probably brushite. Phosphorus was further retained in the alum-treated biosolids by precipitation of an Al-P phase with an Al/P molar ratio of about 1:1, while in the FeSul-treated biosolids, P was retained by both precipitation with Fe/P molar ratios of 1:1 or 1.5:1, and by adsorption onto newly formed Fe hydroxides exhibiting an Fe/P molar ratio of up to 11:1. All of these mechanisms efficiently reduced P solubility and are crucial in biosolids environmentally safe agronomic beneficial use for this waste product; however, each P phase formed may react differently in the amended soil, depending on soil properties. Thus, the proper P stabilization method would depend on the target soil.

  1. Solid phase synthesis of a GHRP analog containing C-terminal thioamide group.

    PubMed

    Majer, Z; Zewdu, M; Hollósi, M; Sepródi, J; Vadász, Z; Teplán, I

    1988-02-15

    [Lyst6]GHRP, the C-terminally thionated analog of the highly potent growth hormone releasing hexapeptide His-D-Trp-Ala-Trp-D-Phe-Lys-NH2 was prepared by using solid support. The success of the synthesis showed that Lawesson's reagent can be used for selective thionation of an amide group not only in solution but also on the surface of a resin. The C-terminal thioamide group proved to be stable under the conditions of the solid phase synthesis.

  2. Characterization of rhamnolipids by liquid chromatography/mass spectrometry after solid-phase extraction.

    PubMed

    Behrens, Beate; Engelen, Jeannine; Tiso, Till; Blank, Lars Mathias; Hayen, Heiko

    2016-04-01

    Rhamnolipids are surface-active agents with a broad application potential that are produced in complex mixtures by bacteria of the genus Pseudomonas. Analysis from fermentation broth is often characterized by laborious sample preparation and requires hyphenated analytical techniques like liquid chromatography coupled to mass spectrometry (LC-MS) to obtain detailed information about sample composition. In this study, an analytical procedure based on chromatographic method development and characterization of rhamnolipid sample material by LC-MS as well as a comparison of two sample preparation methods, i.e., liquid-liquid extraction and solid-phase extraction, is presented. Efficient separation was achieved under reversed-phase conditions using a mixed propylphenyl and octadecylsilyl-modified silica gel stationary phase. LC-MS/MS analysis of a supernatant from Pseudomonas putida strain KT2440 pVLT33_rhlABC grown on glucose as sole carbon source and purified by solid-phase extraction revealed a total of 20 congeners of di-rhamnolipids, mono-rhamnolipids, and their biosynthetic precursors 3-(3-hydroxyalkanoyloxy)alkanoic acids (HAAs) with different carbon chain lengths from C8 to C14, including three rhamnolipids with uncommon C9 and C11 fatty acid residues. LC-MS and the orcinol assay were used to evaluate the developed solid-phase extraction method in comparison with the established liquid-liquid extraction. Solid-phase extraction exhibited higher yields and reproducibility as well as lower experimental effort.

  3. Solid solution, phase separation, and cathodoluminescence of GaP-ZnS nanostructures.

    PubMed

    Liu, Baodan; Bando, Yoshio; Dierre, Benjamin; Sekiguchi, Takashi; Golberg, Dmitri; Jiang, Xin

    2013-09-25

    Quaternary solid-solution nanowires made of GaP and ZnS have been synthesized through well-designed synthetic routines. The as-synthesized GaP-ZnS solid-solution nanowires exhibit decent crystallinity with the GaP phase as the host, while a large amount of twin structural defects are observed in ZnS-rich nanowires. Cathodoluminescence studies showed that GaP-rich solid-solution nanowires have a strong visible emission centered at 600 nm and the ZnS-rich solid-solution nanowires exhibited a weak emission peak in the UV range and a broad band in the range 400-600 nm. The formation mechanism, processes, and optical emissions of GaP-ZnS solid-solution nanowires were discussed in detail.

  4. Biological nitrate removal from water and wastewater by solid-phase denitrification process.

    PubMed

    Wang, Jianlong; Chu, Libing

    2016-11-01

    Nitrate pollution in receiving waters has become a serious issue worldwide. Solid-phase denitrification process is an emerging technology, which has received increasing attention in recent years. It uses biodegradable polymers as both the carbon source and biofilm carrier for denitrifying microorganisms. A vast array of natural and synthetic biopolymers, including woodchips, sawdust, straw, cotton, maize cobs, seaweed, bark, polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene succinate (PBS) and polylactic acid (PLA), have been widely used for denitrification due to their good performance, low cost and large available quantities. This paper presents an overview on the application of solid-phase denitrification in nitrate removal from drinking water, groundwater, aquaculture wastewater, the secondary effluent and wastewater with low C/N ratio. The types of solid carbon source, the influencing factors, the microbial community of biofilm attached on the biodegradable carriers, the potential adverse effect, and the cost of denitrification process are introduced and evaluated. Woodchips and polycaprolactone are the popular and competitive natural plant-like and synthetic biodegradable polymers used for denitrification, respectively. Most of the denitrifiers reported in solid-phase denitrification affiliated to the family Comamonadaceae in the class Betaproteobacteria. The members of genera Diaphorobacter, Acidovorax and Simplicispira were mostly reported. In future study, more attention should be paid to the simultaneous removal of nitrate and toxic organic contaminants such as pesticide and PPCPs by solid-phase denitrification, to the elucidation of the metabolic and regulatory relationship between decomposition of solid carbon source and denitrification, and to the post-treatment of the municipal secondary effluent. Solid-phase denitrification process is a promising technology for the removal of nitrate from water and wastewater.

  5. Structural and optical properties of solid-phase singlet oxygen photosensitizers based on fullerene aqueous suspensions

    NASA Astrophysics Data System (ADS)

    Belousova, I. M.; Belousov, V. P.; Kiselev, V. M.; Murav'eva, T. D.; Kislyakov, I. M.; Sirotkin, A. K.; Starodubtsev, A. M.; Kris'ko, T. K.; Bagrov, I. V.; Ermakov, A. V.

    2008-11-01

    The relationship between the structural and photosensitizing properties of solid-phase particles of fullerene C60 in aqueous suspensions is studied using the methods of absorption spectroscopy, electron spin resonance spectroscopy (ESR), X-ray diffraction, and spectrophotometry of solutions of singlet oxygen chemical traps—histidine in combination with p-nitrosodimethylaniline. Two new variants are proposed for obtaining aqueous suspensions of particles of solid-phase fullerene whose structures are disordered and whose degrees of amorphization are 67 and 40%, respectively. It is shown that an increase in the disorder of the structure of particles in suspensions and a decrease in their average size facilitate an increase in the formation efficiency of singlet oxygen by solid-phase fullerene presumably due to an in increase in the concentration of surface localized excitons.

  6. The use of coal in a solid phase reduction of iron oxide

    NASA Astrophysics Data System (ADS)

    Nokhrina, O. I.; Rozhihina, I. D.; Hodosov, I. E.

    2015-09-01

    The results of the research process of producing metalized products by solid-phase reduction of iron using solid carbonaceous reducing agents. Thermodynamic modeling was carried out on the model of the unit the Fe-C-O and system with iron ore and coal. As a result of modeling the thermodynamic boundary reducing, oxidizing, and transition areas and the value of the ratio of carbon and oxygen in the system. Simulation of real systems carried out with the gas phase obtained in the pyrolys of coal. The simulation results allow to determine the optimal cost of coal required for complete reduction of iron ore from a given composition. The kinetics of the processes of solid-phase reduction of iron using coal of various technological brands.

  7. Solid-Phase Synthesis of Amine/Carboxyl Substituted Prolines and Proline Homologues: Scope and Limitations.

    PubMed

    Zhou, Ziniu; Scott, William L; O'Donnell, Martin J

    2016-03-15

    A solid-phase procedure is used to synthesize racemic peptidomimetics based on the fundamental peptide unit. The peptidomimetics are constructed around proline or proline homologues variably substituted at the amine and carbonyl sites. The procedure expands the diversity of substituted peptidomimetic molecules available to the Distributed Drug Discovery (D3) project. Using a BAL-based solid-phase synthetic sequence the proline or proline homologue subunit is both constructed and incorporated into the peptidomimetic by an α-alkylation, hydrolysis and intramolecular cyclization sequence. Further transformations on solid-phase provide access to a variety of piperazine derivatives representing a class of molecules known to exhibit central nervous system activity. The procedure works well with proline cores, but with larger six- and seven-membered ring homologues the nature of the carboxylic acid acylating the cyclic amine can lead to side reactions and result in poor overall yields.

  8. Fe-Solid Phase Transformations Under Highly Basic Conditions

    SciTech Connect

    Qafoku, Nik; Qafoku, Odeta; Ainsworth, Calvin C.; Dohnalkova, Alice; McKinley, Susan G.

    2007-09-01

    Hyperalkaline and saline radioactive waste fluids with elevated temperatures from S-SX high-level waste tank farm at Hanford, WA accidentally leaked into sediments beneath the tanks, initiating a series of geochemical processes and reactions whose significance and extent was unknown. Among the most important processes was the dissolution of soil minerals and precipitation of stable secondary phases. The objective of this investigation was to study the release of Fe into the aqueous phase upon dissolution of Fe-bearing soil minerals, and the subsequent formation of Fe rich precipitates. Batch reactors were used to conduct experiments at 50 0C using solutions similar in composition to the waste fluids. Results clearly showed that, similarly to Si and Al, Fe was released from the dissolution of soil minerals (most likely phyllosilicates such as biotite, smectite, and chlorite). The extent of Fe release increased with base concentration and decreased with Al concentration in the contacting solution. The maximum apparent rate of Fe release (0.566 × 10-13 mol m-2 s-1) was measured in the treatment with no Al and a concentration of 4.32 mol L-1 NaOH in the contacting solution. Results from electron microscopy indicated that while Si and Al precipitated together to form feldspathoids in the groups of cancrinite and/or sodalite, Fe precipitation followed a different pathway leading to the formation of hematite and goethite. The newly formed Fe oxy-hydroxides may increase the sorption capacity of the sediments, promote surface mediated reactions such as precipitation and heterogeneous redox reactions, and affect the phase distribution of contaminant and radionuclides.

  9. Numerical simulation and analysis of solid-liquid two-phase flow in centrifugal pump

    NASA Astrophysics Data System (ADS)

    Zhang, Yuliang; Li, Yi; Cui, Baoling; Zhu, Zuchao; Dou, Huashu

    2013-01-01

    The flow with solid-liquid two-phase media inside centrifugal pumps is very complicated and the relevant method for the hydraulic design is still immature so far. There exist two main problems in the operation of the two-phase flow pumps, i.e., low overall efficiency and severe abrasion. In this study, the three-dimensional, steady, incompressible, and turbulent solid-liquid two-phase flows in a low-specific-speed centrifugal pump are numerically simulated and analyzed by using a computational fluid dynamics (CFD) code based on the mixture model of the two-phase flow and the RNG k- ɛ two-equation turbulence model, in which the influences of rotation and curvature are fully taken into account. The coupling between impeller and volute is implemented by means of the frozen rotor method. The simulation results predicted indicate that the solid phase properties in two-phase flow, especially the concentration, the particle diameter and the density, have strong effects on the hydraulic performance of the pump. Both the pump head and the efficiency are reduced with increasing particle diameter or concentration. However, the effect of particle density on the performance is relatively minor. An obvious jet-wake flow structure is presented near the volute tongue and becomes more remarkable with increasing solid phase concentration. The suction side of the blade is subject to much more severe abrasion than the pressure side. The obtained results preliminarily reveal the characteristics of solid-liquid two-phase flow in the centrifugal pump, and are helpful for improvement and empirical correction in the hydraulic design of centrifugal pumps.

  10. Solid phase sequencing of double-stranded nucleic acids

    DOEpatents

    Fu, Dong-Jing; Cantor, Charles R.; Koster, Hubert; Smith, Cassandra L.

    2002-01-01

    This invention relates to methods for detecting and sequencing of target double-stranded nucleic acid sequences, to nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probe comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include nucleic acids in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated determination of molecular weights and identification of the target sequence.

  11. NASA satellite communications application research. Phase 2: Efficient high power, solid state amplifier for EFH communications

    NASA Technical Reports Server (NTRS)

    Benet, James

    1993-01-01

    The final report describes the work performed from 9 Jun. 1992 to 31 Jul. 1993 on the NASA Satellite Communications Application Research (SCAR) Phase 2 program, Efficient High Power, Solid State Amplifier for EHF Communications. The purpose of the program was to demonstrate the feasibility of high-efficiency, high-power, EHF solid state amplifiers that are smaller, lighter, more efficient, and less costly than existing traveling wave tube (TWT) amplifiers by combining the output power from up to several hundred solid state amplifiers using a unique orthomode spatial power combiner (OSPC).

  12. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    ERIC Educational Resources Information Center

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

    2014-01-01

    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

  13. Leaching behavior and solubility -- Controlling solid phases of heavy metals in municipal solid waste incinerator ash

    SciTech Connect

    Johnson, C.A.; Ziegler, F.; Kersten, M.; Moor, H.C.

    1996-12-31

    This paper highlights the uses and limitations of thermodynamic calculations in the planning of leach tests in the laboratory or for research in the field. Heavy metal solubility has been studied in leachate from Landfill Lostorf, AG, Switzerland. Also, the influence of pH on the solubility of Cu, Pb, Cd and Zn has been determined in the laboratory. The results have been compared with the maximum allowable heavy metal concentrations in equilibrium with the appropriate (hydr)oxides and carbonates. Copper is supersaturated with respect to Cu(OH){sub 2} in both laboratory and field studies. Complexation with organic ligands is a probable explanation for this observation. Both Zn and Pb are undersaturated with respect to pure (hydr)oxides and carbonates, though agreement between calculations and measurements are close enough, that PbCO{sub 3} could be controlling the solubility in the laboratory experiments. The markedly lower concentrations of Pb in the field in comparison with the laboratory data could be explained by the affinity for Pb to bind to solids and the higher solid:solution ratio in field conditions. The solubility of Cd could be controlled by the formation of CdCO{sub 3}. The relatively high concentrations of Mo in the landfill leachate could be limited by the precipitation of CaMoO{sub 4}.

  14. Influence of calcium on microbial reduction of solid phase uranium(VI).

    PubMed

    Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

    2007-08-15

    The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium.

  15. Collector phase transitions during vapor-solid-solid nucleation of GaN nanowires.

    PubMed

    Chèze, Caroline; Geelhaar, Lutz; Trampert, Achim; Brandt, Oliver; Riechert, Henning

    2010-09-08

    We investigate the nucleation of Ni-induced GaN nanowires by in situ and ex situ experiments. Three nucleation stages are evidenced. In the first two stages, different crystal structures of the Ni collectors are identified. Real-time monitoring of the Ga desorption allows the amount of Ga incorporated in the collectors to be quantified. A transition of their crystal structure prior to nanowire growth is found to be in agreement with the thermodynamically stable phase sequence of the relevant phase diagrams.

  16. Dynamic speciation analysis of atrazine in aqueous latex nanoparticle dispersions using solid phase microextraction (SPME).

    PubMed

    Benhabib, Karim; Town, Raewyn M; van Leeuwen, Herman P

    2009-04-09

    Solid phase microextraction (SPME) is applied in the dynamic speciation analysis of the pesticide atrazine in an aqueous medium containing sorbing latex nanoparticles. It is found that the overall rate of extraction of the analyte is faster than in the absence of nanoparticles and governed by the coupled diffusion of free and particle-bound atrazine toward the solid/sample solution interface. In the eventual equilibrium the total atrazine concentration in the solid phase is dictated by the solid phase/water partition coefficient (K(sw)) and the concentration of the free atrazine in the sample solution. These observations demonstrate that the nanoparticles do not enter the solid phase. The experimental data show that the rate of release of sorbed atrazine from the latex particles is fast on the effective time scale of the microextraction process. A lability criterion is derived to quantitatively describe the relative rates of these two processes. All together, the results indicate that SPME has a strong potential for dynamic speciation analysis of organic compounds in media containing sorbing nanoparticles.

  17. CuAAC: An Efficient Click Chemistry Reaction on Solid Phase.

    PubMed

    Castro, Vida; Rodríguez, Hortensia; Albericio, Fernando

    2016-01-11

    Click chemistry is an approach that uses efficient and reliable reactions, such as Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), to bind two molecular building blocks. CuAAC has broad applications in medicinal chemistry and other fields of chemistry. This review describes the general features and applications of CuAAC in solid-phase synthesis (CuAAC-SP), highlighting the suitability of this kind of reaction for peptides, nucleotides, small molecules, supramolecular structures, and polymers, among others. This versatile reaction is expected to become pivotal for meeting future challenges in solid-phase chemistry.

  18. Preferential extraction of hydrocarbons from fire debris samples by solid phase microextraction.

    PubMed

    Lloyd, Julie A; Edmiston, Paul L

    2003-01-01

    Headspace analysis by extraction/GC-MS is a common method of detecting volatile hydrocarbon accelerants in fire debris samples. Solid-phase microextraction was tested to determine if there is selective extraction of chemically distinct compounds. It was found that both the polydimethylsiloxane (PDMS) and Carboxen/PDMS solid phase microextraction fibers show preferential extraction of aliphatic or aromatic compounds from the headspace depending on fiber type and temperature. The Carboxen/PDMS fiber type showed particular (although not exclusive) selectivity for extraction of aromatic hydrocarbons. Other experimental considerations of SPME are noted.

  19. Resin Capsules: Permeable Containers for Parallel/Combinatorial Solid-Phase Organic Synthesis

    PubMed Central

    Bouillon, Isabelle; Soural, Miroslav; Krchňák, Viktor

    2009-01-01

    A resin capsule is a permeable container for resin beads designed for multiple/combinatorial solid-phase organic synthesis. Resin capsules consist of a high density polyethylene ring sealed with peek mesh on both sides. The cylindrical shape of resin capsules enabled space-saving packing into plastic column-like reaction vessels commonly used for solid-phase organic synthesis. Resin capsules have been evaluated for their use in combinatorial synthesis, and a set of model compounds with excellent purity was prepared. PMID:18656988

  20. Optical Measurement for Solid- and Liquid-Phase Sb2Te3 around Its Melting Point

    NASA Astrophysics Data System (ADS)

    Kuwahara, Masashi; Endo, Rie; Tsutsumi, Kouichi; Morikasa, Fukuyoshi; Tsuruoka, Tohru; Fukaya, Toshio; Suzuki, Michio; Susa, Masahiro; Endo, Tomoyoshi; Tadokoro, Toshiyasu

    2013-11-01

    We have developed a system for measuring the complex refractive index of liquid- and solid-phase chalcogenide around their melting points. The system consists of a spectroscopic ellipsometer, an infrared heating system, and prism optics. As a container for the chalcogenide, we use a customized quartz cell, evacuated to several pascal level to avoid sample degradation. We adopted a measurement configuration that uses access from the bottom side, because a mirror-like surface which is necessary for optical measurement was naturally and easily created at the container bottom by gravity. We succeeded in observing the remarkable difference on the indices between liquid- and solid-phase Sb2Te3.

  1. Detection of ibuprofen and ciprofloxacin by solid-phase extraction and UV/Vis spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Zhengwei; Jiang, Jia Qian

    2012-07-01

    A simple and economic solid-phase extraction coupled with UV/Vis spectrophotometric method is described for the analysis of ibuprofen and ciprofloxacin. Following solid-phase extraction from model wastewater samples containing standard ibuprofen or ciprofloxacin, elutes were analyzed by a UV/Vis spectrophotometer at 225 nm for ibuprofen and 280 nm for ciprofloxacin. The assay was linear for both compounds with good coefficients of correlation. This method shows good recoveries for both compounds with 101.0 ± 9.8% for ibuprofen and 99.4 ± 11.8% ciprofloxacin.

  2. Solid-Phase Spectrophotometric Analysis of 1-Naphthol Using Silica Functionalized with m-Diazophenylarsonic Acid.

    PubMed

    Zaitseva, Nataliya; Alekseev, Sergei; Zaitsev, Vladimir; Raks, Viktoria

    2016-12-01

    The m-aminophenylarsonic acid (m-APAA) was immobilized onto the silica gel surface with covalently grafted quaternary ammonium groups via ion exchange. The diazotization of ion-bonded m-APAA resulted in a new solid-phase spectrophotometric reagent for detection of 1-naphtol in environmental water samples. The procedure of solid-phase spectrophotometric analysis is characterized by 20 μg L(-1) limit of detection (LOD) of 1-naphtol, up to 2000 concentration factor, and insensitivity to the presence of natural water components as well as to 30-fold excess of phenol, resorcinol, and catechol.

  3. Selective enrichment of phenols from coal liquefaction oil by solid phase extraction method

    SciTech Connect

    Tian, M.; Feng, J.

    2009-07-01

    This study focuses on the solid phase extraction method for the enrichment and separation of phenol from coal liquefaction oil. The phenols' separation efficiency was compared on different solid phase extraction (SPE) cartridges, and the effect of solvents with different polarity and solubility parameter on amino-bonded silica was compared for selection of optimal elution solution. The result showed that amino-bonded silica has the highest selectivity and best extraction capability due to two factors, weak anion exchange adsorption and polar attraction adsorption.

  4. Use of the 2-chlorotrityl chloride resin for microwave-assisted solid phase peptide synthesis.

    PubMed

    Ieronymaki, Matthaia; Androutsou, Maria Eleni; Pantelia, Anna; Friligou, Irene; Crisp, Molly; High, Kirsty; Penkman, Kirsty; Gatos, Dimitrios; Tselios, Theodore

    2015-09-01

    A fast and efficient microwave (MW)-assisted solid-phase peptide synthesis protocol using the 2-chlorotrityl chloride resin and the Fmoc/tBu methodology, has been developed. The established protocol combines the advantages of MW irradiation and the acid labile 2-chlorotrityl chloride resin. The effect of temperature during the MW irradiation, the degree of resin substitution during the coupling of the first amino acids and the rate of racemization for each amino acid were evaluated. The suggested solid phase methodology is applicable for orthogonal peptide synthesis and for the synthesis of cyclic peptides.

  5. Solid-Phase Spectrophotometric Analysis of 1-Naphthol Using Silica Functionalized with m-Diazophenylarsonic Acid

    NASA Astrophysics Data System (ADS)

    Zaitseva, Nataliya; Alekseev, Sergei; Zaitsev, Vladimir; Raks, Viktoria

    2016-03-01

    The m-aminophenylarsonic acid (m-APAA) was immobilized onto the silica gel surface with covalently grafted quaternary ammonium groups via ion exchange. The diazotization of ion-bonded m-APAA resulted in a new solid-phase spectrophotometric reagent for detection of 1-naphtol in environmental water samples. The procedure of solid-phase spectrophotometric analysis is characterized by 20 μg L-1 limit of detection (LOD) of 1-naphtol, up to 2000 concentration factor, and insensitivity to the presence of natural water components as well as to 30-fold excess of phenol, resorcinol, and catechol.

  6. Development of orthogonally protected hypusine for solid-phase peptide synthesis.

    PubMed

    Song, Aimin; Tom, Jeffrey; Yu, Zhiyong; Pham, Victoria; Tan, Dajin; Zhang, Dengxiong; Fang, Guoyong; Yu, Tao; Deshayes, Kurt

    2015-04-03

    An orthogonally protected hypusine reagent was developed for solid-phase synthesis of hypusinated peptides using the Fmoc/t-Bu protection strategy. The reagent was synthesized in an overall yield of 27% after seven steps from Cbz-Lys-OBzl and (R)-3-hydroxypyrrolidin-2-one. The side-chain protecting groups (Boc and t-Bu) are fully compatible with standard Fmoc chemistry and can be readily removed during the peptide cleavage step. The utility of the reagent was demonstrated by solid-phase synthesis of hypusinated peptides.

  7. Study on phase-locked coherence of evanescent wave coupling in solid-state laser

    NASA Astrophysics Data System (ADS)

    Chen, Yong; Liu, Xu; Zhu, Mengzhen; Lu, Changyong; Lu, Yimin; Tan, Caoyong; Wei, Shangfang

    2016-01-01

    The mechanism and characteristics of evanescent-wave coupling in solid-state laser is analyzed theoretically and experimentally. The results shown that self-organized phase locking between laser modes can be realized by evanescentwave coupling in solid-state laser. Based on "mutual injection and evanescent wave" characteristics of corner-cube prism, the paper reveals that far-field output of corner-cube laser is the inner reason and mechanism of coherent combining distribution by theory of evanescent wave and its coherence is better than plane parallel resonator. And "mutually coupled phase locking of six lasers based cube-corner resonator" scheme is proposed on this basis.

  8. Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts.

    PubMed

    Li, Na; Wang, Zhibing; Zhang, Liyuan; Nian, Li; Lei, Lei; Yang, Xiao; Zhang, Hanqi; Yu, Aimin

    2014-10-01

    Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction was developed and applied to the extraction of pesticides in high fatty matrices. The herbicides were ultrasonically extracted from peanut using ethyl acetate as extraction solvent. The separation of the analytes from a large amount of co-extractive fat was achieved by dispersive solid-phase extraction using MIL-101(Cr) as sorbent. In this step, the analytes were adsorbed on MIL-101(Cr) and the fat remained in bulk. The herbicides were separated and determined by high-performance liquid chromatography. The experimental parameters, including type and volume of extraction solvent, ultrasonication time, volume of hexane and eluting solvent, amount of MIL-101(Cr) and dispersive solid phase extraction time, were optimized. The limits of detection for herbicides range from 0.98 to 1.9 μg/kg. The recoveries of the herbicides are in the range of 89.5-102.7% and relative standard deviations are equal or lower than 7.0%. The proposed method is simple, effective and suitable for treatment of the samples containing high content of fat.

  9. Novel functionalized polymeric fabric and fiber material as solid support for solid-phase synthesis and biomedical applications

    NASA Astrophysics Data System (ADS)

    Xiang, Bei

    The aim of the research is to develop novel polymer solid support by modifying or fabricating polymeric fibrous materials for peptide synthesis and biomedical applications. Originally chemical inert isotactic polypropylene (iPP) fabric was utilized and modified to serve as a functional flexible planar solid support for solid phase peptide synthesis. The modification was achieved through thermal initiated radical grafting polymerization using acrylic acid, poly (ethylene glycol) diacrylate as monomers, and benzoyl peroxide as radical initiator. The iPP fabric was successfully functionalized and possessing as high as 0.7mmol/g carboxylic acid groups. Peptide ligand LHPQF was successfully synthesized on the new functional planar support. Specific enzyme immobilization was fulfilled on the functional iPP fabric support. A commercially available ethylene-acrylic acid copolymer was made into ultrafine copolymer fiber bundles which are composed of nanofibers with diameters ranging from 200nm to 800nm. Various mixing ratios of copolymer/matrix materials were utilized to explore the effect on the final nanofiber physical properties including morphology and stability in solvents. The surface carboxylic acid groups were further converted to amino groups before the functional nanofibers can be applied in solid phase peptide synthesis. Two peptide ligands, LHPQF and HWRGWV, were also successfully synthesized on the nanofiber bundles. Streptavidin and human immunoglobulin G specific binding with the corresponding ligand which was anchored on the nanofibers was conducted successfully to illustrate the potential applications of the nanofiber materials in biomedical field. Further study on the dispersion of the ethylene-acrylic acid nanofiber bundles was pursued to take advantage of the super high active surface area of functional nanofibers. To manipulate the polymer nanofibers during synthesis and bio-assays, a technique was developed to controllably assemble and disperse the

  10. Influence of Geometry on a High Surface Area-Solid Phase Microextraction Sampler for Chemical Vapor Collection

    DTIC Science & Technology

    2007-06-04

    Title of Thesis: Influence of Geometry on a High Surface Area-Solid Phase Microextraction Sampler for Chemical Vapor Collection Name of...TITLE AND SUBTITLE Influence of Geometry on a High Surface Area-Solid Phase Microextraction Sampler for Chemical Vapor Collection 5a. CONTRACT...SUPPLEMENTARY NOTES 14. ABSTRACT The High Surface Area Solid Phase Microextraction (HSA-SPME) device is an internally heated sampling device designed for

  11. The Chemistry, Crystallization, Physicochemical Properties and Behavior of Sodium Aluminosilicate Solid Phases: Final Report

    SciTech Connect

    Rosencrance, S.

    2003-03-12

    The synthesis of sodium aluminosilicate solids phases precipitated from NO{sub 2}/NO{sub 3}-free and NO{sub 2}/NO{sub 3}-rich liquors has been performed. Four sodium aluminosilicate precipitation products were formed. These are (1) X-ray/electron diffraction-indifferent amorphous phase; (2) crystalline zeolite A; (3)NO{sub 2}/NO{sub 3}-rich crystalline sodalite; and (4) NO{sub 2}/NO{sub 3}-rich crystalline cancrinite phase. Characterization of the physicochemical properties for these phases has been performed under conditions simulating Westinghouse Savannah River Company liquid waste processing.

  12. Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids

    NASA Technical Reports Server (NTRS)

    Larson, D. J., Jr.

    1975-01-01

    Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.

  13. Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry.

    PubMed

    Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek

    2013-12-20

    Solid phase microextraction find increasing applications in the sample preparation step before chromatographic determination of analytes in samples with a complex composition. These techniques allow for integrating several operations, such as sample collection, extraction, analyte enrichment above the detection limit of a given measuring instrument and the isolation of analytes from sample matrix. In this work the information about novel methodological and instrumental solutions in relation to different variants of solid phase extraction techniques, solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE) and magnetic solid phase extraction (MSPE) is presented, including practical applications of these techniques and a critical discussion about their advantages and disadvantages. The proposed solutions fulfill the requirements resulting from the concept of sustainable development, and specifically from the implementation of green chemistry principles in analytical laboratories. Therefore, particular attention was paid to the description of possible uses of novel, selective stationary phases in extraction techniques, inter alia, polymeric ionic liquids, carbon nanotubes, and silica- and carbon-based sorbents. The methodological solutions, together with properly matched sampling devices for collecting analytes from samples with varying matrix composition, enable us to reduce the number of errors during the sample preparation prior to chromatographic analysis as well as to limit the negative impact of this analytical step on the natural environment and the health of laboratory employees.

  14. Liquid versus solid phase bioassays for dredged material toxicity assessment.

    PubMed

    Casado-Martínez, M C; Fernández, N; Forja, J M; DelValls, T A

    2007-05-01

    Since 1994 the results of the analyses of key chemical compounds (trace metals, polychlorinated biphenyls and polycyclic aromatic hydrocarbons) and the comparison with the corresponding sediment quality guidelines (SQGs) are used in decision-making for dredged material management in Spain. Nonetheless in the last decades a tiered testing approach is promoted for assessing the physical and chemical characteristics of dredged sediments and their potential biological effects in the environment. Bioassays have been used for sediment toxicity assessment in Spain but few or no experiences are reported on harbour sediments. We studied the incidence of toxicity in the 7 d bioassay using rotifers (Brachionus plicatilis) and the 48 h bioassay using sea urchin (Paracentrotus lividus) embryos over a series of experiments employing 22 different elutriates. The relative performance of this exposure phase was not comparable to data on the 10-d acute toxicity test using the burrowing amphipod Corophium volutator and the polychaete Arenicola marina, carried out on the whole sediments. These results evidence the importance of the exposure route and the test selected in decision-making, as the toxicity registered for the undiluted elutriates was largely due to the different solubility of sediment-bound contaminants. This work and other studies indicate that for many sediments, a complete battery of test is recommended together with physico-chemical analyses to decide whether dredged sediments are suitable for open water disposal or not.

  15. High-pressure chemistry of molecular solids: evidences for novel extended phases of carbon dioxide

    SciTech Connect

    Yoo, C S

    1999-07-22

    At high pressures and temperatures, many molecular solids become unstable and transform into denser extended phases. Recently, we have discovered evidences for two novel extended phases of carbon dioxide at high pressures and temperatures: (1) an ionic form of dimeric CO,, C02+C03*- at 8-13 GPa and above 2000 K [I] and (2) a polymeric phase CO,-V above 35 GPa and 1800 K [2,3]. These extended phases can be quenched at room temperature at low pressures, from which their molecular and crystal structures have been determined. These transitions occur to soften highly repulsive intermolecular potentials via delocalization of electrons at high pressures and temperatures. Based on these and other previous results, we conjecture that three fundamental mechanisms of high-pressure chemistry are ionization, polymerization, and metallization, occurring in high-density molecular solids and fluids. [carbon dioxide, polymeric COZ, ionic CO, dimer, high-pressure chemistry, electron delocalization

  16. Pressure-induced phase transition in solid hydrogen sulfide at 11 GPa

    NASA Astrophysics Data System (ADS)

    Shimizu, H.; Nakamichi, Y.; Sasaki, S.

    1991-08-01

    The Raman spectra of hydrogen-bonded molecular solid H2S have been measured up to 23 GPa at 300 K in a gasketed diamond-anvil cell. In the orientationally disordered phase I between 0.47 and 11 GPa, the symmetric stretching mode ν1 shows a red-shift in frequency (dν1/dP=-10.1 cm-1/GPa ) and a dramatic broadening with pressure. At about 11 GPa, the antisymmetric stretching band ν3 appears at the higher-frequency side of ν1. Near this same pressure five low-frequency vibrational modes also appear and show pressure-sensitive features. These results indicate a pressure-induced phase transition near 11 GPa. This new solid phase, which persists to at least 23 GPa at 300 K, seems to be the same phase as previously found above 3.3 GPa at 25 K.

  17. Features of the phase dynamics in a ring solid-state laser

    SciTech Connect

    Kravtsov, Nikolai V; Lariontsev, E G

    2005-07-31

    The peculiarities of the phase dynamics are studied in a ring solid-state laser operating in transient quasi-sinusoidal oscillation regimes of the first and second kinds (QS-1 and QS-2) appearing upon periodic modulation of the pump power. It is shown that recording of a change in the phase difference of counterpropagating waves in the QS-2 regime under certain conditions makes it possible to determine directly the mutual nonreciprocity of the laser resonator. (control of laser radiation parameters)

  18. Enhancing a phase measurement by sequentially probing a solid-state system

    NASA Astrophysics Data System (ADS)

    Knott, P. A.; Munro, W. J.; Dunningham, J. A.

    2016-05-01

    In a recent paper, Liu et al. [Nat. Commun. 6:6726 (2015)] claim to perform the first room temperature entanglement-enhanced phase measurement in a solid-state system. We argue here that this claim is incorrect: their measurement is not enhanced because of the entanglement in their system, but instead the enhancement comes from the fact that the phase shift is applied twice to their state.

  19. Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.

    PubMed

    Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K

    2012-12-01

    The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model.

  20. Direct injection of solid-phase extraction eluents onto silica columns for the analysis of polar compounds isoniazid and cetirizine in plasma using hydrophilic interaction chromatography with tandem mass spectrometry.

    PubMed

    Li, Austin C; Junga, Heiko; Shou, Wilson Z; Bryant, Matthew S; Jiang, Xiang-yu; Naidong, Weng

    2004-01-01

    Isoniazid and cetirizine do not retain well on reversed-phase columns due to their high polarity. Silica columns, when operated under hydrophilic interaction conditions, do provide excellent retention of these compounds. We have developed simple and proof of concept analytical methods for the analysis of isoniazid and cetirizine in animal and human plasma, respectively. Both methods employed the approach of direct injection of solid-phase extraction (SPE) organic eluents onto silica columns for analysis, thus eliminating evaporation and reconstitution steps that are typically needed for reversed-phase liquid chromatographic analysis. Isoniazid was extracted from animal plasma samples using a Waters Oasis HLB 96-well plate and then eluted with acetonitrile, while cetirizine was extracted from human plasma with a Waters MCX mu-Elute plate and then eluted with acetonitrile containing 5% concentrated ammonium hydroxide. The direct injection of the SPE eluent onto the analytical column was necessary since significant loss of isoniazid was found during the evaporation and reconstitution steps. The method for isoniazid also enabled ultra-fast analysis due to the relatively low back-pressure exhibited by silica columns even under high flow conditions. Both methods show good linearity, accuracy and precision covering the range of 10-2000 ng/mL of isoniazid, and 1-1000 ng/mL of cetirizine in plasma. Substantial time savings were realized as a result of both the elimination of the evaporation and reconstitution steps and the fast chromatographic analysis.

  1. Phase behavior, intermolecular interaction, and solid state characterization of amorphous solid dispersion of Febuxostat.

    PubMed

    Kini, Ashwini; Patel, Sarsvatkumar B

    2017-02-01

    The aim of this work was to prepare and characterize the amorphous molecular dispersion of Febuxostat (FXT) using PVP K30, HPMC-AS, Soluplus®, and PVP VA64. The solid dispersions were prepared by solvent evaporation technique. Their physical properties were studied by differential scanning calorimetry, powder X-ray diffraction, Fourier transformation infrared spectroscopy, and compared to that of same physical mixtures. The success of physicochemical stability of the dispersions is often revealed as glass transition temperature (Tg) versus composition (w) dependencies. The shape of the Tg versus composition was mathematically modeled using the Gordon-Taylor equation, Couchman-Karasz equation, Brekner-Schneider-Cantow equation, and a three-parameter BCKV equation. In this work, different types of Tg patterns obtained for FXT-polymer binary mixtures are analyzed in terms of the above equations and relations between their prime fitting parameters are presented. The theoretical values and modeled parameters were compared using various results obtained by thermal analysis. The influence of important physicochemical phenomena and properties of the mixtures on the shape of the Tg versus composition patterns are also illustrated. The interaction between drug and polymers and the model parameters were analyzed, aiming to assess the state of mixing and intermolecular interactions.

  2. Direct molecular dynamics simulation of liquid-solid phase equilibria for two-component plasmas.

    PubMed

    Schneider, A S; Hughto, J; Horowitz, C J; Berry, D K

    2012-06-01

    We determine the liquid-solid phase diagram for carbon-oxygen and oxygen-selenium plasma mixtures using two-phase molecular dynamics simulations. We identify liquid, solid, and interface regions using a bond angle metric. To study finite-size effects, we perform 27,648- and 55,296-ion simulations. To help monitor nonequilibrium effects, we calculate diffusion constants D(i). For the carbon-oxygen system we find that D(O) for oxygen ions in the solid is much smaller than D(C) for carbon ions and that both diffusion constants are 80 or more times smaller than diffusion constants in the liquid phase. There is excellent agreement between our carbon-oxygen phase diagram and that predicted by Medin and Cumming. This suggests that errors from finite-size and nonequilibrium effects are small and that the carbon-oxygen phase diagram is now accurately known. The oxygen-selenium system is a simple two-component model for more complex rapid proton capture nucleosynthesis ash compositions for an accreting neutron star. Diffusion of oxygen, in a predominantly selenium crystal, is remarkably fast, comparable to diffusion in the liquid phase. We find a somewhat lower melting temperature for the oxygen-selenium system than that predicted by Medin and Cumming. This is probably because of electron screening effects.

  3. Phase equilibria and solid state transformations in niobium-rich niobium-titanium-aluminum intermetallic alloys

    NASA Astrophysics Data System (ADS)

    Leonard, Keith John

    The phase equilibria and solid state transformations within seven Nb-rich Nb-Ti-Al alloys were investigated. The alloys ranged in composition between 15 and 40 at.% Al with Nb:Ti ratios of 1.5:1 to 4:1. Examination of the as-cast microstructures revealed that all alloys solidified from the beta phase field, with subsequent solid-state transformations occurring within four of the alloys during cooling. The range of primary beta phase solidification was determined to extend beyond the limits of previous liquidus projections. The high temperature beta phase field was verified in each alloy through quenching experiments. The beta phase exhibited B2 ordering at room temperature with the order-disorder transition temperatures increasing with Ti concentration. The site occupancy preferences within the beta phase were evaluated through the ALCHEMI technique, which determined that Ti substitution occurred for Nb on Nb sublattice sites with the degree of sublattice partitioning found to depend upon alloy composition. The phase equilibria and transformations that occurred within the alloys were explored over a complete range of temperatures, with experimental isotherms produced at 1400, 1100, 900 and 700°C. Formation of metastable O-Ti 2AlNb plates occurred within the 15 at.% Al alloys at 700°C, instead of the delta-Nb3Al phase due to the slow diffusion growth kinetics of the delta phase below 900°C. A new phase with a body centered tetragonal structure belonging to the I41/amd space group was discovered in the Nb-24Ti-40Al alloy below 1100°C. This phase formed as lamella with the gamma-TiAl phase from the beta solid solution at 900 and 700°C, and was also present following treatments at 1100 + 900, 1100 + 700°C and within material oil quenched from elevated temperatures. No correlation existed between this phase and either the r-TiAl2 phase, which also has the I41/amd structure, or the gamma1 phase, which was not observed within this work. The formation of a metastable

  4. Solid-liquid phase epitaxial growth of Li4Ti5O12 thin film

    NASA Astrophysics Data System (ADS)

    Li, Ning; Katase, Takayoshi; Zhu, Yanbei; Matsumoto, Takao; Umemura, Tomonari; Ikuhara, Yuichi; Ohta, Hiromichi

    2016-12-01

    A thin film of Li4Ti5O12, a candidate anode material for solid-state Li-ion batteries, was heteroepitaxially grown on a (001) SrTiO3 substrate using solid-liquid phase epitaxy. An amorphous Li4Ti5O12 film deposited at room temperature was first heated with LiNO3 powder in air and then washed with distilled water. The Li4Ti5O12 epitaxial film was obtained by heating with molten LiNO3 at 600 °C the liquid LiNO3 completely covered the film, suppressing the formation of Li deficiencies and enhancing the low-temperature crystal growth. Solid-liquid phase epitaxy is a powerful approach to grow Li-containing-oxide films, which are difficult to fabricate because of the loss of Li species at high temperature.

  5. Advances in automatic, manual and microwave-assisted solid-phase peptide synthesis.

    PubMed

    Sabatino, Giuseppina; Papini, Anna M

    2008-11-01

    Solid-phase strategies speed up the production of both short- and long-sequence peptides compared with solution methodologies. Therefore, solid-phase peptide synthesis (SPPS), proposed by Merrifield in the early 1960s, contributed to the 'Peptide Revolution' in the fields of diagnostics, and drug and vaccine development. Since then, peptide chemistry research has aimed to optimize these synthetic procedures, focusing on areas such as amide bond formation (the coupling step), solid supports and automation. Particular attention was devoted to the environmental impact of SPPS: the requirement for large amounts of organic solvents meant high costs for industrial peptide manufacturing that needed to be reduced. SPPS, alone or in hybrid technologies, has become strategic for the production of peptides as active pharmaceutical ingredients on a commercial scale.

  6. The synthesis and chemical durability of Nd-doped single-phase zirconolite solid solutions

    NASA Astrophysics Data System (ADS)

    Cai, Xin; Teng, Yuancheng; Wu, Lang; Zhang, Kuibao; Huang, Yi

    2016-10-01

    Nd-doped single-phase zirconolite solid solutions was synthesized by solid-state reaction and following two steps of acid treatment. The phase composition, microstructure, and chemical durability of the zirconolite solid solutions were investigated. About 15 at% Nd was successfully stabilized into the zirconolite. The element mapping images of Ca, Zr, Nd and Ti show that all the elements are almost distributed homogeneously in the zirconolite waste forms. Product Consistency Test (PCT) was conducted under different pH values (pH = 5, 7 and 9) to evaluate the chemical durability of the Nd-doped zirconolite waste forms. The normalized element release rate of Ca (LRCa) in pH = 5 medium is higher than that of pH = 7 and 9, while the LRNd value remains almost unchanged under different pH values. The LRNd value is as low as 10-5 g m-2 d-1 after 42 days.

  7. Soxhlet-assisted matrix solid phase dispersion to extract flavonoids from rape (Brassica campestris) bee pollen.

    PubMed

    Ma, Shuangqin; Tu, Xijuan; Dong, Jiangtao; Long, Peng; Yang, Wenchao; Miao, Xiaoqing; Chen, Wenbin; Wu, Zhenhong

    2015-11-15

    Soxhlet-assisted matrix solid phase dispersion (SA-MSPD) method was developed to extract flavonoids from rape (Brassica campestris) bee pollen. Extraction parameters including the extraction solvent, the extraction time, and the solid support conditions were investigated and optimized. The best extraction yields were obtained using ethanol as the extraction solvent, silica gel as the solid support with 1:2 samples to solid support ratio, and the extraction time of one hour. Comparing with the conventional solvent extraction and Soxhlet method, our results show that SA-MSPD method is a more effective technique with clean-up ability. In the test of six different samples of rape bee pollen, the extracted content of flavonoids was close to 10mg/g. The present work provided a simple and effective method for extracting flavonoids from rape bee pollen, and it could be applied in the studies of other kinds of bee pollen.

  8. THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

    EPA Science Inventory

    Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

  9. Use of Solid Phase Extraction in the Biochemistry Laboratory to Separate Different Lipids

    ERIC Educational Resources Information Center

    Flurkey, William H.

    2005-01-01

    Solid-phase extraction (SPE) was used to demonstrate how various lipids and lipid classes could be separated in a biochemistry laboratory setting. Three different SPE methods were chosen on their ability to separate a lipid mixture, consisting of a combination of a either a fatty acid, a triacylglycerol, a mono- or diacylglycerol, phospholipid,…

  10. Effects of inoculum size on solid-phase fermentation of fodder beets for fuel ethanol production

    SciTech Connect

    Gibbons, W.R.; Westby, C.A.

    1986-10-01

    This fuel ethanol study examined the effects of Saccharomyces cerevisiae inoculum size on solid-phase fermentation of fodder beet pulp. A 5% inoculum (wt/wt) resulted in rapid yeast and ethanol (9.1% (vol/vol)) production. Higher inocula showed no advantages. Lower inocula resulted in lowered final yeast populations and increased fermentation times.

  11. Determination of Plant Volatiles Using Solid Phase Microextraction GC-MS

    ERIC Educational Resources Information Center

    Van Bramer, Scott; Goodrich, Katherine R.

    2015-01-01

    This experiment combines analytical techniques of solid phase microextraction and gas chromatography-mass spectrometry with easily relatable and accessible plant volatile chemistry (floral and vegetative scents of local/available plants). The biosynthesis and structure of these chemicals are of interest in the areas of organic chemistry,…

  12. Solid phase microextraction for active or passive sampling of methyl bromide during fumigations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The high diffusivity and volatility of methyl bromide make it an ideal compound for Solid Phase Micro Extraction (SPME)-based sampling of air prior to gas-chromatographic quantifications. SPME fibers can be used as active methyl bromide samplers, with high capacities and an equilibrium time of 1-2 m...

  13. Headspace analysis of polar organic compounds in biological matrixes using solid phase microextraction (SPME)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analysis of biological fluids and waste material is difficult and tedious given the sample matrix. A rapid automated method for the determination of volatile fatty acids and phenolic and indole compounds was developed using a multipurpose sampler (MPS) with solid phase microextraction (SPME) and GC-...

  14. SOLID PHASE MICROEXTRACTION FOR TRACE LEVEL ANALYSIS OF DISINFECTION BY-PRODUCTS

    EPA Science Inventory

    This presentation focuses on the development of a solid-phase microextraction (SPME)-gas chromatography (GC)/ion trap mass spectrometry (MS) method for the analysis of semivolatile disinfection by-products (DBPs) in drinking water in the low ug/L range. These DBPs were selected ...

  15. Solid-phase microextraction of hydrocarbons from water in a centrifuge

    NASA Astrophysics Data System (ADS)

    Ryabov, A. Yu.; Chuikin, A. V.; Velikov, A. A.

    2016-06-01

    The results of our study of solid-phase microextraction of substances using a centrifuge for determining the microquantities of hydrocarbon impurities in water are presented. The cartridge diameter, sorbent mass, and solvent volume were shown to affect the percent extraction of substances and the analytical signal intensity. The relationship between the cartridge geometry, the sorbent mass, and the solvent volume was considered.

  16. High performance solid-phase analytical derivatization of phenols for gas chromatography-mass spectrometry.

    PubMed

    Kojima, Miki; Tsunoi, Shinji; Tanaka, Minoru

    2004-07-09

    The solid-phase analytical derivatization of phenols with pentafluoropyridine is performed. Fourteen phenols including chlorophenols and alkylphenols, could be efficiently adsorbed on a strong anion-exchange solid phase, Oasis MAX. The phenols adsorbed on Oasis MAX as phenolate ions were desorbed after derivatization with pentafluoropyridine. After optimization of the adsorption and derivatization, we established a procedure for the determination of the phenols in water samples by means of GC-MS. Under the optimized conditions, calibration curves were linear in the range of 10-1000 ng/l for the alkylphenols (100-10000 ng/l for nonylphenol) and 50-1000 ng/l for the others. By processing 100 ml samples, the method detection limits (MDLs) were in the range of 0.45-2.3 ng/l for the alkylphenols (8.5 ng/l for nonylphenol) and 2.4-16 ng/l for the others. Compared with the biphasic reaction system, the signal-to-noise ratios obtained by the solid-phase analytical derivatization were significantly higher. This is ascribed to the fact that coexisting neutral and acidic compounds are efficiently removed from the sample solution by this solid-phase analytical derivatization system.

  17. A Discovery-Oriented Approach to Solid-Phase Peptide Synthesis

    ERIC Educational Resources Information Center

    Bockman, Matthew R.; Miedema, Christopher J.; Brennan, Brian B.

    2012-01-01

    In this discovery-oriented laboratory experiment, students use solid-phase synthesis techniques to construct a dipeptide containing an unknown amino acid. Following synthesis and cleavage from the polymeric support, electrospray ionization-mass spectrometry is employed to identify the unknown amino acid that was used in the peptide coupling. This…

  18. Development of a Solid Phase Extraction Method for Agricultural Pesticides in Large-Volume Water Samples

    EPA Science Inventory

    An analytical method using solid phase extraction (SPE) and analysis by gas chromatography/mass spectrometry (GC/MS) was developed for the trace determination of a variety of agricultural pesticides and selected transformation products in large-volume high-elevation lake water sa...

  19. Solid-gaseous phase transformation of elemental contaminants during the gasification of biomass.

    PubMed

    Jiang, Ying; Ameh, Abiba; Lei, Mei; Duan, Lunbo; Longhurst, Philip

    2016-09-01

    Disposal of plant biomass removed from heavy metal contaminated land via gasification achieves significant volume reduction and can recover energy. However, these biomass often contain high concentrations of heavy metals leading to hot-corrosion of gasification facilities and toxic gaseous emissions. Therefore, it is of significant interest to gain a further understanding of the solid-gas phase transition of metal(loid)s during gasification. Detailed elemental analyses (C, H, O, N and key metal/metalloid elements) were performed on five plant species collected from a contaminated site. Using multi-phase equilibria modelling software (MTDATA), the analytical data allows modelling of the solid/gas transformation of metal(loid)s during gasification. Thermodynamic modelling based on chemical equilibrium calculations was carried out in this study to predict the fate of metal(loid) elements during typical gasification conditions and to show how these are influenced by metal(loid) composition in the biomass and operational conditions. As, Cd, Zn and Pb tend to transform to their gaseous forms at relatively low temperatures (<1000°C). Ni, Cu, Mn and Co converts to gaseous forms within the typical gasification temperature range of 1000-1200°C. Whereas Cr, Al, Fe and Mg remain in solid phase at higher temperatures (>1200°C). Simulation of pressurised gasification conditions shows that higher pressures increase the temperature at which solid-to-gaseous phase transformations takes place.

  20. Investigating the Retention Mechanisms of Liquid Chromatography Using Solid-Phase Extraction Cartridges

    ERIC Educational Resources Information Center

    O'Donnell, Mary E.; Musial, Beata A.; Bretz, Stacey Lowery; Danielson, Neil D.; Ca, Diep

    2009-01-01

    Liquid chromatography (LC) experiments for the undergraduate analytical laboratory course often illustrate the application of reversed-phase LC to solve a separation problem, but rarely compare LC retention mechanisms. In addition, a high-performance liquid chromatography instrument may be beyond what some small colleges can purchase. Solid-phase…

  1. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  2. AUTOMATED SOLID PHASE EXTRACTION GC/MS FOR ANALYSIS OF SEMIVOLATILES IN WATER AND SEDIMENTS

    EPA Science Inventory

    Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line sampl...

  3. Electronic structure of elements and compounds and electronic phases of solids

    NASA Astrophysics Data System (ADS)

    Nadykto, B. A.

    2000-07-01

    The paper reviews technique [1] and computed energies for various electronic states of many-electron multiply charged ions, molecular ions, and electronic phases of solids. The model used allows computation of the state energy for free many-electron multiply charged ions with relative accuracy ˜10-4 suitable for analysis of spectroscopy data.

  4. COMPARISON OF TWO DIFFERENT SOLID PHASE EXTRACTION/LARGE VOLUME INJECTION PROCEDURES FOR METHOD 8270

    EPA Science Inventory

    Two solid phase (SPE) and one traditional continuous liquid-liquid extraction method are compared for analysis of Method 8270 SVOCs. Productivity parameters include data quality, sample volume, analysis time and solvent waste.

    One SPE system, unique in the U.S., uses aut...

  5. Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

    SciTech Connect

    Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.; Wang, Zheming

    2007-06-27

    The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reduction of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.

  6. Aqueous- and solid-phase biogeochemistry of a calcareous aquifer system downgradient from a municipal solid waste landfill (Winterthur, Switzerland)

    SciTech Connect

    Amirbahman, A.; Schoenenberger, R.; Johnson, C.A.; Sigg, L. |

    1998-07-01

    This study addresses the biogeochemical changes that take place in a calcareous aquifer system under and down-gradient from a municipal solid waste landfill. Aqueous-phase chemical analysis of the redox-sensitive species indicates the presence of aerobic respiration, denitrification/NO{sub 3}{sup {minus}} reduction, and Fe(III), Mn(III/IV), and SO{sub 4} reduction processes under the landfill. Because available and released organic matter is limited, reduction processes downgradient from the landfill do not go far beyond aerobic respiration, denitrification, and Mn(III/IV) reduction. Assuming steady-state conditions, STEADYQL computer program has been used to model the biogeochemical processes by taking into account the kinetics of the redox reactions, calcite precipitation and dilution. Dilution has the most significant influence on the concentrations of the dissolved organic and inorganic carbon. Dissolved Mn(II) concentrations in the entire anaerobic zone are controlled by the solubility of rhodocrocite [MnCO{sub 3}(S)]. At selected locations under the landfill where SO{sub 4} reduction takes place, dissolved Fe(II) concentrations are regulated by the solubility of amorphous FeS. Chemical extraction of the aquifer solid phase indicates that the oxidation capacity of this aquifer system is largely controlled by iron(III)(hydr)-oxides.

  7. Reorientational dynamics and solid-phase transformation of ammonium dicyanamide into dicyandiamide: a (2)H solid-state NMR study.

    PubMed

    Lotsch, Bettina V; Schnick, Wolfgang; Naumann, Ernst; Senker, Jürgen

    2007-10-11

    The reorientational dynamics of ammonium dicyanamide ND4[N(C[triple bond]N)2] and the kinetics as well as the mechanism of the solid-state isomerization reaction from ammonium dicyanamide into dicyandiamide (N[triple bond]C-N==C(NH2)2) was studied by means of 2H and 14N solid-state NMR spectroscopy in a temperature range between 38 and 390 K. Whereas in previous investigations the mechanism of the solid-state transformation was investigated by means of vibrational and magic angle spinning solid-state NMR spectroscopy as well as neutron diffraction, we here present a comprehensive 2H study of the ammonium ion dynamics prior to and during the course of the reaction, thereby highlighting possible cross correlations between dynamics and reactivity involving the ammonium ion. The ND4+ group was found to undergo thermally activated random jumps in a tetrahedral potential, which is increasingly distorted with increasing temperature, giving rise to an asymmetrically compressed or elongated tetrahedron with deviations from the tetrahedral angle of up to 6 degrees . The correlation time follows an Arrhenius law with an activation energy of Ea = 25.8(2) kJ mol(-1) and an attempt frequency of tau0(-1) = 440(80) THz. The spin-lattice relaxation times were fitted according to a simple Bloembergen-Purcell-Pound type model with a T1 minimum of 4 ms at 230 K. Temperature-dependent librational amplitudes were extracted by line-shape simulations between 38 and 390 K and contrasted with those obtained by neutron diffraction, their values ranging between 5 and 28 degrees . The onset and progress of the solid-phase transformation were followed in situ at temperatures above 372 K and could be classified as a strongly temperature-dependent, heterogeneous two-step reaction proceeding with rapid evolution of ammonia and comparatively slow subsequent reintegration into the solid. On the microscopic level, this correlates with a rapid proton transfer -- possibly triggered by a coupling

  8. First-principles investigation of iron pentacarbonyl molecular solid phases at high pressure

    NASA Astrophysics Data System (ADS)

    Cong, Kien Nguyen; Steele, Brad A.; Landerville, Aaron C.; Oleynik, Ivan I.

    2017-01-01

    The polymeric phases of carbon monoxide (p-CO), an extended non-molecular solid, represent a new class of low-Z energetic materials. The presence of transition metal ions is believed to stabilize polymeric carbon monoxide (p-CO) at ambient conditions. Since p-CO forms at high pressures, it becomes important to investigate the high-pressure behavior of one of the potential precursors, iron pentacarbonyl Fe(CO)5. In this work, a first-principles evolutionary structure search method is used to determine the crystal phases of Fe(CO)5 at high pressure. The calculations predict the crystal structure of Phase I in agreement with experiment. Moreover, the previously unidentified crystal structure of Phase II is found. The calculated pressure-dependent Raman spectra are used to demonstrate that the changes in Raman spectra as a function of pressure observed in recent experiment can be explained without invoking a phase transition to a new phase III.

  9. Profilometry of three-dimensional discontinuous solids by combining two-steps temporal phase unwrapping, co-phased profilometry and phase-shifting interferometry

    NASA Astrophysics Data System (ADS)

    Servin, Manuel; Padilla, Moises; Garnica, Guillermo; Gonzalez, Adonai

    2016-12-01

    In this work we review and combine two techniques that have been recently published for three-dimensional (3D) fringe projection profilometry and phase unwrapping, namely: co-phased profilometry and 2-steps temporal phase-unwrapping. By combining these two methods we get a more accurate, higher signal-to-noise 3D profilometer for discontinuous industrial objects. In single-camera single-projector (standard) profilometry, the camera and the projector must form an angle between them. The phase-sensitivity of the profilometer depends on this angle, so it cannot be avoided. This angle produces regions with self-occluding shadows and glare from the solid as viewed from the camera's perspective, making impossible the demodulation of the fringe-pattern there. In other words, the phase data is undefined at those shadow regions. As published recently, this limitation can be solved by using several co-phased fringe-projectors and a single camera. These co-phased projectors are positioned at different directions towards the object, and as a consequence most shadows are compensated. In addition to this, most industrial objects are highly discontinuous, which precludes the use of spatial phase-unwrappers. One way to avoid spatial unwrapping is to decrease the phase-sensitivity to a point where the demodulated phase is bounded to one lambda, so the need for phase-unwrapping disappears. By doing this, however, the recovered non-wrapped phase contains too much harmonic distortion and noise. Using our recently proposed two-step temporal phase-unwrapping technique, the high-sensitivity phase is unwrapped using the low-frequency one as initial gross estimation. This two-step unwrapping technique solves the 3D object discontinuities while keeping the accuracy of the high-frequency profilometry data. In scientific research, new art are derived as logical and consistent result of previous efforts in the same direction. Here we present a new 3D-profilometer combining these two recently

  10. New methodological improvements in the Microtox® solid phase assay.

    PubMed

    Burga Pérez, Karen F; Charlatchka, Rayna; Sahli, Leila; Férard, Jean-François

    2012-01-01

    The classic Microtox® solid phase assay (MSPA) based on the inhibition of light production of the marine bacteria recently renamed Aliivibrio fischeri suffers from various bias and interferences, mainly due to physico-chemical characteristics of the tested solid phase. To precisely assess ecotoxicity of sediments, we have developed an alternative method, named Microtox® leachate phase assay (MLPA), in order to measure the action of dissolved pollutants in the aqueous phase. Two hypotheses were formulated to explain the observed difference between MSPA and MLPA results: a real ecotoxicity of the solid phase or the fixation of bacteria to fine particles and/or organic matter. To estimate the latter, flow cytometry analyses were performed with two fluorochromes (known for their ability to stain bacterial DNA), allowing correction of MSPA measurements and generation of new (corrected) IC50. Comparison of results of MLPA with the new IC50 MSPA allows differentiating real ecotoxic and fixation effect in classic MSPA especially for samples with high amount of fines and/or organic matter.

  11. Phase separation kinetics in amorphous solid dispersions upon exposure to water.

    PubMed

    Purohit, Hitesh S; Taylor, Lynne S

    2015-05-04

    The purpose of this study was to develop a novel fluorescence technique employing environment-sensitive fluorescent probes to study phase separation kinetics in hydrated matrices of amorphous solid dispersions (ASDs) following storage at high humidity and during dissolution. The initial miscibility of the ASDs was confirmed using infrared (IR) spectroscopy and differential scanning calorimetry (DSC). Fluorescence spectroscopy, as an independent primary technique, was used together with conventional confirmatory techniques including DSC, X-ray diffraction (XRD), fluorescence microscopy, and IR spectroscopy to study phase separation phenomena. By monitoring the emission characteristics of the environment-sensitive fluorescent probes, it was possible to successfully monitor amorphous-amorphous phase separation (AAPS) as a function of time in probucol-poly(vinylpyrrolidone) (PVP) and ritonavir-PVP ASDs after exposure to water. In contrast, a ritonavir-hydroxypropylmethylcellulose acetate succinate (HPMCAS) ASD, did not show AAPS and was used as a control to demonstrate the capability of the newly developed fluorescence method to differentiate systems that showed no phase separation following exposure to water versus those that did. The results from the fluorescence studies were in good agreement with results obtained using various other complementary techniques. Thus, fluorescence spectroscopy can be utilized as a fast and efficient tool to detect and monitor the kinetics of phase transformations in amorphous solid dispersions during hydration and will help provide mechanistic insight into the stability and dissolution behavior of amorphous solid dispersions.

  12. Accelerated exploration of multi-principal element alloys with solid solution phases.

    PubMed

    Senkov, O N; Miller, J D; Miracle, D B; Woodward, C

    2015-03-05

    Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge--how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs--that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction.

  13. Accelerated exploration of multi-principal element alloys with solid solution phases

    NASA Astrophysics Data System (ADS)

    Senkov, O. N.; Miller, J. D.; Miracle, D. B.; Woodward, C.

    2015-03-01

    Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge—how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs—that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction.

  14. Evidence for Two Different Solid Phases of Two-Dimensional Electrons in High Magnetic Fields

    NASA Astrophysics Data System (ADS)

    Chen, Yong P.; Lewis, R. M.; Engel, L. W.; Tsui, D. C.; Ye, P. D.; Wang, Z. H.; Pfeiffer, L. N.; West, K. W.

    2004-11-01

    We have observed two different rf resonances in the frequency dependent real diagonal conductivity of very high quality two-dimensional electron systems in the high magnetic field insulating phase and interpret them as coming from two different pinned electron solid phases (labeled as “A” and “B”). The “A” resonance is observable for Landau level filling ν<2/9 [reentrant around the ν=1/5 fractional quantum Hall effect (FQHE)] and then crosses over to the different “B” resonance which dominates at sufficiently low ν. Moreover, the “A” resonance is found to show dispersion with respect to the size of the transmission line, indicating that the “A” phase has a large correlation length. We suggest that quantum correlations such as those responsible for FQHE may play an important role in giving rise to such different solids.

  15. Three-body interactions and solid-liquid phase equilibria: application of a molecular dynamics algorithm.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-09-01

    The effect of three-body interactions on the solid-liquid phase boundaries of argon, krypton, and xenon is investigated via a novel technique that combines both nonequilibrium and equilibrium molecular dynamics. The simulations involve the evaluation of two- and three-body forces using accurate two-body and three-body intermolecular potentials. The effect of three-body interactions is to substantially increase the coexistence pressure and to lower the densities of liquid and solid phases. Comparison with experiment indicates that three-body interactions are required to accurately determine the total pressure. In contrast to vapor-liquid phase equilibria, the relative contribution of three-body interactions to the freezing pressure exceeds the contribution of two-body interactions at all temperatures.

  16. Multiresidue analysis of neonicotinoids by solid-phase extraction technique using high-performance liquid chromatography.

    PubMed

    Mohan, Chander; Kumar, Yogesh; Madan, Jyotsana; Saxena, Navneet

    2010-06-01

    For routine monitoring of pesticides, a multiresidue analysis through solid-phase extraction technique and using high-performance liquid chromatography (HPLC) in cotton seed cake (CSC) has been developed. Extraction of fortified samples was carried out with aqueous acetone under vacuum. The concentrated extract was loaded onto the solid-phase extraction units, preconditioned with acetonitrile. The extraction units were then washed with hexane and finally eluted with acetonitrile. The pesticide residues were determined using a multiresidue method by reversed-phase HPLC. The average percentage recoveries were found to range between 65.47% and 110% at spiking levels of 10 to 40 mg/kg. The method developed shows a healthy rate of recovery and can successfully be utilized for the extraction and screening of neonicotinoid residues in CSC. The detection limits for imidacloprid, acetamiprid, and thiacloprid using this method were found to be 5, 10, and 20 mg/kg, respectively.

  17. A phase-field approach to nonequilibrium phase transformations in elastic solids via an intermediate phase (melt) allowing for interface stresses.

    PubMed

    Momeni, Kasra; Levitas, Valery I

    2016-04-28

    A phase-field approach for phase transformations (PTs) between three different phases at nonequilibrium temperatures is developed. It includes advanced mechanics, thermodynamically consistent interfacial stresses, and interface interactions. A thermodynamic Landau-Ginzburg potential developed in terms of polar order parameters satisfies the desired instability and equilibrium conditions for homogeneous phases. The interfacial stresses were introduced with some terms from large-strain formulation even though the small-strain assumption was utilized. The developed model is applied to study the PTs between two solid phases via a highly disordered intermediate phase (IP) or an intermediate melt (IM) hundreds of degrees below the melting temperature. In particular, the β ↔ δ PTs in HMX energetic crystals via IM are analyzed. The effects of various parameters (temperature, ratios of widths and energies of solid-solid (SS) to solid-melt (SM) interfaces, elastic energy, and interfacial stresses) on the formation, stability, and structure of the IM within a propagating SS interface are studied. Interfacial and elastic stresses within a SS interphase and their relaxation and redistribution with the appearance of a partial or complete IM are analyzed. The energy and structure of the critical nucleus (CN) of the IM are studied as well. In particular, the interfacial stresses increase the aspect-ratio of the CN. Although including elastic energy can drastically reduce the energy of the CN of the IM, the activation energy of the CN of the IM within the SS interface increases when interfacial tension is taken into account. The developed thermodynamic potential can also be modified to model other multiphase physical phenomena, such as multi-variant martensitic PTs, grain boundary and surface-induced pre-melting and PTs, as well as developing phase diagrams for IPs.

  18. Quantitative analysis of simvastatin and its beta-hydroxy acid in human plasma using automated liquid-liquid extraction based on 96-well plate format and liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Nanyan; Yang, Amy; Rogers, John Douglas; Zhao, Jamie J

    2004-01-27

    An assay based on automated liquid-liquid extraction (LLE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) has been developed and validated for the quantitative analysis of simvastatin (SV) and its beta-hydroxy acid (SVA) in human plasma. A Packard MultiProbe II workstation was used to convert human plasma samples collected following administration of simvastatin and quality control (QC) samples from individual tubes into 96-well plate format. The workstation was also used to prepare calibration standards and spike internal standards. A Tomtec Quadra 96-channel liquid handling workstation was used to perform LLE based on 96-well plates including adding solvents, separating organic from aqueous layer and reconstitution. SV and SVA were separated through a Kromasil C18 column (50 mm x 2 mm i.d., 5 microm) and detected by tandem mass spectrometry with a TurboIonspray interface. Stable isotope-labeled SV and SVA, 13CD(3)-SV and 13 CD(3)-SVA, were used as the internal standards for SV and SVA, respectively. The automated procedures reduced the overall analytical time (96 samples) to 1/3 of that of manual LLE. Most importantly, an analyst spent only a fraction of time on the 96-well LLE. A limit of quantitation of 50 pg/ml was achieved for both SV and SVA. The interconversion between SV and SVA during the 96-well LLE was found to be negligible. The assay showed very good reproducibility, with intra- and inter-assay precision (%R.S.D.) of less than 7.5%, and accuracy of 98.7-102.3% of nominal values for both analytes. By using this method, sample throughput should be enhanced at least three-fold compared to that of the manual procedure.

  19. Electron Irradiation Induced Phase Transition of an Amorphous Phase and Face-Centered Cubic Solid Solutions in Zr66.7Pd33.3 Metallic Glass

    NASA Astrophysics Data System (ADS)

    Nagase, Takeshi; Hosokawa, Takashi; Umakoshi, Yukichi

    2007-02-01

    Both amorphization and crystallization were observed in Zr66.7Pd33.3 metallic glass under electron irradiation. The melt-spun amorphous phase was not stable under 2.0 MV electron irradiation and two kinds of fcc-solid solution were precipitated through electron irradiation induced crystallization at 103 and 298 K. The fcc-solid solution obtained by electron irradiation induced crystallization at 298 K transformed to an amorphous phase during irradiation at 103 K. Electron irradiation induced phase transformation behavior in Zr66.7Pd33.3 metallic glass can be explained by phase stability of an amorphous phase and crystalline phases against electron irradiation.

  20. Subscale solid motor nozzle tests, phase 4 and nozzle materials screening and thermal characterization, phase 5

    NASA Technical Reports Server (NTRS)

    Arnold, J.; Dodson, J.; Laub, B.

    1979-01-01

    Subscale solid motor nozzles containing a baseline material or low cost materials to be considered as potential replacements for the baseline material are designed and tested. Data are presented from tests of four identically designed 2.5 inch throat diameter nozzles and one 7 inch throat diameter nozzle. The screening of new candidate low cost materials, as well as their thermophysical and thermochemical characterization is also discussed.

  1. Solid/Liquid phase diagram of the ammonium sulfate/maleic acid/water system.

    PubMed

    Beyer, Keith D; Schroeder, Jason R; Pearson, Christian S

    2011-12-01

    We have studied the low temperature phase diagram and water activities of the ammonium sulfate/maleic acid/water system using differential scanning calorimetry and infrared spectroscopy of thin films. Using the results from our experiments, we have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/maleic acid phase boundary as well as the ternary eutectic composition and temperature. We also compare our results to the predictions of the extended AIM aerosol thermodynamics model and find good agreement for the ice melting points in the ice primary phase field of this system; however significant differences were found with respect to phase boundaries, maleic acid dissolution, and ammonium sulfate dissolution.

  2. Two-phase region of vortex-solid melting: 3D XY theory

    NASA Astrophysics Data System (ADS)

    Friesen, M.; Muzikar, P.

    1998-07-01

    In clean enough samples of the high-Tc oxide materials, the phase transition into the superconducting state occurs along a first-order line in the H-T plane. This means that a two-phase region occurs in the B-T plane, in which the liquid and solid vortex phases coexist. We discuss the thermodynamics of this two-phase region, developing formulae relating experimental quantities of interest. We then apply the 3D XY scaling theory to the problem, obtaining detailed predictions for the boundaries of the coexistence region. By using published data, we are able to predict the width of the two-phase region, and determine the physical parameters involved in the 3D XY description.

  3. Determination of triazine herbicides in seaweeds: development of a sample preparation method based on Matrix Solid Phase Dispersion and Solid Phase Extraction Clean-up.

    PubMed

    Rodríguez-González, N; González-Castro, M J; Beceiro-González, E; Muniategui-Lorenzo, S; Prada-Rodríguez, D

    2014-04-01

    A method using dual process columns of Matrix Solid Phase Dispersion (MSPD) and Solid Phase Extraction (SPE) has been developed for extracting and cleaning-up of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) in seaweed samples. Under optimized conditions, samples were blended with 2g of octasilyl-derivatized silica (C8) and transferred into an SPE cartridge containing ENVI-Carb II/PSA (0.5/0.5 g) as a clean up co-sorbent. Then the dispersed sample was washed with 10 mL of n-hexane and triazines were eluted with 20 mL ethyl acetate and 5 mL acetonitrile. Finally the extract was concentrated to dryness, re-constituted with 1 mL methanol:water (1:1) and injected into the HPLC-DAD system. The linearity of the calibration curves was excellent in matrix matched standards, and yielded the coefficients of determination>0.995 for all the target analytes. The recoveries ranged from 75% to 100% with relative standard deviations lower than 7%. The achieved LOQs (<10 µg kg(-1)) for all triazines under study permits to ensure proper determination at the maximum allowed residue levels set in the European Union Legislation. Samples of three seaweeds were subjected to the procedure proving the suitability of MSPD method for the analysis of triazines in different seaweeds samples.

  4. Identification of unwanted photoproducts of cosmetic preservatives in personal care products under ultraviolet-light using solid-phase microextraction and micro-matrix solid-phase dispersion.

    PubMed

    Alvarez-Rivera, Gerardo; Llompart, Maria; Garcia-Jares, Carmen; Lores, Marta

    2015-04-17

    The photochemical transformation of widely used cosmetic preservatives including benzoates, parabens, BHA, BHT and triclosan has been investigated in this work applying an innovative double-approach strategy: identification of transformation products in aqueous photodegradation experiments (UV-light, 254nm), followed by targeted screening analysis of such photoproducts in UV-irradiated cosmetic samples. Solid-phase microextraction (SPME) was applied, using different fiber coatings, in order to widen the range of detectable photoproducts in water, whereas UV-irradiated personal care products (PCPs) containing the target preservatives were extracted by micro-matrix solid-phase dispersion (micro-MSPD). Both SPME and micro-MSPD-based methodologies were successfully optimized and validated. Degradation kinetics of parent species, and photoformation of their transformation by-products were monitored by gas chromatography coupled to mass spectrometry (GC-MS). Thirty nine photoproducts were detected in aqueous photodegradation experiments, being tentatively identified based on their mass spectra. Transformation pathways between structurally related by-products, consistent with their kinetic behavior were postulated. The photoformation of unexpected photoproducts such as 2- and 4-hydroxybenzophenones, and 2,8-dichlorodibenzo-p-dioxin in PCPs are reported in this work for the first time.

  5. Rheology of sludge from double phase anaerobic digestion of organic fraction of municipal solid waste.

    PubMed

    Battistoni, P; Pavan, P; Mata-Alvarez, J; Prisciandaro, M; Cecchi, F

    2000-01-01

    In this paper experimental results on the anaerobic digestion of sewage sludge and organic fraction of municipal solid waste (OFMSW) by using a double phase process are reported. The long-term experiment has been carried out on a pilot scale plant, performed in different sets of operative conditions, during which granulometric distributions of particles in sludges and rheological properties of sludges were monitored. A significant fluidification of sludge was evidenced in the meso-thermo process, especially taking into account the variation in sludge behaviour from the first to the second phase. In the thermo-thermo process a fluidification higher than that shown in meso-thermo conditions is not observed, this suggesting that better results in terms of sludge conditioning can be obtained in a long time spent in thermophilic anaerobic digestion. Total volatile solids (TVS) and total fixed solids (TFS) become the most important parameters when mathematical modelling is applied to these processes. In the acidogenic phase, hydraulic retention time (HRT) and temperature are used to determine rigidity coefficient (RC), while only temperature is needed for yield stress (YC). Organic loading rate (OLR) and specific gas production (SGP) exert an important role in methanogenic phase description.

  6. The isolation of soyasaponins by fractional precipitation, solid phase extraction, and low pressure liquid chromatography.

    PubMed

    Gurfinkel, D M; Reynolds, W F; Rao, A V

    2005-11-01

    Bioactive soyasaponins are present in soybean (Glycine max). In this study, the isolation of soyasaponins in relatively pure form (>80%) using precipitation, solid phase extraction and reverse phase low pressure liquid chromatography (RP-LPLC) is described. Soy flour soyasaponins were separated from non-saponins by methanol extraction and precipitation with ammonium sulphate. Acetylated group A soyasaponins were isolated first by solid phase extraction followed by RP-LPLC (solvent: ethanol-water). Soyasaponins, from a commercial preparation, were saponified and fractionated into deacetylated group A and group B soyasaponins by solid phase extraction (methanol-water). Partial hydrolysis of group B soyasaponins produced a mixture of soyasaponin III and soyasapogenol B monoglucuronide. RP-LPLC of deacetylated group A soyasaponins separated soyasaponin A1 and A2 (38% methanol); of group B soyasaponins isolated soyasaponin I (50% ethanol); and of the partial hydrolysate separated soyasaponin III from soyasapogenol B monoglucuronide (50% ethanol). This methodology provides soyasaponin fractions that are suitable for biological evaluation.

  7. Investigating the solid-liquid phase transition of water nanofilms using the generalized replica exchange method

    NASA Astrophysics Data System (ADS)

    Lu, Qing; Kim, Jaegil; Farrell, James D.; Wales, David J.; Straub, John E.

    2014-11-01

    The generalized Replica Exchange Method (gREM) was applied to study a solid-liquid phase transition in a nanoconfined bilayer water system using the monatomic water (mW) model. Exploiting optimally designed non-Boltzmann sampling weights with replica exchanges, gREM enables an effective sampling of configurations that are metastable or unstable in the canonical ensemble via successive unimodal energy distributions across phase transition regions, often characterized by S-loop or backbending in the statistical temperature. Extensive gREM simulations combined with Statistical Temperature Weighted Histogram Analysis Method (ST-WHAM) for nanoconfined mW water at various densities provide a comprehensive characterization of diverse thermodynamic and structural properties intrinsic to phase transitions. Graph representation of minimized structures of bilayer water systems determined by the basin-hopping global optimization revealed heterogeneous ice structures composed of pentagons, hexagons, and heptagons, consistent with an increasingly ordered solid phase with decreasing density. Apparent crossover from a first-order solid-liquid transition to a continuous one in nanoconfined mW water with increasing density of the system was observed in terms of a diminishing S-loop in the statistical temperature, smooth variation of internal energies and heat capacities, and a characteristic variation of lateral radial distribution functions, and transverse density profiles across transition regions.

  8. Investigating the solid-liquid phase transition of water nanofilms using the generalized replica exchange method

    SciTech Connect

    Lu, Qing; Kim, Jaegil; Straub, John E.; Farrell, James D.; Wales, David J.

    2014-11-14

    The generalized Replica Exchange Method (gREM) was applied to study a solid-liquid phase transition in a nanoconfined bilayer water system using the monatomic water (mW) model. Exploiting optimally designed non-Boltzmann sampling weights with replica exchanges, gREM enables an effective sampling of configurations that are metastable or unstable in the canonical ensemble via successive unimodal energy distributions across phase transition regions, often characterized by S-loop or backbending in the statistical temperature. Extensive gREM simulations combined with Statistical Temperature Weighted Histogram Analysis Method (ST-WHAM) for nanoconfined mW water at various densities provide a comprehensive characterization of diverse thermodynamic and structural properties intrinsic to phase transitions. Graph representation of minimized structures of bilayer water systems determined by the basin-hopping global optimization revealed heterogeneous ice structures composed of pentagons, hexagons, and heptagons, consistent with an increasingly ordered solid phase with decreasing density. Apparent crossover from a first-order solid-liquid transition to a continuous one in nanoconfined mW water with increasing density of the system was observed in terms of a diminishing S-loop in the statistical temperature, smooth variation of internal energies and heat capacities, and a characteristic variation of lateral radial distribution functions, and transverse density profiles across transition regions.

  9. Electron Shuttling Capacity of Solid-Phase Organic Matter in Forest Soils

    NASA Astrophysics Data System (ADS)

    Patel, A.; Zhao, Q.; Yang, Y.

    2015-12-01

    Soil organic matter, as an electron shuttle, plays an important role in regulating the biogeochemical cycles of metals, especially the redox reactions for iron. Microorganisms can reduce soil organic matter under anaerobic conditions, and biotically-reduced soil organic matter can abiotically donate electrons to ferric oxides. Such soil organic matter-mediated electron transport can facilitate the interactions between microorganisms and insoluble terminal electron acceptors, i.e. iron minerals. Most previous studies have been focused on the electron shuttling processes through dissolved soil organic matter, and scant information is available for solid-phase soil organic matter. In this study, we aim to quantify the electron accepting capacity for solid-phase organic matter in soils collected from four different forests in the United States, including Truckee (CA), Little Valley (NV), Howland (ME) and Hart (MI). We used Shewanella oneidensisMR-1 to biotically reduce soil slurries, and then quantified the electrons transferred to solid-phase and solution-phase organic matter by reacting them with Fe(III)-nitrilotriacetic acid (Fe(III)-NTA). The generation of Fe(II) was measured by a ferrozine assay to calculate the electron accepting capacity of soil organic matter. Our preliminary results showed that the Truckee soil organic matter can accept 0.51±0.07 mM e-/mol carbon. We will measure the electron accepting capacity for four different soils and correlate them to the physicochemical properties of soils. Potential results will provide information about the electron accepting capacity of solid-phase soil organic matter and its governing factors, with broad implication on the coupled biogeochemical cycles of carbon and iron.

  10. The Role of Biogeochemical Dynamics in the Alteration of Uranium Solid Phases Under Oxic Conditions.

    NASA Astrophysics Data System (ADS)

    Letain, T. E.; Silva, R. J.; Nitsche, H.; Nitsche, H.; Hazen, T. C.; Clark, S. B.; Douglas, M.; Gillaspie, C.; Knopp, R.; Panak, P. J.

    2001-12-01

    Microbial reduction of uranium has been shown to lower groundwater concentrations of uranium in anoxic systems, but such biological alterations must be considered temporary unless long-term anoxia can be guaranteed. Under oxic conditions, the more soluble higher oxidation state of uranium, e.g. the uranyl cation UO2(2+), is thermodynamically favored. For example, in U ore deposits in which uraninite - consisting of reduced U(IV) as UO(2+x) - is the parent material, exposure to oxidizing conditions results in alteration to U(VI) minerals, with the U(VI)-phosphates frequently defining the boundaries of the ore body. U(VI)-phosphates are of interest because of their relatively low solubilities compared to other U(VI) solid phases. Since microorganisms are undoubtedly present in such ore deposits, they likely play a role in the formation of U(VI)-phosphate solid phases. To assist the U.S. Department of Energy (DOE) with long-term stewardship issues associated with bioremediation of uranium, the overall goal of this project is to work with model biological systems to define the mechanisms by which microorganisms facilitate the formation of U(VI)-phosphate solid phases. This information can then be used by DOE to design remediation systems that stimulate biological activity to favor the formation of U(VI)-phosphate phases. In this project, we are investigating the role of some individual bacterial strains (Bacillus sphaericus and Shewanella putrefaciens) as well as microbial consortia isolated from the NABIR Field Research Center at Oak Ridge National Laboratory on the alteration of U(VI) solid phases. These strains were selected to reflect a variety of subsurface conditions including aerobic, microaerophilic, and episodically anaerobic. These bacteria or similar species are found throughout subsurface environments. They are believed to influence actinide geochemistry through various mechanisms. These mechanisms are not independent of one another, and together they

  11. Phase Transitions in Solids Stimulated by Simultaneous Exposure to High Pressure and Relativistic Heavy Ions

    SciTech Connect

    Glasmacher, Ulrich A.; Lang, Maik; Neumann, Reinhard; Schardt, Dieter; Trautmann, Christina; Keppler, Hans; Langenhorst, Falko; Wagner, Guenther A.

    2006-05-19

    In many solids, heavy ions of high kinetic energy (MeV-GeV) produce long cylindrical damage trails with diameters of order 10 nm. Up to now, no information was available how solids cope with the simultaneous exposure to these energetic projectiles and to high pressure. We report the first experiments where relativistic uranium and gold ions from the SIS heavy-ion synchrotron at GSI were injected through several mm of diamond into solid samples pressurized up to 14 GPa in a diamond anvil cell. In synthetic graphite and natural zircon, the combination of pressure and ion beams triggered drastic structural changes not caused by the applied pressure or the ions alone. The modifications comprise long-range amorphization of graphite rather than individual track formation, and in the case of zircon the decomposition into nanocrystals and nucleation of the high-pressure phase reidite.

  12. Radioactivity concentration in liquid and solid phases of scale and sludge generated in the petroleum industry.

    PubMed

    Paranhos Gazineu, Maria Helena; de Araújo, Andressa Arruda; Brandão, Yana Batista; Hazin, Clovis Abrahão; de O Godoy, José Marcos

    2005-01-01

    Scales and sludge generated during oil extraction and production can contain uranium, thorium, radium and other natural radionuclides, which can cause exposure of maintenance personnel. This work shows how the oil content can influence the results of measurements of radionuclide concentration in scale and sludge. Samples were taken from a PETROBRAS unit in Northeast Brazil. They were collected directly from the inner surface of water pipes or from barrels stored in the waste storage area of the E&P unit. The oil was separated from the solids with a Soxhlet extractor by using aguarras at 90+/-5 degrees C as solvent. Concentrations of 226Ra and 228Ra in the samples were determined before and after oil extraction by using an HPGe gamma spectrometric system. The results showed an increase in the radionuclide concentration in the solid (dry) phase, indicating that the above radionuclides concentrate mostly in the solid material.

  13. Method and apparatus for acoustic plate mode liquid-solid phase transition detection

    DOEpatents

    Blair, Dianna S.; Freye, Gregory C.; Hughes, Robert C.; Martin, Stephen J.; Ricco, Antonio J.

    1993-01-01

    A method and apparatus for sensing a liquid-solid phase transition event is provided which comprises an acoustic plate mode detecting element placed in contact with a liquid or solid material which generates a high-frequency acoustic wave that is attenuated to an extent based on the physical state of the material is contact with the detecting element. The attenuation caused by the material in contact with the acoustic plate mode detecting element is used to determine the physical state of the material being detected. The method and device are particularly suited for detecting conditions such as the icing and deicing of wings of an aircraft. In another aspect of the present invention, a method is provided wherein the adhesion of a solid material to the detecting element can be measured using the apparatus of the invention.

  14. Method and apparatus for acoustic plate mode liquid-solid phase transition detection

    NASA Astrophysics Data System (ADS)

    Blair, D. S.; Frye, G. C.; Hughes, R. C.; Martin, S. J.; Ricco, A. J.

    1990-05-01

    A method and apparatus for sensing a liquid-solid phase transition event is provided which comprises an acoustic plate mode detecting element placed in contact with a liquid or solid material which generates a high-frequency acoustic wave that is attenuated to an extent based on the physical state of the material in contact with the detecting element. The attenuation caused by the material in contact with the acoustic plate mode detecting element is used to determine the physical state of the material being detected. The method and device are particularly suited for detecting conditions such as the icing and deicing of wings of an aircraft. In another aspect of the present invention, a method is provided wherein the adhesion of a solid material to the detecting element can be measured using the apparatus of the invention.

  15. Solid-state NMR identification and quantification of newly formed aluminosilicate phases in weathered kaolinite systems.

    PubMed

    Crosson, Garry S; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary Kay; O'Day, Peggy A; Mueller, Karl T

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3-, 1 mol kg-1 of OH-, and pH approximately 13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10(-3), 10(-4), and 10(-5) molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10(-5) m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10(-3) m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and

  16. Solid-State NMR Identification and Quantification of Newly Formed Aluminosilicate Phases in Weathered Kaolinite Systems

    SciTech Connect

    Crosson, Garry S.; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary K.; O'Day, Peggy A.; Mueller, Karl T.

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3 -, 1 mol kg-1 of OH-, and pH ~13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10-3, 10-4, and 10-5 molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10-5 m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10-3 m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and the quantitative

  17. SOLID PHASE CHARACTERIZATION OF HEEL SAMPLES FROM TANK 241-C-110

    SciTech Connect

    PAGE JS; COOKE GA; PESTOVICH JA; HUBER HJ

    2011-12-01

    During sluicing operations of tank 241-C-110, a significant amount of solids were unable to be retrieved. These solids (often referred to as the tank 'heel') were sampled in 2010 and chemically and mineralogically analyzed in the 222-S Laboratory. Additionally, dissolution tests were performed to identify the amount of undissolvable material after using multiple water contacts. This report covers the solid phase characterization of six samples from these tests using scanning electron microscopy, polarized light microscopy, and X-ray diffraction. The chemical analyses, particle size distribution analysis, and dissolution test results are reported separately. Two of the samples were from composites created from as-received material - Composite A and Composite B. The main phase in these samples was sodium-fluoride-phosphate hydrate (natrophosphate) - in the X-ray diffraction spectra, this phase was the only phase identifiable. Polarized light microscopy showed the presence of minor amounts of gibbsite and other phases. These phases were identified by scanning electron microscopy - energy dispersive X-ray spectroscopy as sodium aluminosilicates, sodium diuranate, and sodium strontium phosphate hydrate (nastrophite) crystals. The natrophosphate crystals in the scanning electron microscopy analysis showed a variety of erosive and dissolution features from perfectly shaped octahedral to well-rounded appearance. Two samples were from water-washed Composites A and B, with no change in mineralogy compared to the as-received samples. This is not surprising, since the water wash had only a short period of water contact with the material as opposed to the water dissolution tests. The last two samples were residual solids from the water dissolution tests. These tests included multiple additions of water at 15 C and 45 C. The samples were sieved to separate a coarser fraction of > 710 {mu}m and a finer fraction of < 710 {mu}m. These two fractions were analyzed separately. The

  18. Double-antibody solid-phase radioimmunoassay: a simplified phase-separation procedure applied to various ligands

    SciTech Connect

    Tevaarwerk, G.J.M.; Boyle, D.A.; Hurst, C.J.; Anguish, I.; Uksik, P.

    1980-06-01

    The purpose was to develop a simplified and reliable method of separating free from antibody-bound ligand using a precipitating antibody linked to a cellulose derivative. Dose-response curves and control sera were set up in parallel for various pituitary and placental polypeptides, steroid hormones, insulin, glucagon, triiodothyronine, thyroxine, angiotensin I, calcitonin, gastrin, cyclic AMP, and digoxin. After first-antibody reactions had reached equilibrium, free and bound ligand were separated using a double-antibody solid-phase system in parallel with conventional methods, including dextran-coated charcoal, double-antibody precipitation, single-antibody solid phase, organic solvents, salt precipitation, and anion-exchange resins. The effect of variations in temperature, incubation time, protein content, pH, and amount of separating material added were studied. The results showed that separation was complete within 1 hr for small ligand molecules and within 2 hr for larger ones. Dose-response curves and control-sera results closely paralleled those obtained with conventional methods. The method was not affected by moderate variations in incubation variables. Nonspecific binding was less than 3% in all assays, while intra-assay and interassay coefficients of variation were similar to those obtained with conventional phase-separation methods. It is concluded that the method is a simple and rapid alternative phase-separation system. It has the advantage of being free from common nonspecific intersample variations, and can be applied to any assay system based on rabbit or guinea pig antibodies without preliminay time- or reagent-consuming titration or adjustments to establish optimum phase-separating conditions.

  19. Solid-phase assay of lectin activity using HRP-conjugated glycoproteins.

    PubMed

    Kojima-Aikawa, Kyoko

    2014-01-01

    Various enzyme-conjugated probes have been widely used for detection of specific interactions between biomolecules. In the case of glycan-protein interaction, horseradish peroxidase (HRP)-conjugated glycoproteins (HRP-GPs) are useful for the detection of carbohydrate-binding activity of plant and animal lectins. In this chapter, a typical solid-phase assay of the carbohydrate-binding activity of Sophora japonica agglutinin I, a Gal/GalNAc-specific lectin, using HRP-conjugated asialofetuin is described. HRP-GPs are versatile tools for probing lectin activities in crude extracts, screening many samples at one time, and applicable not only for solid-phase binding assays but also samples which are dot- or Western-blotted onto the membrane.

  20. Solid phase graft copolymerization of acrylic monomers onto thermoplastics and their use as blend compatibilizers

    NASA Astrophysics Data System (ADS)

    Subramanian, Srinivas

    This research work is an extension of some of the earlier work done on the development of solid phase grafting technique to graft various monomers onto polymers as well as postulation of the usefulness of the graft copolymers thus synthesized. Polystyrene grafted with acrylic acid, previously developed in bench scale, was synthesized in pilot-plant scale batches. Process parameter studies on the grafting of acrylic acid onto polypropylene and developmental studies on the grafting of maleic anhydride onto polystyrene were also done. Polymers grafted with polar molecules such as maleic anhydride and acrylic acid have been used to compatibilize immiscible blends of polar and non-polar polymers. On the same note, the applicability of the solid phase graft copolymers as blend compatibilizers were investigated and their performance was compared to commercially available compatibilizers. Solid phase graft copolymerization process is a technique to synthesize graft copolymers. Some of its salient features are use of minimal solvent to conduct the reaction and easy equipment modification. It is a low pressure and low temperature process. This technique provides a viable alternative to the environmentally hazardous, and time consuming conventional process currently in use. Hence, development of this technique could be beneficial not only to the plastics industry, but also to mankind. Also, this technique provides a low-cost and extremely easy method to develop graft copolymers such as acrylic acid functionalized polymers that are rapidly gaining popularity as blend compatibilizers and polymer reinforcing agents. A study that proves the potential of these solid phase graft copolymers as good blend compatibilizers for industrially important immiscible polymers will develop interest in the industries about this grafting process. The free radical solid phase graft copolymerization process was carried in a modified Brabender-type mixer fitted with specially designed blades to

  1. Experimental setup for investigating silicon solid phase crystallization at high temperatures.

    PubMed

    Schmidt, Thomas; Gawlik, Annett; Schneidewind, Henrik; Ihring, Andreas; Andrä, Gudrun; Falk, Fritz

    2013-07-15

    An experimental setup is presented to measure and interpret the solid phase crystallization of amorphous silicon thin films on glass at very high temperatures of about 800 °C. Molybdenum-SiO(2)-silicon film stacks were irradiated by a diode laser with a well-shaped top hat profile. From the relevant thermal and optical parameters of the system the temperature evolution can be calculated accurately. A time evolution of the laser power was applied which leads to a temperature constant in time in the center of the sample. Such a process will allow the observation and interpretation of solid phase crystallization in terms of nucleation and growth in further work.

  2. Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials.

    PubMed

    Gao, Jun; Manard, Benjamin T; Castro, Alonso; Montoya, Dennis P; Xu, Ning; Chamberlin, Rebecca M

    2017-05-15

    Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of nine materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. The microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.

  3. Solid-phase antibody capture hemadsorption assay for detection of hepatitis A virus immunoglobulin M antibodies.

    PubMed Central

    Summers, P L; Dubois, D R; Cohen, W H; Macarthy, P O; Binn, L N; Sjogren, M H; Snitbhan, R; Innis, B L; Eckels, K H

    1993-01-01

    A solid-phase antibody capture hemadsorption (SPACH) assay was developed to detect hepatitis A virus (HAV)-specific immunoglobulin M (IgM) antibodies in sera from humans recently infected with hepatitis. The assay is performed with microtiter plates coated with anti-human IgM antibodies to capture IgM antibodies from the test sera. HAV-specific IgM antibody is detected by the addition of HAV hemagglutinating antigen and goose erythrocytes. Hemadsorption of erythrocytes to antigen-antibody complexes attached to the solid phase indicate the presence of IgM antibodies. The SPACH assay was compared to a commercial radioimmunoassay and was found to be equally or more sensitive and specific for the detection of HAV IgM antibodies. The SPACH assay is an alternative, rapid assay that doesn't require hazardous substrates or radioactivity for the detection of HAV-specific antibodies. PMID:8388890

  4. Quantitation of Binding, Recovery and Desalting Efficiency in Solid Phase Extraction Micropipette Tips

    SciTech Connect

    Palmblad, M N; Vogel, J S

    2004-08-02

    Micropipette-tip solid phase extraction systems are common in proteomic analyses for desalting and concentrating samples for mass spectrometry, removing interferences, and increasing sensitivity. These systems are inexpensive, disposable, and highly efficient. Here we show micropipette-tip solid phase extraction is a direct sample preparation method for {sup 14}C-accelerator mass spectrometry (AMS), removing salts or reagent from labeled macromolecules. We compared loading, recovery and desalting efficiency in commercially available SPE micro-tips using {sup 14}C-labeled peptides and proteins, AMS, and alpha spectrometry ion energy loss quantitation. The polypropylene in the tips was nearly {sup 14}C-free and simultaneously provided low-background carrier for AMS. The silica material did not interfere with the analysis. Alpha spectrometry provided an absolute measurement of desalting efficiency.

  5. Solid-phase extraction using hierarchical organosilicates for enhanced detection of nitroenergetic targets.

    PubMed

    Johnson, Brandy J; Melde, Brian J; Leska, Iwona A; Charles, Paul T; Hewitt, Alan D

    2011-05-01

    A novel porous organosilicate material was evaluated for application as a solid phase extraction sorbent for preconcentration of nitroenergetic targets from aqueous solution prior to HPLC analysis. The performance of the sorbent in spiked deionized water, groundwater, and surface water was evaluated. Targets considered included 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, RDX, HMX, and nitroglycerin. The sorbent was shown to provide improved performance over Sep-Pak RDX. The impact of complex matrices on target preconcentration by the sorbent was also found to be less dramatic than that observed for LiChrolut EN. The impact of changes in pH on target preconcentration was considered. Aqueous soil extracts generated from samples collected at sites of ordnance testing were also used to evaluate the materials. The results presented here demonstrate the potential of this novel sorbent for application as a solid phase extraction material for the preconcentration of nitroenergetic targets from aqueous solutions.

  6. Solid-phase epitaxy of silicon amorphized by implantation of the alkali elements rubidium and cesium

    SciTech Connect

    Maier, R.; Haeublein, V.; Ryssel, H.; Voellm, H.; Feili, D.; Seidel, H.; Frey, L.

    2012-11-06

    The redistribution of implanted Rb and Cs profiles in amorphous silicon during solid-phase epitaxial recrystallization has been investigated by Rutherford backscattering spectroscopy and secondary ion mass spectroscopy. For the implantation dose used in these experiments, the alkali atoms segregate at the a-Si/c-Si interface during annealing resulting in concentration peaks near the interface. In this way, the alkali atoms are moved towards the surface. Rutherford backscattering spectroscopy in ion channeling configuration was performed to measure average recrystallization rates of the amorphous silicon layers. Preliminary studies on the influence of the alkali atoms on the solid-phase epitaxial regrowth rate reveal a strong retardation compared to the intrinsic recrystallization rate.

  7. The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

    SciTech Connect

    Woo, Y; Mitchell, A R; Camarero, J A

    2006-11-03

    Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis of C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.

  8. Orthogonally Protected Furanoid Sugar Diamino Acids for Solid-Phase Synthesis of Oligosaccharide Mimetics.

    PubMed

    John, Franklin; Wittmann, Valentin

    2015-08-07

    Sugar diamino acids (SDAs), which differ from the widely used sugar amino acids in the presence of a second amino group connected to the carbohydrate core, share structural features of both amino acids and carbohydrates. They can be used for the preparation of linear and branched amide-linked oligosaccharide mimetics. Such oligomers carry free amino groups, which are positively charged at neutral pH, in a spatially defined way and, thus, represent a potential class of aminoglycoside mimetics. We report here the first examples of orthogonally protected furanoid SDAs and their use in solid-phase synthesis. Starting from d-glucose, we developed a divergent synthetic route to three derivatives of 3,5-diamino-3,5-dideoxy-d-ribofuranose. These building blocks are compatible with solid-phase peptide synthesis following the 9-fluorenylmethoxycarbonyl (Fmoc) strategy, which we demonstrate by the synthesis of an SDA tetramer.

  9. Investigation of phase diagrams and physical stability of drug-polymer solid dispersions.

    PubMed

    Lu, Jiannan; Shah, Sejal; Jo, Seongbong; Majumdar, Soumyajit; Gryczke, Andreas; Kolter, Karl; Langley, Nigel; Repka, Michael A

    2015-01-01

    Solid dispersion technology has been widely explored to improve the solubility and bioavailability of poorly water-soluble compounds. One of the critical drawbacks associated with this technology is the lack of physical stability, i.e. the solid dispersion would undergo recrystallization or phase separation thus limiting a product's shelf life. In the current study, the melting point depression method was utilized to construct a complete phase diagram for felodipine (FEL)-Soluplus® (SOL) and ketoconazole (KTZ)-Soluplus® (SOL) binary systems, respectively, based on the Flory-Huggins theory. The miscibility or solubility of the two compounds in SOL was also determined. The Flory-Huggins interaction parameter χ values of both systems were calculated as positive at room temperature (25 °C), indicating either compound was miscible with SOL. In addition, the glass transition temperatures of both solid dispersion systems were theoretically predicted using three empirical equations and compared with the practical values. Furthermore, the FEL-SOL solid dispersions were subjected to accelerated stability studies for up to 3 months.

  10. Thermodynamic Model Formulations for Inhomogeneous Solids with Application to Non-isothermal Phase Field Modelling

    NASA Astrophysics Data System (ADS)

    Gladkov, Svyatoslav; Kochmann, Julian; Reese, Stefanie; Hütter, Markus; Svendsen, Bob

    2016-04-01

    The purpose of the current work is the comparison of thermodynamic model formulations for chemically and structurally inhomogeneous solids at finite deformation based on "standard" non-equilibrium thermodynamics [SNET: e. g. S. de Groot and P. Mazur, Non-equilibrium Thermodynamics, North Holland, 1962] and the general equation for non-equilibrium reversible-irreversible coupling (GENERIC) [H. C. Öttinger, Beyond Equilibrium Thermodynamics, Wiley Interscience, 2005]. In the process, non-isothermal generalizations of standard isothermal conservative [e. g. J. W. Cahn and J. E. Hilliard, Free energy of a non-uniform system. I. Interfacial energy. J. Chem. Phys. 28 (1958), 258-267] and non-conservative [e. g. S. M. Allen and J. W. Cahn, A macroscopic theory for antiphase boundary motion and its application to antiphase domain coarsening. Acta Metall. 27 (1979), 1085-1095; A. G. Khachaturyan, Theory of Structural Transformations in Solids, Wiley, New York, 1983] diffuse interface or "phase-field" models [e. g. P. C. Hohenberg and B. I. Halperin, Theory of dynamic critical phenomena, Rev. Modern Phys. 49 (1977), 435-479; N. Provatas and K. Elder, Phase Field Methods in Material Science and Engineering, Wiley-VCH, 2010.] for solids are obtained. The current treatment is consistent with, and includes, previous works [e. g. O. Penrose and P. C. Fife, Thermodynamically consistent models of phase-field type for the kinetics of phase transitions, Phys. D 43 (1990), 44-62; O. Penrose and P. C. Fife, On the relation between the standard phase-field model and a "thermodynamically consistent" phase-field model. Phys. D 69 (1993), 107-113] on non-isothermal systems as a special case. In the context of no-flux boundary conditions, the SNET- and GENERIC-based approaches are shown to be completely consistent with each other and result in equivalent temperature evolution relations.

  11. Model of cohesive properties and structural phase transitions in non-metallic solids

    SciTech Connect

    Majewski, J.A.; Vogl, P.

    1986-01-01

    We have developed a simple, yet microscopic and universal model for cohesive properties of solids. This model explains the physical mechanisms determining the chemical and predicts semiquantitatively static and dynamic cohesive properties. It predicts a substantial softening of the long-wavelength transverse optical phonons across the pressure induced phase transition from the zincblenda to rocksalt structure in II-VI compounds. The origin of this softening is shown to be closely related to ferroelectricity.

  12. Numerical study of light-induced phase behavior of smectic solids

    NASA Astrophysics Data System (ADS)

    Chung, Hayoung; Park, Jaesung; Cho, Maenghyo

    2016-10-01

    By the chemical cross-linking of rigid molecules, liquid crystal polymer (LCP) has been envisaged as a novel heterogeneous material due to the fact that various optical and geometric states of the liquid crystalline (LC) phases are projected onto the polymeric constituents. The phase behavior, which refers to the macroscopic shape change of LCP under thermotropic phase change, is a compelling example of such optical-mechanical coupling. In this study, the photomechanical behavior, which broadly refers to the thermal- or light-induced actuation of smectic solids, is investigated using three-dimensional nonlinear finite element analysis (FEA). First, the various phases of LC are considered as well as their relation to polymeric conformation defined by the strain energy of the smectic polymer; a comprehensive constitutive equation that bridges the strong, optomechanical coupling is then derived. Such photomechanical coupling is incorporated in the FEA considering geometric nonlinearity, which is vital to understanding the large-scale light-induced bending behavior of the smectic solid.To demonstrate the simulation capability of the present model, numerous examples of photomechanical deformations are investigated parametrically, either by changing the operating conditions such as stimuli (postsynthesis) or the intrinsic properties (presynthesis). When compared to nematic solids, distinguished behaviors due to smectic substances are found herein and discussed through experiments. The quasisoftness that bidirectionally couples microscopic variables to mechanical behavior is also explained, while considering the effect of nonlinearity. In addition to providing a comprehensive measure that could deepen the knowledge of photomechanical coupling, the use of the proposed finite element framework offers an insight into the design of light-responsive actuating systems made of smectic solids.

  13. Solid phase microextraction analysis of B83 SLTS and Core B compatibility test units

    SciTech Connect

    Chambers, D M; Ithaca, J; King, H A; Malcolm, S

    1999-03-26

    Solid phase microextraction has permitted the efficient collection and analysis of a broad range of volatile and semivolatile compounds outgassed from materials. In 1998, we implemented a microextraction protocol at Mason and Hanger, Pantex Plant, for the analysis of weapons and compatibility test units. The chemical information that was obtained from this work is interpreted by determining the source and outgas mechanism for each compound in the weapon signature, which is a task only accomplished by analysis of material standards.

  14. R. Bruce Merrifield and Solid-Phase Peptide Synthesis: A Historical Assessment

    SciTech Connect

    Mitchell, A R

    2007-12-04

    Bruce Merrifield, trained as a biochemist, had to address three major challenges related to the development and acceptance of solid-phase peptide synthesis (SPPS). The challenges were (1) to reduce the concept of peptide synthesis on a insoluble support to practice, (2) overcome the resistance of synthetic chemists to this novel approach, and (3) establish that a biochemist had the scientific credentials to effect the proposed revolutionary change in chemical synthesis. How these challenges were met is discussed in this article.

  15. Application of solid-phase microextraction to the analysis of volatile compounds in virgin olive oils.

    PubMed

    Jiménez, A; Beltrán, G; Aguilera, M P

    2004-03-05

    Solid-phase microextraction was used as a technique for headspace sampling of extra virgin olive oil and virgin olive oil samples with different off-flavours. A 100 microm coated polydimethylsiloxane fiber was used to extract volatile aldehydes, the sampling temperature was 45 degrees C and the fiber has been exposed to the headspace for 15 min. Nonanal and 2-decenal were present in all the olive oils with extraction off-flavours but were not in extra virgin olive oil sample.

  16. α -β and β -γ phase boundaries of solid oxygen observed by adiabatic magnetocaloric effect

    NASA Astrophysics Data System (ADS)

    Nomura, T.; Kohama, Y.; Matsuda, Y. H.; Kindo, K.; Kobayashi, T. C.

    2017-03-01

    The magnetic-field-temperature phase diagram of solid oxygen is investigated by the adiabatic magnetocaloric effect (MCE) measurement with pulsed magnetic fields. Relatively large temperature decrease with hysteresis is observed at just below the β -γ and α -β phase-transition temperatures owing to the field-induced transitions. The magnetic field dependence of these phase boundaries are obtained as Tβ γ(H ) =43.8 -1.55 ×10-3H2 K and Tα β(H ) =23.9 -0.73 ×10-3H2 K. The magnetic Clausius-Clapeyron equation quantitatively explains the H dependence of Tβ γ, but does not Tα β. The MCE curve at Tβ γ is of typical first order, while the curve at Tα β seems to have both characteristics of first- and second-order transitions. We discuss the order of the α -β phase transition and propose possible reasons for the unusual behaviors.

  17. Solid/liquid phase diagram of the ammonium sulfate/succinic acid/water system.

    PubMed

    Pearson, Christian S; Beyer, Keith D

    2015-05-14

    We have studied the low-temperature phase diagram and water activities of the ammonium sulfate/succinic acid/water system using differential scanning calorimetry and infrared spectroscopy of thin films. Using the results from our experiments, we have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/succinic acid phase boundary as well as the ternary eutectic composition and temperature. We also compared our results to the predictions of the extended AIM aerosol thermodynamics model (E-AIM) and found good agreement for the ice melting points in the ice primary phase field of this system; however, differences were found with respect to succinic acid solubility temperatures. We also compared the results of this study with those of previous studies that we have published on ammonium sulfate/dicarboxylic acid/water systems.

  18. Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures.

    PubMed

    Drummond, N D; Monserrat, Bartomeu; Lloyd-Williams, Jonathan H; López Ríos, P; Pickard, Chris J; Needs, R J

    2015-07-28

    Establishing the phase diagram of hydrogen is a major challenge for experimental and theoretical physics. Experiment alone cannot establish the atomic structure of solid hydrogen at high pressure, because hydrogen scatters X-rays only weakly. Instead, our understanding of the atomic structure is largely based on density functional theory (DFT). By comparing Raman spectra for low-energy structures found in DFT searches with experimental spectra, candidate atomic structures have been identified for each experimentally observed phase. Unfortunately, DFT predicts a metallic structure to be energetically favoured at a broad range of pressures up to 400 GPa, where it is known experimentally that hydrogen is non-metallic. Here we show that more advanced theoretical methods (diffusion quantum Monte Carlo calculations) find the metallic structure to be uncompetitive, and predict a phase diagram in reasonable agreement with experiment. This greatly strengthens the claim that the candidate atomic structures accurately model the experimentally observed phases.

  19. Chromatographic Separations Using Solid-Phase Extraction Cartridges: Separation of Wine Phenolics

    NASA Astrophysics Data System (ADS)

    Brenneman, Charles A.; Ebeler, Susan E.

    1999-12-01

    We describe a simple laboratory experiment that demonstrates the principles of chromatographic separation using solid-phase extraction columns and red wine. By adjusting pH and mobile phase composition, the wine is separated into three fractions of differing polarity. The content of each fraction can be monitored by UV-vis spectroscopy. When the experiment is combined with experiments involving HPLC or GC separations, students gain a greater appreciation for and understanding of the highly automated instrumental systems currently available. In addition, they learn about the chemistry of polyphenolic compounds, which are present in many foods and beverages and which are receiving much attention for their potentially beneficial health effects.

  20. The role of energetic processing on solid-phase chemistry in star forming regions

    NASA Astrophysics Data System (ADS)

    Palumbo, M. E.; Urso, R. G.; Kaňuchová, Z.; Scirè, C.; Accolla, M.; Baratta, G. A.; Strazzulla, G.

    2016-05-01

    It is generally accepted that complex molecules observed in star forming regions are formed in the solid phase on icy grain mantles and are released to the gas-phase after desorption of icy mantles. Most of our knowledge on the physical and chemical properties of ices in star forming regions is based on the comparison between observations and laboratory experiments performed at low temperature (10-100 K). Here we present some recent laboratory experiments which show the formation of (complex) molecular species after ion bombardment of simple ices.

  1. Numerical simulation study on gas solid two-phase flow in pre-calciner

    NASA Astrophysics Data System (ADS)

    Hu, Zhijuan; Lu, Jidong; Huang, Lai; Wang, Shijie

    2006-06-01

    A three-dimensional numerical simulation of DD (dual combustion and denitratior process) pre-calciner for cement production was conducted in this paper. In Euler coordinate system, the fluid phase is expressed with RNG k- ɛ two-equation model and the solid phase is expressed with particle stochastic trajectory model in Lagrange coordinate system. Four mixture fractions are deduced in this article to simulate the gas compositions. The results of numerical simulation predicted the burn-out ratio of coal and the decomposition ratio of limestone particles along with particle trajectories. It also supplied theoretical foundation for industrial analysis of the coupling relation between coal combustion and calcium carbonate decomposition.

  2. Measurements on Melting Pressure, Metastable Solid Phases, and Molar Volume of Univariant Saturated Helium Mixture

    NASA Astrophysics Data System (ADS)

    Rysti, J.; Manninen, M. S.; Tuoriniemi, J.

    2014-06-01

    A concentration-saturated helium mixture at the melting pressure consists of two liquid phases and one or two solid phases. The equilibrium system is univariant, whose properties depend uniquely on temperature. Four coexisting phases can exist on singular points, which are called quadruple points. As a univariant system, the melting pressure could be used as a thermometric standard. It would provide some advantages compared to the current reference, namely pure He, especially at the lowest temperatures below 1 mK. We have extended the melting pressure measurements of the concentration-saturated helium mixture from 10 to 460 mK. The density of the dilute liquid phase was also recorded. The effect of the equilibrium crystal structure changing from hcp to bcc was clearly seen at mK at the melting pressure MPa. We observed the existence of metastable solid phases around this point. No evidence was found for the presence of another, disputed, quadruple point at around 400 mK. The experimental results agree well with our previous calculations at low temperatures, but deviate above 200 mK.

  3. High-pressure phase transitions of solid HF, HCl, and HBr: An ab initio evolutionary study

    NASA Astrophysics Data System (ADS)

    Zhang, Lijun; Wang, Yanchao; Zhang, Xinxin; Ma, Yanming

    2010-07-01

    Using ab initio evolutionary methodology for structure predictions, we investigated the high-pressure phase diagram for solid-state HF, HCl, and HBr at zero temperature. The ambient-pressure chain-type Cmc21 structure and sequent high-pressure symmetric hydrogen-bonded Cmcm structure were successfully reproduced by structural simulations with the only known information of chemical compositions. We have also presented insight into the underlying mechanism of hydrogen-bond symmetrization at the Cmc21→Cmcm transformation, by analysis of electron localization functions, potential wells, and zone-center phonons with pressure. At higher pressures, it was predicted that HF transforms from the Cmcm phase to another chain-type Pnma structure at ˜143GPa while the post- Cmcm phase of HCl and HBr adopts an intriguing triclinic P1¯ structure at above 108 GPa and 59 GPa, respectively, which consists of nearly planar squares resembling the ambient phase of HI. The newly predicted high-pressure phases of these halides all contain symmetric hydrogen bonds and satisfy lattice dynamical stability. As for the earlier proposed dissociation of HBr, we found that this can only occur at rather high pressures (above 120 GPa) with the formation of monatomic Br and solid H2 .

  4. Solid phase extraction for the speciation and preconcentration of inorganic selenium in water samples: a review.

    PubMed

    Herrero Latorre, C; Barciela García, J; García Martín, S; Peña Crecente, R M

    2013-12-04

    Selenium is an essential element for the normal cellular function of living organisms. However, selenium is toxic at concentrations of only three to five times higher than the essential concentration. The inorganic forms (mainly selenite and selenate) present in environmental water generally exhibit higher toxicity (up to 40 times) than organic forms. Therefore, the determination of low levels of different inorganic selenium species in water is an analytical challenge. Solid-phase extraction has been used as a separation and/or preconcentration technique prior to the determination of selenium species due to the need for accurate measurements for Se species in water at extremely low levels. The present paper provides a critical review of the published methods for inorganic selenium speciation in water samples using solid phase extraction as a preconcentration procedure. On the basis of more than 75 references, the different speciation strategies used for this task have been highlighted and classified. The solid-phase extraction sorbents and the performance and analytical characteristics of the developed methods for Se speciation are also discussed.

  5. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    NASA Astrophysics Data System (ADS)

    Reis, Martina Costa; Wang, Yongqi

    2016-12-01

    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  6. Detection of antinuclear antibodies by indirect immunofluorescence and by solid phase assay.

    PubMed

    Op De Beeck, Katrijn; Vermeersch, Pieter; Verschueren, Patrick; Westhovens, René; Mariën, Godelieve; Blockmans, Daniel; Bossuyt, Xavier

    2011-10-01

    Testing for antinuclear antibodies is useful for the diagnosis of systemic rheumatic diseases. Solid phase assays are increasingly replacing indirect immunofluorescence for detection of antinuclear antibodies. In the most recent generation of solid phase assays, manufacturers attempt to improve the performance of the assays by adding extra antigens. Solid phase assay (EliA CTD Screen, Phadia, in which antibodies to 17 antigens are detected) was compared to indirect immunofluorescence for the detection of antinuclear antibodies in diagnostic samples of 236 patients with autoimmune connective tissue diseases, in 149 healthy blood donors, 139 patients with chronic fatigue syndrome, and 134 diseased controls. The sensitivity of EliA CTD Screen for systemic lupus erythematosus, systemic sclerosis, primary Sjögren's syndrome, mixed connective tissue disease, and inflammatory myopathy was 74%, 72%, 89%, 100%, and 39%, respectively. The reactivity in blood donors, in patients with chronic fatigue syndrome, and in diseased controls was <4%. Likelihood ratios increased with increasing antibody concentrations. Generally, a positive test result by EliA CTD Screen had a higher likelihood ratio for systemic rheumatic disease than a positive test result by indirect immunofluorescence. A negative test result by indirect immunofluorescence, however, had a lower likelihood ratio than a negative test result by EliA CTD Screen, indicating that the negative predictive value was higher for indirect immunofluorescence than for EliA CTD screen.

  7. Solid-phase receptor binding assay for /sup 125/I-hCG

    SciTech Connect

    Bortolussi, M.; Selmin, O.; Colombatti, A.

    1987-01-01

    A solid-phase radioligand-receptor assay (RRA) to measure the binding of /sup 125/I-labelled human chorionic gonadotropin (/sup 125/I-hCG) to target cell membranes has been developed. The binding of /sup 125/I-hCG to membranes immobilized on the wells of microtitration plates reached a maximum at about 3 hours at 37 degrees C, was saturable, displayed a high affinity (Ka = 2.4 X 10(9) M-1) and was specifically inhibited by unlabelled hCG. In comparison with RRAs carried out with membranes in suspension, the solid-phase RRA is significantly simpler and much faster to perform as it avoids centrifugation or filtration procedures. The solid-phase RRA was adapted profitably to process large numbers of samples at the same time. It proved particularly useful as a screening assay to detect anti-hCG monoclonal antibodies with high inhibitory activity for binding of /sup 125/I-hCG to its receptors.

  8. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    NASA Astrophysics Data System (ADS)

    Reis, Martina Costa; Wang, Yongqi

    2017-03-01

    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  9. Bacterial migration and motion in a fluid phase and near a solid surface

    SciTech Connect

    Frymier, P.D. Jr.

    1995-01-01

    An understanding of the migration and motion of bacteria in a fluid phase and near solid surfaces is necessary to characterize processes such as the bioremediation of hazardous waste, the pathogenesis of infection, industrial biofouling and wastewater treatment, among others. This study addresses three questions concerning the prediction of the distribution of a population of bacteria in a fluid phase and the motion of bacteria near a solid surface: Under what conditions does a one-dimensional phenomenological model for the density of a population of chemotactic bacteria yield an adequate representation of the migration of bacteria subject to a one-dimensional attractant gradient? How are the values of transport coefficients obtained from experimental data affected by the use of the one-dimensional phenomenological model and also by the use of different descriptions of bacterial swimming behavior in a mathematically rigorous balance equation? How is the characteristic motion of bacteria swimming in a fluid affected by the presence of a solid phase? A computer simulation that rigorously models the movement of a large population of individual chemotactic bacteria in three dimensions is developed to test the validity of a one-dimensional phenomenological model for bacterial migration in a fluid.

  10. Solid-state synthesis and phase transformations in Ni/Fe films: Structural and magnetic studies

    NASA Astrophysics Data System (ADS)

    Myagkov, V. G.; Zhigalov, V. C.; Bykova, L. E.; Bondarenko, G. N.

    2006-10-01

    We have used X-ray diffraction, volume magnetocrystalline anisotropy constant and resistance measurements to study solid-state synthesis in Ni(0 0 1)/Fe(0 0 1), Ni/Fe(0 0 1) and Ni/Fe thin films with the atomic ratio between Fe and Ni of 1:1 (1Fe:1Ni), and 3:1 (3Fe:1Ni). We have found that the formation of Ni 3Fe and NiFe phases in the 1Fe:1Ni films takes place at temperatures ˜620 and ˜720 K, correspondingly. In the case of the 3Fe:1Ni films the solid-state synthesis starts with Ni 3Fe and NiFe phase formation at the same temperatures as for the 1Fe:1Ni films. The increasing of annealing temperature above 820 K leads to the nucleation of a paramagnetic γpar phase at the FeNi/Fe interface. The final products of solid-state synthesis in the Ni(0 0 1)/Fe(0 0 1) thin films are crystallites which consist of the epitaxially intergrown NiFe and γpar phases according to the [1 0 0](0 0 1)NiFe||[1 0 0](0 0 1) γpar orientation relationship. The crystalline perfection and epitaxial growth of the (NiFe+ γpar) crystallites on the MgO(0 0 1) surface allow to distinguish (0 0 2) γpar and (0 0 2)NiFe X-ray peaks (the cell parameters are: a( γpar)=0.3600±0.0005 nm and a(NiFe)=0.3578±0.0005 nm, correspondingly). At low temperatures the paramagnetic γpar phase undergoes the martensite γ→α' phase transition which can be hindered by thermal and epitaxial strains and epitaxial clamping with a MgO substrate. On the basis of the studies of the thin-film solid-state synthesis we predict the existence of two novel structural phase transformations at the temperatures of about 720 and 820 K for alloys of the invar region of the Fe-Ni system.

  11. Geochemistry, mineralogy, solid-phase fractionation and oral bioaccessibility of lead in urban soils of Lisbon.

    PubMed

    Reis, A P; Patinha, C; Wragg, J; Dias, A C; Cave, M; Sousa, A J; Costa, C; Cachada, A; Ferreira da Silva, E; Rocha, F; Duarte, A

    2014-10-01

    An urban survey of Lisbon, the largest city in Portugal, was carried out to investigate its environmental burden, emphasizing metallic elements and their public health impacts. This paper examines the geochemistry of lead (Pb) and its influence on human health data. A total of 51 soil samples were collected from urban recreational areas used by children to play outdoors. The semi-quantitative analysis of Pb was carried out by inductively coupled plasma mass spectrometry after an acid digestion. X-ray diffraction was used to characterize the soil mineralogy. The solid-phase distribution of Pb in the urban soils was investigated on a subset of 7 soils, out of a total of 51 samples, using a non-specific sequential extraction method coupled with chemometric analysis. Oral bioaccessibility measurements were obtained using the Unified BARGE Method developed by the Bioaccessibility Research Group of Europe. The objectives of the study are as follows: (1) investigation of Pb solid-phase distribution; (2) interpretation of Pb oral bioaccessibility measurements; (3) integration of metal geochemistry with human health data; and (4) understanding the influence of geochemistry and mineralogy on oral bioaccessibility. The results show that the bioaccessible fraction of Pb is lower when major metal fractions are associated with less soluble soil phases such as Fe oxyhydroxides, and more increased when the metal is in the highly soluble carbonate phase. However, there is some evidence that the proportion of carbonates in the soil environment is also a key control over the oral bioaccessibility of Pb, irrespective of its solid-phase fractionation.

  12. A two-phase restricted equilibrium model for combustion of metalized solid propellants

    NASA Technical Reports Server (NTRS)

    Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

    1992-01-01

    An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

  13. Application of the phase method in radioisotope measurements of the liquid - solid particles flow in the vertical pipeline

    NASA Astrophysics Data System (ADS)

    Hanus, Robert; Zych, Marcin; Petryka, Leszek; Mosorov, Volodymyr; Hanus, Paweł

    2015-05-01

    The paper presents idea and an application of the gamma-absorption method to a two-phase flow investigation in a vertical pipeline, where the flow of solid particles transported by water was examined by a set of two 241Am radioactive sources and probes with NaI(Tl) scintillation crystals. In the described experiments as solid phase the ceramic models representing natural polymetallic ocean nodules were used. For advanced analysis of electrical signals obtained from detectors the phase of cross-spectral density function has been applied. Results of the average solid-phase velocity measurements were compared with one obtained by application of the classical cross-correlation. It was found that the combined uncertainties of the velocity of solid particles evaluation in the presented experiment did not exceed 0.6% in phase method and 3.2% in cross-correlation method.

  14. Numerical Computation of Flame Spread over a Thin Solid in Forced Concurrent Flow with Gas-phase Radiation

    NASA Technical Reports Server (NTRS)

    Jiang, Ching-Biau; T'ien, James S.

    1994-01-01

    Excerpts from a paper describing the numerical examination of concurrent-flow flame spread over a thin solid in purely forced flow with gas-phase radiation are presented. The computational model solves the two-dimensional, elliptic, steady, and laminar conservation equations for mass, momentum, energy, and chemical species. Gas-phase combustion is modeled via a one-step, second order finite rate Arrhenius reaction. Gas-phase radiation considering gray non-scattering medium is solved by a S-N discrete ordinates method. A simplified solid phase treatment assumes a zeroth order pyrolysis relation and includes radiative interaction between the surface and the gas phase.

  15. Immobilization and functional reconstitution of antibody Fab fragment by solid-phase refolding.

    PubMed

    Kumada, Yoichi; Hamasaki, Kyoto; Nakagawa, Aya; Sasaki, Eiju; Shirai, Tatsunori; Okumura, Masahiro; Inoue, Manami; Kishimoto, Michimasa

    2013-12-31

    In this study, we demonstrated the successful preparation of a Fab antibody-immobilized hydrophilic polystyrene (phi-PS) plate via one- and two-step solid-phase refolding methods. Both polystyrene-binding peptide (PS-tag)-fused Fd fragment of heavy chain (Fab H-PS) and full-length of light-chain (Fab L-PS) were individually produced in insoluble fractions of Escherichia coli cells, and they were highly purified in the presence of 8M of urea. Antigen-binding activities of Fab antibody immobilized were correctly recovered by the one-step solid-phase refolding method that a mixture of Fab H-PS and Fab L-PS was immobilized in the presence of 0.5-2M urea, followed by surface washing of the phi-PS plate with PBST. These results indicate that by genetic fusion of a PS-tag, a complex between Fab H and Fab L was efficiently immobilized on the surface of a phi-PS plate even in the presence of a low concentration of urea, and was then correctly refolded to retain its high antigen-binding activity via removal of the urea. A two-step solid-phase refolding method whereby Fab H-PS and Fab L-PS were successively refolded on the surface of a phi-PS plate also resulted in Fab antibody formation on the plate. Furthermore, both the binding affinity and the specificity of the Fab antibody produced by the two-step method were highly maintained, according to the results of sandwich ELISA and competitive ELISA using Fab antibody-immobilized plate via two-step solid-phase refolding. Thus, the solid-phase refolding method demonstrated in this study should be quite useful for the preparation of a Fab antibody-immobilized PS surface with high efficiency from individually produced Fab H-PS and Fab L-PS. This method will be applicable to the preparation of a large Fab antibody library on the surface of a PS plate for use in antibody screening.

  16. Variable-cell double-ended surface walking method for fast transition state location of solid phase transitions.

    PubMed

    Zhang, Xiao-Jie; Liu, Zhi-Pan

    2015-10-13

    To identify the low energy pathway for solid-to-solid phase transition has been a great challenge in physics and material science. This work develops a new theoretical method, namely, variable-cell double-ended surface walking (VC-DESW) to locate the transition state (TS) and deduce the pathway in solid phase transition. Inherited from the DESW method ( J. Chem. Theory Comput. 2013 , 9 , 5745 ) for molecular systems, the VC-DESW method implements an efficient mechanism to couple the lattice and atom degrees of freedom. The method features with fast pseudopathway building and accurate TS location for solid phase transition systems without requiring expensive Hessian computation and iterative pathway optimization. A generalized coordinate, consisting of the lattice vectors and the scaled atomic coordinates, is designed for describing the crystal potential energy surface (PES), which is able to capture the anisotropic behavior in phase transition. By comparing with the existing method for solid phase transition in different systems, we show that the VC-DESW method can be much more efficient for finding the TS in crystal phase transition. With the combination of the recently developed unbiased stochastic surface walking pathway sampling method, the VC-DESW is further utilized to resolve the lowest energy pathway of SiO2 α-quartz to quartz-II phase transition from many likely reaction pathways. These new methods provide a powerful platform for understanding and predicting the solid phase transition mechanism and kinetics.

  17. A two-phase solid/fluid model for dense granular flows including dilatancy effects

    NASA Astrophysics Data System (ADS)

    Mangeney, Anne; Bouchut, Francois; Fernandez-Nieto, Enrique; Koné, El-Hadj; Narbona-Reina, Gladys

    2016-04-01

    Describing grain/fluid interaction in debris flows models is still an open and challenging issue with key impact on hazard assessment [{Iverson et al.}, 2010]. We present here a two-phase two-thin-layer model for fluidized debris flows that takes into account dilatancy effects. It describes the velocity of both the solid and the fluid phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure [{Bouchut et al.}, 2016]. The model is derived from a 3D two-phase model proposed by {Jackson} [2000] based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work [{Bouchut et al.}, 2015]. In particular, {Pitman and Le} [2005] replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's model by closing the mixture equations by a weak compressibility relation following {Roux and Radjai} [1998]. This relation implies that the occurrence of dilation or contraction of the granular material in the model depends on whether the solid volume fraction is respectively higher or lower than a critical value. When dilation occurs, the fluid is sucked into the granular material, the pore pressure decreases and the friction force on the granular phase increases. On the contrary, in the case of contraction, the fluid is expelled from the mixture, the pore pressure increases and the friction force diminishes. To

  18. The organic matter of Comet Halley as inferred by joint gas phase and solid phase analyses

    NASA Astrophysics Data System (ADS)

    Krueger, F. R.; Korth, A.; Kissel, J.

    1991-04-01

    During encounters with Comet Halley, the experiment PICCA onboard Giotto measured the gas-phase organic ion composition of the coma, and the experiment PUMA onboard Vega-1 measured the dust composition. Joining both results gives a consistent picture of the parent organic matter from which dust and gas is produced: a complex unsaturated polycondensate, which splits during coma formation into the more refractory C=C,C-N-containing dust part and the more volatile C=C,C-O-containing gas part. The responsible exothermal chemical reactions, which are triggered by sunlight, may play a major role in the dynamics of coma formation.

  19. Polymer Microchips Integrating Solid Phase Extraction and High Performance Liquid Chromatography Using Reversed-Phase Polymethacrylate Monoliths

    PubMed Central

    Liu, Jikun; Chen, C. F.; Tsao, C. W.; Chang, C. C.; Chu, C. C.; DeVoe, D. L.

    2009-01-01

    Polymer microfluidic chips employing in situ photopolymerized polymethacrylate monoliths for high performance liquid chromatography separations of peptides is described. The integrated chip design employs a 15 cm long separation column containing a reversed-phase polymethacrylate monolith as a stationary phase, with its front end seamlessly coupled to a 5 mm long methacrylate monolith which functions as a solid phase extraction (SPE) element for sample cleanup and enrichment, serving to increase both detection sensitivity and separation performance. In addition to sample concentration and separation, solvent splitting is also performed on-chip, allowing the use of a conventional LC pump for the generation of on-chip nano-flow solvent gradients. The integrated platform takes advantage of solvent bonding and a novel high-pressure needle interface which together enable the polymer chips to withstand internal pressures above 20 MPa (~2,900 psi) for efficient pressure-driven HPLC separations. Gradient reversed-phase separation of fluorescein-labeled model peptides and BSA tryptic digest are demonstrated using the microchip HPLC system. On-line removal of free fluorescein and enrichment of labeled proteins are simultaneously achieved using the on-chip SPE column, resulting in a 150-fold improvement in sensitivity and a 10-fold reduction in peak width in the following microchip gradient LC separation. PMID:19267447

  20. Lattice model theory of the equation of state covering the gas, liquid, and solid phases

    NASA Technical Reports Server (NTRS)

    Bonavito, N. L.; Tanaka, T.; Chan, E. M.; Horiguchi, T.; Foreman, J. C.

    1975-01-01

    The three stable states of matter and the corresponding phase transitions were obtained with a single model. Patterned after Lennard-Jones and Devonshires's theory, a simple cubic lattice model containing two fcc sublattices (alpha and beta) is adopted. The interatomic potential is taken to be the Lennard-Jones (6-12) potential. Employing the cluster variation method, the Weiss and the pair approximations on the lattice gas failed to give the correct phase diagrams. Hybrid approximations were devised to describe the lattice term in the free energy. A lattice vibration term corresponding to a free volume correction is included semi-phenomenologically. The combinations of the lattice part and the free volume part yield the three states and the proper phase diagrams. To determine the coexistence regions, the equalities of the pressure and Gibbs free energy per molecule of the coexisting phases were utilized. The ordered branch of the free energy gives rise to the solid phase while the disordered branch yields the gas and liquid phases. It is observed that the triple point and the critical point quantities, the phase diagrams and the coexistence regions plotted are in good agreement with the experimental values and graphs for argon.

  1. Matrix solid-phase dispersion and solid-phase microextraction applied to study the distribution of fenbutatin oxide in grapes and white wine.

    PubMed

    Montes, R; Canosa, P; Lamas, J Pablo; Piñeiro, A; Orriols, I; Cela, R; Rodríguez, I

    2009-12-01

    The fate of the acaricide fenbutatin oxide (FBTO) during the elaboration of white wine is evaluated. Matrix solid-phase dispersion (MSPD) and solid-phase microextraction (SPME) were used as sample preparation techniques applied to the semi-solid and the liquid matrices involved in this research, respectively. Selective determination of FBTO was achieved by gas chromatography with atomic emission detection (GC-AED). GC coupled to mass spectrometry was also used to establish the identity of FBTO by-products detected in must and wine samples. MSPD extractions were accomplished using C18 as dispersant and co-sorbent. Sugars and other polar interferences were first removed with water and water/acetone mixtures, then FBTO was recovered with 8 mL of acetone. When used in combination with GC-AED, the MSPD method provided limits of quantification (LOQs) in the low nanogram per gram range, recoveries around 90% and relative standard deviations below 13% for extractions performed in different days. Performance of SPME for must and wine was mainly controlled by the extraction temperature, time and fibre coating. Under final conditions, FBTO was extracted in the headspace mode for 45 min at 100 degrees C, using a 100 microm poly(dimethylsiloxane)-coated fibre. The achieved LOQs remained around or below 0.1 ng mL(-1), depending on the type of sample, and the inter-day precision ranged from 10% to 13%. FBTO residues in grapes stayed mostly on the skin of the fruit. Although FBTO was not removed during must and white wine elaboration, it remained associated with suspended particles existing in must and lees, settled after must fermentation, with a negligible risk of being transferred to commercialised wine. On the other hand, two by-products of FBTO (bis and mono (2-methyl-2-phenylpropyl) tin) were identified, for first time, in must and final white wines obtained from FBTO treated grapes. Found values for the first species ranged from 0.03 to 0.9 ng mL(-1).

  2. Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

    PubMed

    Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

    2015-09-21

    The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors.

  3. Fixed bed reactor for solid-phase surface derivatization of superparamagnetic nanoparticles.

    PubMed

    Steitz, Benedikt; Salaklang, Jatuporn; Finka, Andrija; O'Neil, Conlin; Hofmann, Heinrich; Petri-Fink, Alke

    2007-01-01

    The functionalization of nanoparticles is conditio sine qua non in studies of specific interaction with a biological target. Often, their biological functionality is achieved by covalent binding of bioactive molecules on a preexisting single surface coating. The yield and quality of the resulting coated and functionalized superparamagnetic iron oxide nanoparticles (SPIONs) can be significantly improved and reaction times reduced by using solid-phase synthesis strategies. In this study, a fixed bed reactor with a quadrupole repulsive arrangement of permanent magnets was assayed for SPION surface derivatization. The magnet array around the fixed bed reactor creates very high magnetic field gradients that enables the immobilization of SPIONs with a diameter as low as 9 nm. The functionalization on the surface of immobilized 25 nm 3-(aminopropyl)trimethoxysilane-coated SPIONs (APS-SPIONs) was performed using fluorescein-isothiocyanate directly, and by the SV40 large T-antigen nuclear localization signal peptide (PKKKRKVGC) conjugated to acryloylpoly(ethylene glycol)-N-hydroxysuccinimide, where the PEG reagent is conjugated first to create a functionalized nanoparticle and the peptide is added to the acryloyl group. We show that the yield of reactant grafted on the surface of the APS-coated SPIONs was higher in solid-phase within the fixed bed reactor compared to conventional liquid-phase chemistry. In summary, the functionalization of SPIONs using a magnetically fixed bed reactor was superior to the liquid-phase reaction in terms of the yield, reaction times required for derivatization, size distribution, and scalability.

  4. Solution- and solid-phase oligosaccharide synthesis using glucosyl iodides: a comparative study.

    PubMed

    Lam, Son N; Gervay-Hague, Jacquelyn

    2002-11-19

    Glycosyl iodide donors have been used in both solid- and solution-phase syntheses yielding alpha-(1 --> 6)-linked glucosyl oligomers in highly efficient protocols. While the solid-phase strategy offers advantages in terms of ease of purification, it requires a total of 7.5 equiv of donor and approximately 12 h to complete the incorporation of one monosaccharide unit. In contrast, solution-phase methods require only 2.5 equiv of donor and 2-3 h reaction time per glycosylation. Moreover, since the reactions are virtually quantitative (> 90%) column chromatography of the material is facile. The overall advantages of solution-phase oligosaccharide synthesis were further illustrated in the convergent synthesis of a hexamer (methoxycarbonylmethyl 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6)-tetrakis-(2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl-(1 --> 6))-2,3,4-tri-O-benzyl-1-thio-alpha-D-glucopyranoside) that was constructed from dimer donor iodides in a two-plus-two and a two-plus-four fashion.

  5. Vapor-phase infrared spectroscopy on solid organic compounds with a pulsed resonant photoacoustic detection scheme

    NASA Astrophysics Data System (ADS)

    Bartlome, Richard; Fischer, Cornelia; Sigrist, Markus W.

    2005-08-01

    There is a great need for a low cost and sensitive method to measure infrared spectra of solid organic compounds in the gas phase. To record such spectra, we propose an optical parametric generator-based photoacoustic spectrometer, which emits in the mid-infrared fingerprint region between 3 and 4 microns. In this system, the sample is heated in a vessel before entering a home built photoacoustic cell, where the gaseous molecules are excited by a tunable laser source with a frequency repetition rate that matches the first longitudinal resonance frequency of the photocaoustic cell. In a first phase, we have focused on low-melting point stimulants such as Nikethamide, Mephentermine sulfate, Methylephedrine, Ephedrine and Pseudoephedrine. The vapor-phase spectra of these doping substances were measured between 2800 and 3100 cm-1, where fundamental C-H stretching vibrations take place. Our spectra show notable differences with commercially available condensed phase spectra. Our scheme enables to measure very low vapor pressures of low-melting point (<160 °C) solid organic compounds. Furthermore, the optical resolution of 8 cm-1 is good enough to distinguish closely related chemical structures such as the Ephedra alkaloids Ephedrine and Methylephedrine, but doesn't allow to differentiate diastereoisomeric pairs such as Ephedrine and Pseudoephedrine, two important neurotransmitters which reveal different biological activities. Therefore, higher resolution and a system capable of measuring organic compounds with higher melting points are required.

  6. Proton or Deuteron Transfer in Phase IV of Solid Hydrogen and Deuterium

    NASA Astrophysics Data System (ADS)

    Liu, Hanyu; Ma, Yanming

    2013-01-01

    The recent discovery of phase IV of solid hydrogen and deuterium consisting of two alternate layers of graphenelike three-molecule rings and unbound H2 molecules have generated great interest. However, the vibrational nature of phase IV remains poorly understood. Here, we report a peculiar proton or deuteron transfer and a simultaneous rotation of three-molecule rings in graphenelike layers predicted by ab initio variable-cell molecular dynamics simulations for phase IV of solid hydrogen and deuterium at pressure ranges of 250-350 GPa and temperature range of 300-500 K. This proton or deuteron transfer is intimately related to the particular elongation of molecules in graphenelike layers, and it becomes more pronounced with increasing pressure at the course of larger elongation of molecules. As the consequence of proton transfer, hydrogen molecules in graphenelike layers are short lived and hydrogen vibration is strongly anharmonic. Our findings provide direct explanations on the observed abrupt increase of Raman width at the formation of phase IV and its large increase with pressure.

  7. Phase shift method to estimate solids circulation rate in circulating fluidized beds

    SciTech Connect

    Ludlow, James Christopher; Panday, Rupen; Shadle, Lawrence J.

    2013-01-01

    While solids circulation rate is a critical design and control parameter in circulating fluidized bed (CFB) reactor systems, there are no available techniques to measure it directly at conditions of industrial interest. Cold flow tests have been conducted at NETL in an industrial scale CFB unit where the solids flow has been the topic of research in order to develop an independent method which could be applied to CFBs operating under the erosive and corrosive high temperatures and pressures of a coal fired boiler or gasifier. The dynamic responses of the CFB loop to modest modulated aeration flows in the return leg or standpipe were imposed to establish a periodic response in the unit without causing upset in the process performance. The resulting periodic behavior could then be analyzed with a dynamic model and the average solids circulation rate could be established. This method was applied to the CFB unit operated under a wide range of operating conditions including fast fluidization, core annular flow, dilute and dense transport, and dense suspension upflow. In addition, the system was operated in both low and high total solids inventories to explore the influence of inventory limiting cases on the estimated results. The technique was able to estimate the solids circulation rate for all transport circulating fluidized beds when operating above upper transport velocity, U{sub tr2}. For CFB operating in the fast fluidized bed regime (i.e., U{sub g}< U{sub tr2}), the phase shift technique was not successful. The riser pressure drop becomes independent of the solids circulation rate and the mass flow rate out of the riser does not show modulated behavior even when the riser pressure drop does.

  8. Computation of solid/liquid phase change including free convection - Comparison with data

    NASA Technical Reports Server (NTRS)

    Schneider, G. E.

    1990-01-01

    A computational model is presented for solid/liquid phase-change energy transport including free convection fluid flow in the liquid phase. The computational model considers the velocity components of all nonliquid control volumes to be zero but fully solves the coupled mass-momentum problem within the liquid. The thermal energy model includes the entire domain and employs an enthalpy-like model and a recently developed method for handling the phase-change interface nonlinearity. Convergence studies are performed and comparisons made with experimental data for two different problems. Grid independence is achieved, and the comparison with experimental data indicates excellent quantitative prediction of the melt fraction evolution. Qualitative data are also provided as velocity vector and isotherm plots. The computational costs incurred are quite low by comparison with other models.

  9. Superfluid, solid, and supersolid phases of dipolar bosons in a quasi-one-dimensional optical lattice

    SciTech Connect

    Fellows, Jonathan M.; Carr, Sam T.

    2011-11-15

    We discuss a model of dipolar bosons trapped in a weakly coupled planar array of one-dimensional tubes. We consider the situation where the dipolar moments are aligned by an external field, and we find a rich phase diagram as a function of the angle of this field exhibiting quantum phase transitions between solid, superfluid, and supersolid phases. In the low energy limit, the model turns out to be identical to one describing quasi-one-dimensional superconductivity in condensed matter systems. This opens the possibility of using bosons as a quantum analog simulator of electronic systems, a scenario arising from the intricate relation between statistics and interactions in quasi-one-dimensional systems.

  10. Phase separation in dilute solutions of 3He in solid 4He

    NASA Astrophysics Data System (ADS)

    Huan, C.; Yin, L.; Xia, J. S.; Candela, D.; Cowan, B. P.; Sullivan, N. S.

    2017-03-01

    We report the results of studies of the phase separation of solid solutions of dilute concentrations of 3He in 4He. The temperatures and the kinetics of the phase separation were determined from NMR experiments for 3He concentrations 1.6 ×10-5phase separation temperatures are found to be in excellent agreement with regular solution theory as augmented by Edwards and Balibar [Phys. Rev. B 39, 4083 (1989), 10.1103/PhysRevB.39.4083]. The growth of 3He droplets shows a t1 /3 time dependence at long times consistent with Ostwald ripening.

  11. Surface Specularity as an Indicator of Shock-Induced Solid-Liquid Phase Transitions

    SciTech Connect

    Gerald Stevens, Stephen Lutz, William Turley, Lynn Veeser

    2007-06-29

    When highly polished metal surfaces melt upon release after shock loading, they exhibit a number of features that suggest that significant surface changes accompany the phase transition. The reflection of light from such surfaces changes from specular (pre-shock) to diffuse upon melting. A familiar manifestation of this phenomenon is the loss of signal light in velocimetric measurements typically observed above pressures high enough to melt the free-surface. Unlike many other potential material phase-sensitive diagnostics (e.g., reflectometery, conductivity), changes in the specularity of reflection provide a dramatic, sensitive indicator of the solid-liquid phase transition. Data will be presented from multiple diagnostics that support the hypothesis that specularity changes indicate melt. These diagnostics include shadowgraphy, infrared imagery, high-magnification surface images, interferometric velocimetry, and most recently scattering angle measurements.

  12. Surface Specularity as an Indicator of Shock-induced Solid-liquid Phase Transitions in Tin

    SciTech Connect

    G. D. Stevens, S. S. Lutz, B. R. Marshall, W.D. Turley, et al.

    2007-12-01

    When highly polished metal surfaces melt upon release after shock loading, they exhibit features that suggest significant surface changes accompany the phase transition. The reflection of light from such surfaces changes from specular (pre-shock) to diffuse upon melting. Typical of this phenomenon is the loss of signal light in velocity interferometer system for any reflector (VISAR) measurements, which usually occurs at pressures high enough to melt the free surface. Unlike many other potential material phase-sensitive diagnostics (e.g., reflectometry, conductivity), that show relatively small (1%-10%) changes, the specularity of reflection provides a more sensitive and definitive (>10x) indication of the solid-liquid phase transition. Data will be presented that support the hypothesis that specularity changes indicate melt in a way that can be measured easily and unambiguously.

  13. Syringe-cartridge solid-phase extraction method for patulin in apple juice.

    PubMed

    Eisele, Thomas A; Gibson, Midori Z

    2003-01-01

    A syringe-cartridge solid-phase extraction (SPE) method was developed for determination of patulin in apple juice. A 2.5 mL portion of test sample was passed through a conditioned macroporous SPE cartridge and washed with 2 mL 1% sodium bicarbonate followed by 2 mL 1% acetic acid. Patulin was eluted with 1 mL 10% ethyl acetate in ethyl ether and determined by reversed-phase liquid chromatography using a mobile phase consisting of 81% acetonitrile, 9% water, and 10% 0.05M potassium phosphate buffer, pH 2.4. Recoveries averaged 92% and the relative standard deviation was 8.0% in test samples spiked with 50 ng/mL patulin. The method appears to be applicable for monitoring apple juice samples to meet the U.S. Food and Drug Administration compliance action level of 50 microg/kg in an industrial quality assurance laboratory environment.

  14. MULTI-PHASE CFD MODELING OF A SOLID SORBENT CARBON CAPTURE SYSTEM

    SciTech Connect

    Ryan, Emily M.; Xu, Wei; DeCroix, David; Saha, Kringan; Huckaby, E. D.; Darteville, Sebastien; Sun, Xin

    2012-05-01

    Post-combustion solid sorbent carbon capture systems are being studied via computational modeling as part of the U.S. Department of Energy’s Carbon Capture Simulation Initiative (CCSI). The work focuses on computational modeling of device-scale multi-phase computational fluid dynamics (CFD) simulations for given carbon capture reactor configurations to predict flow properties, outlet compositions, temperature and pressure. The detailed outputs of the device-scale models provide valuable insight into the operation of new carbon capture devices and will help in the design and optimization of carbon capture systems. As a first step in this project we have focused on modeling a 1 kWe solid sorbent carbon capture system using the commercial CFD software ANSYS FLUENT®. Using the multi-phase models available in ANSYS FLUENT®, we are investigating the use of Eulerian-Eulerian and Eulerian-Lagrangian methods for modeling a fluidized bed carbon capture design. The applicability of the dense discrete phase method (DDPM) is being considered along with the more traditional Eulerian-Eulerian multi-phase model. In this paper we will discuss the design of the 1 kWe solid sorbent system and the setup of the DDPM and Eulerian-Eulerian models used to simulate the system. The results of the hydrodynamics in the system will be discussed and the predictions of the DDPM and Eulerian-Eulerian simulations will be compared. A discussion of the sensitivity of the model to boundary and initial conditions, computational meshing, granular pressure, and drag sub-models will also be presented.

  15. Laboratory investigation of aluminum solubility and solid-phase properties following alum treatment of lake waters.

    PubMed

    Berkowitz, Jacob; Anderson, Michael A; Graham, Robert C

    2005-10-01

    Water samples from two southern California lakes adversely affected by internal nutrient loading were treated with a 20 mg/L dose of Al3+ in laboratory studies to examine Al solubility and solid-phase speciation over time. Alum [Al2(SO4)3 . 18 H2O] applications to water samples from Big Bear Lake and Lake Elsinore resulted in a rapid initial decrease in pH and alkalinity followed by a gradual recovery in pH over several weeks. Dissolved Al concentrations increased following treatment, reaching a maximum of 2.54 mg/L after 17 days in Lake Elsinore water and 0.91 mg/L after 48 days in Big Bear Lake water; concentrations in both waters then decreased to <0.25 mg/L after 150 days. The solid phase was periodically collected and analyzed using X-ray diffraction (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), scanning electron microscopy (SEM), and surface area analyses to investigate the nature of the reaction products and crystallinity development over time. Poorly ordered, X-ray amorphous solid phases transformed over time to relatively well-ordered gibbsite, with strong diffraction peaks at 4.8 and 4.3 A. XRD also indicated the formation of a second (possibly aluminosilicate) crystalline phase after 150 days in Lake Elsinore water. Surface areas also decreased over time as crystals reordered to form gibbsite/microcrystalline gibbsite species. DSC-TGA results suggested that the initially formed amorphous Al(OH)3 underwent transformation to >45% gibbsite. These results were supported by geochemical modeling using Visual MINTEQ, with Al solubility putatively controlled by amorphous Al(OH)3 shortly after treatment and approaching that of microcrystalline gibbsite after about 150 days. These findings indicate that Al(OH)3 formed after alum treatment undergoes significant chemical and mineralogical changes that may alter its effectiveness as a reactive barrier to phosphorus release from lake sediments.

  16. Solid-phase extraction and HPLC assay of nicotine and cotinine in plasma and brain.

    PubMed

    Dawson, Ralph; Messina, S M; Stokes, C; Salyani, S; Alcalay, N; De Fiebre, N C; De Fiebre, C M

    2002-01-01

    The aim of this study was to develop a simple and reliable assay for nicotine (NIC) and its major metabolite, cotinine (COT), in plasma and brain. A method was developed that uses an extraction method compatible with reverse-phase high-performance liquid chromatography (HPLC) separation and ultraviolet (UV) detection. Sequential solid-phase extraction on silica columns followed by extraction using octadecyl (C18) columns resulted in mean percent recovery (n = 5) of 51 +/- 5, 64 +/- 10, and 52 +/- 10% for NIC, COT, and phenylimidazole (PI), respectively, in spiked 1-mL serum samples. Recovery (mean +/- SEM) of the internal standard (PI) from spiked samples of nicotine-injected rats averaged 64.1 +/- 1.5% (n = 138) from plasma, and 20.7+/-0.8% (n = 128) from brain. The limits of detection of NIC in plasma samples were approximately 8 ng per mL, and of COT, 13.6 ng per mL. Further optimization of our extraction method, using slower flow rates and solid-phase extraction on silica columns, followed by C18 column extraction, yielded somewhat better recoveries (38 +/-3%) for 1-mL brain homogenates. Interassay precision (coefficient of variation) was determined on the basis of daily calibrations for 2 months and was found to be 7%, 9%, and 9% for NIC, COT, and PI, respectively, whereas intra-assay variability was 3.9% for both NIC and COT. Limited studies were performed on analytical columns for comparison of retention, resolution, asymmetry, and column capacity. We concluded that a simple two-step solid-phase extraction method, coupled with HPLC separation and UV detection, can be used routinely to measure NIC and COT in biological fluids and tissues.

  17. Aplication of Phase Shift Projection Moire Technique in Solid Surfaces Topographic Survey

    NASA Astrophysics Data System (ADS)

    Lino, A. C. L.; Dal Fabbro, I. M.; Enes, A. M.

    2008-04-01

    The application of projection moiré with phase shift techniques in vegetable organs surface topography survey had to step up basic procedures before reaching significant conclusions. As recommended by [1], the proposed method should be tested on virtual surfaces [1] before being carried on solid symmetric surfaces [2], followed by tests on asymmetric surfaces as fruits [3] and finally a generation of a 3D digital models of solid figures as well as of fruits [4]. In this research, identified as the step [2], tested objects included cylinders, cubes and spheres. In this sense a Ronchi grid named G1 was generated in a PC, from which other grids referred as G2, G3, and G4 were set out of phase by 1/4, 1/2 and 3/4 of period from G1. Grid G1 was then projected onto the samples surface instead of being virtually distorted, receiving the name of Gd. The difference between Gd and G1, G2, G3, and G4 followed by filtration generated the moiré fringes M1, M2, M3 and M4 respectively. Fringes are out of phase one from each other by 1/4 of period, which were processed by the Rising Sun Moiré software to produce packed phase and further on, the unpacked fringes. Final representations in gray levels as well as in contour lines showed the topography of the deformed grid Gd. Parallel line segments were projected onto moiré generated surface images to evaluate the approximation to the real surface. Line segments images were then captured by means of the ImageJ software and the corresponding curve fitting obtained. The work conclusions included the reliability of the proposed method in surveying solid figures shape.

  18. New Computational Approach to Determine Liquid-Solid Phase Equilibria of Water Confined to Slit Nanopores.

    PubMed

    Kaneko, Toshihiro; Bai, Jaeil; Yasuoka, Kenji; Mitsutake, Ayori; Zeng, Xiao Cheng

    2013-08-13

    We devise a new computational approach to compute solid-liquid phase equilibria of confined fluids. Specifically, we extend the multibaric-multithermal ensemble method with an anisotropic pressure control to achieve the solid-liquid phase equilibrium for confined water inside slit nanopores (with slit width h ranging from 5.4 Å to 7.2 Å). A unique feature of this multibaric-multithermal ensemble is that the freezing points of confined water can be determined from the heat-capacity peaks. The new approach has been applied to compute the freezing point of two monolayer ices, namely, a high-density flat rhombic monolayer ice (HD-fRMI) and a high-density puckered rhombic monolayer ice (HD-pRMI) observed in our simulation. We find that the liquid-to-solid transition temperature (or the freezing point) of HD-pRMI is dependent on the slit width h, whereas that of HD-fRMI is nearly independent of the h.

  19. Characterization of Human Skin Emanations by Solid Phase Microextraction (SPME) Extraction of Volatiles and Subsequent Analysis by Gas Chromatography-Mass Spectrometry (GC-MS)

    DTIC Science & Technology

    2007-11-02

    1 Characterization of Human Skin Emanations by Solid Phase Microextraction (SPME) Extraction of Volatiles and Subsequent Analysis by Gas...DATES COVERED - 4. TITLE AND SUBTITLE Characterization of Human Skin Emanations by Solid Phase Microextraction (SPME) Extraction of Volatiles...3 Characterization of Human Skin Emanations by Solid Phase Microextraction (SPME) Extraction of Volatiles and Subsequent Analysis by Gas

  20. β-Cyclodextrin enhanced on-line organic solvent field-amplified sample stacking in capillary zone electrophoresis for analysis of ambroxol in human plasma, following liquid-liquid extraction in the 96-well format.

    PubMed

    Li, Ji; Bi, Youwei; Wang, Li; Sun, Fanlu; Chen, Zhao; Xu, Guili; Fan, Guorong

    2012-07-01

    A field-amplified sample stacking (FASS) and capillary zone electrophoresis (CZE) method is described for the quantification of ambroxol hydrochloride in human plasma, following liquid-liquid extraction in the 96-well format. The separation was carried out at 25 °C in a 31.2 cm × 75 μm fused-silica capillary with an applied voltage of 15 kV. The background electrolyte (BGE) was composed of 6.25 mM borate-25 mM phosphate (pH 3.0) and 1mM β-cyclodextrin. The detection wavelength was 210 nm. Clean-up and preconcentration of plasma biosamples were developed by 96-well format liquid-liquid extraction (LLE). In this study, FASS in combination with β-cyclodextrin enhanced the sensitivity about 60-70 fold in total. The method was suitably validated with respect to stability, specificity, linearity, lower limit of quantitation, accuracy, precision, extraction recovery and robustness. The calibration graph was linear for ambroxol hydrochloride from 2 to 500 ng/ml. The lower limit of quantification was 2 ng/ml. The intra- and inter-day precisions of lowest limit of quantification (LLOQ) were 9.61 and 11.80%, respectively. The method developed was successfully applied to the evaluation of clinical pharmacokinetic study of ambroxol hydrochloride tablet after oral administration to 12 healthy volunteers.

  1. Solid/liquid phase diagram of the ammonium sulfate/glutaric acid/water system.

    PubMed

    Beyer, Keith D; Pearson, Christian S; Henningfield, Drew S

    2013-05-02

    We have studied the low temperature phase diagram and water activities of the ammonium sulfate/glutaric acid/water system using differential scanning calorimetry, infrared spectroscopy of thin films, and a new technique: differential scanning calorimetry-video microscopy. Using these techniques, we have determined that there is a temperature-dependent kinetic effect to the dissolution of glutaric acid in aqueous solution. We have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/glutaric acid phase boundary as well as the ternary eutectic composition and temperature. We have also modified our glutaric acid/water binary phase diagram previously published based on these new results. We compare our results for the ternary system to the predictions of the Extended AIM Aerosol Thermodynamics Model (E-AIM), and find good agreement for the ice melting points in the ice primary phase field of this system; however, significant differences were found with respect to phase boundaries, concentration and temperature of the ternary eutectic, and glutaric acid dissolution.

  2. Selective Separation of Fe-Concentrates in EAF Slags Using Mechanical Dissimilarity of Solid Phases

    NASA Astrophysics Data System (ADS)

    Jung, Sung Suk; Jung, Keeyoung; Sohn, Il

    2017-02-01

    We sought to develop an optimized particle size-dependent separation method to lower the Fe content of pulverized glass-ceramic electric arc furnace (EAF) slag for its improved reclamation as construction materials by considering the structures and the mechanical behavior of the discrete solid phases. After an isothermal crystallization process to enhance the spinel growth, the Vickers hardness and fracture toughness were measured on the spinel and amorphous phases separately from the solidified slag using indentation methods. The characteristic differences in the hardness of the phases were magnified when this glass-ceramic composite was isothermally crystallized. The hardness of the spinel was observed to be lower in slags with higher FetO/Al2O3 mass ratios due to the triclinic unit cell expansion of the spinel, whereas the hardness of the amorphous phase decreased with increasing isothermal period because of the structural transformation into a silicate-dominant network. Fracture toughness could be calculated based on the hardness and crack length, where the Young's modulus was determined using nanoindentation. The amorphous phase with a lower Fe content and lower fracture toughness resulted in finer powder distribution after pulverization, allowing better separation of the primary crystalline spinel containing higher Fe content from the Fe-deficient amorphous phase according to the particle size.

  3. UV-visible spectroscopy as an alternative to liquid chromatography for determination of everolimus in surfactant-containing dissolution media: a useful approach based on solid-phase extraction.

    PubMed

    Kamberi, Marika; Tran, Thu-Ngoc

    2012-11-01

    High-throughput 96-well solid phase extraction (SPE) plate with C-18 reversed phase sorbent followed by UV-visible (UV-Vis) microplate reader was applied to the analysis of hydrophobic drugs in surfactant-containing dissolution media, which are often used to evaluate the in-vitro drug release of drug eluting stents (DES). Everolimus and dissolution medium containing Triton X-405 were selected as representatives, and the appropriate SPE conditions (adsorption, washing and elution) were investigated to obtain a practical and reliable sample clean-up. It was shown that the developed SPE procedure was capable of removing interfering components (Triton X-405 and its impurities), allowing for an accurate automated spectrophotometric analysis to be performed. The proposed UV-Vis spectrophotometric method yielded equivalent results compared to a classical LC analysis method. Linear regression analysis indicated that both methods have the ability to obtain test results that are directly proportional to the concentration of analyte in the sample within the selected range of 1.0-10 μg/ml for everolimus, with a coefficient of correlation (r(2)) value of >0.998 and standard deviation of the residuals (Syx) of <2%. The individual recoveries of everolimus ranged from 97 to 104% for the UV-Vis spectrophotometric method and from 98 to 102 for the HPLC method, respectively. The 95% CI of the mean recovery for the UV-Vis spectrophotometric method was 99-102% and for the HPLC method was 99-101%. No statistical difference was found between the mean recoveries of the methods (p=0.42). Hence the methods are free from interference due to Triton and other chemicals present in the dissolution medium. The variation in the amount of everolimus estimated by UV-Vis spectrophotometric and HPLC methods was ≤3.5%, and the drug release profiles obtained by both methods were found to be equivalent by evaluation with two-one-sided t-test (two-tailed, p=0.62; mean of differences, 0.17; 95% CI, 0

  4. Liquid-solid sample preparation followed by headspace solid-phase microextraction determination of multiclass pesticides in soil.

    PubMed

    Durović, Rada D; Dordević, Tijana M; Santrić, Ljiljana R

    2012-01-01

    This paper describes development and validation of a multiresidue method for the determination of five pesticides (terbufos, prochloraz, chloridazon, pendimethalin, and fluorochloridone) belonging to different pesticide groups in soil samples by GC/MS, followed by its application in the analysis of some agricultural soil samples. The method is based on a headspace solid-phase microextraction method. Microextraction conditions, namely temperature, extraction time, and NaCI content, were tested and optimized using a 100 microm polydimethylsiloxane fiber. Three extraction solvents [methanol, methanol-acetone (1 + 1, v/v), and methanol-acetone-hexane (2 + 2 + 1, v/v/v)] and the optimum number of extraction steps within the sample preparation stage were optimized for the extraction procedure. LOD values for all the studied compounds were less than 12 microg/kg. Recovery values for multiple analyses of soil samples fortified at 30 microg/kg of each pesticide were higher than 64%. The method was proven to be repeatable, with RSD lower than 15%.

  5. Iron solid-phase differentiation along a redox gradient in basaltic soils

    NASA Astrophysics Data System (ADS)

    Thompson, Aaron; Rancourt, Denis G.; Chadwick, Oliver A.; Chorover, Jon

    2011-01-01

    Iron compounds in soil are multifunctional, providing physical structure, ion sorption sites, catalytic reaction-centers, and a sink for respiratory electrons. Basaltic soils contain large quantities of iron that reside in different mineral and organic phases depending on their age and redox status. We investigated changes in soil iron concentration and its solid-phase speciation across a single-aged (400 ky) lava flow subjected to a gradient in precipitation (2200-4200 mm yr -1) and hence redox history. With increasing rainfall and decreasing Eh, total Fe decreased from about 25% to <1% of the soil mass. Quantitative speciation of soil solid-phase iron was constrained by combining 57Fe Mössbauer spectroscopy (MBS) at 295 and 4.2 K with powder X-ray diffraction, selective chemical extractions, and magnetic susceptibility measurements. This approach allowed us to partition iron into (1) nanoparticulate and microcrystalline Fe III-(oxy)hydroxides, (2) microcrystalline and bulk Fe III-oxides, (3) organic/silicate bound Fe III, and (4) ferrous iron. The Fe III-(oxy)hydroxide fraction dominated solid-phase Fe, exhibiting a crystallinity continuum based on magnetic ordering temperature. The continuum extended from well-ordered microcrystalline goethite through nanocrystalline Fe III-(oxy)hydroxides to a nano Fe III-(oxy)hydroxide phase of extremely low crystallinity. Magnetic susceptibility was correlated ( R2 = 0.77) with Fe III-oxide concentration, consistent with a contribution of maghemite to the otherwise hematite dominated Fe-oxide fraction. The Fe III-(oxy)hydroxide fraction of total Fe decreased with increasing rainfall and was replaced by corresponding increase in the organic/silicate Fe III fraction. The crystallinity of the Fe III-(oxy)hydroxides also decreased with increasing rainfall and leaching, with the most disordered members of the crystallinity continuum, the nano Fe III-(oxy)hydroxides, gaining proportional abundance in the wetter sites. This finding

  6. A Two-Phase Solid/Fluid Model for Dense Granular Flows Including Dilatancy Effects

    NASA Astrophysics Data System (ADS)

    Mangeney, A.; Bouchut, F.; Fernández-Nieto, E. D.; Narbona-Reina, G.; Kone, E. H.

    2014-12-01

    We propose a thin layer depth-averaged two-phase model to describe solid-fluid mixtures such as debris flows. It describes the velocity of the two phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure, that itself modifies the friction within the granular phase (Iverson et al., 2010). The model is derived from a 3D two-phase model proposed by Jackson (2000) based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work (Bouchut et al., 2014). In particular, Pitman and Le replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's equations. We close the mixture equations by a weak compressibility relation involving a critical density, or equivalently a critical pressure. Moreover, we relax one boundary condition, making it possible for the fluid to escape the granular media when compression of the granular mass occurs. Furthermore, we introduce second order terms in the equations making it possible to describe the evolution of the pore fluid pressure in response to the compression/dilatation of the granular mass without prescribing an extra ad-hoc equation for the pore pressure. We prove that the energy balance associated with this Jackson closure is dissipative, as well as its thin layer associated model. We present several numerical tests for the 1D case that are compared to the

  7. A Two-Phase Solid/Fluid Model for Dense Granular Flows Including Dilatancy Effects

    NASA Astrophysics Data System (ADS)

    Mangeney, Anne; Bouchut, Francois; Fernandez-Nieto, Enrique; Narbona-Reina, Gladys

    2015-04-01

    We propose a thin layer depth-averaged two-phase model to describe solid-fluid mixtures such as debris flows. It describes the velocity of the two phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure, that itself modifies the friction within the granular phase (Iverson et al., 2010). The model is derived from a 3D two-phase model proposed by Jackson (2000) based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work (Bouchut et al., 2014). In particular, Pitman and Le replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's equations. We close the mixture equations by a weak compressibility relation involving a critical density, or equivalently a critical pressure. Moreover, we relax one boundary condition, making it possible for the fluid to escape the granular media when compression of the granular mass occurs. Furthermore, we introduce second order terms in the equations making it possible to describe the evolution of the pore fluid pressure in response to the compression/dilatation of the granular mass without prescribing an extra ad-hoc equation for the pore pressure. We prove that the energy balance associated with this Jackson closure is dissipative, as well as its thin layer associated model. We present several numerical tests for the 1D case that are compared to the

  8. Analysis of ecologically relevant pharmaceuticals in wastewater and surface water using selective solid phase extraction and UPLC/MS/MS

    EPA Science Inventory

    A rapid and sensitive method has been developed for the analysis of 48 human prescription active pharmaceutical ingredients (APIs) and 6 metabolites of interest, utilizing selective solid-phase extraction (SPE) and ultra performance liquid chromatography in combination with tripl...

  9. Phase transformations and the spectral reflectance of solid sulfur - Can metastable sulfur allotropes exist on Io?

    NASA Technical Reports Server (NTRS)

    Moses, Julianne I.; Nash, Douglas B.

    1991-01-01

    Laboratory investigations have been conducted on the effects of variations in sulfur sample histories on their solid-state transformation rate and the corresponding spectral variation of freshly frozen sulfur. The temporal variations in question may be due to differences in the amount and type of metastable allotropes present in the sulfur after solidification, as well as to the physics of the phase-transformation process itself. The results obtained are pertinent to the physical behavior and spectral variation of such freshly solidified sulfur as may exist on the Jupiter moon Io; this would initially solidify into a glassy solid or monoclinic crystalline lattice, then approach ambient dayside temperatures. Laboratory results imply that the monoclinic or polymeric allotropes can in these circumstances be maintained, and will take years to convert to the stable orthorhombic crystalline form.

  10. Liquid-solid phase transition of hydrogen and deuterium in silica aerogel

    NASA Astrophysics Data System (ADS)

    Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

    2014-10-01

    Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H2 and D2 in an ˜85%-porous base-catalyzed silica aerogel. We find that liquid-solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ˜4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H2 and D2 confined inside the aerogel monolith. Results for H2 and D2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.

  11. Explosive ordnance detection in land and water environments with solid phase extraction/ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Chambers, William B.; Phelan, James M.; Rodacy, Philip J.; Reber, Steven; Woodfin, Ronald L.

    1999-08-01

    The qualitative and quantitative determination of nitroaromatic compounds such as trinitrotoluene (TNT) and dinitrotoluene (DNT) in water and soil has applications to environmental remediation and the detection of buried military ordnance. Recent results of laboratory and field test have shown that trace level concentrations of these compounds can be detected in water, soil, and solid gas samples taken from the vicinity of submerged or buried ordnance using specialized sampling and signal enhancement techniques. Solid phase micro-extraction methods have been combined with Ion Mobility Spectroscopy to provide rapid, sub-parts-per-billion analysis of these compounds. In this paper, we will describe the gas. These sampling systems, when combined with field-portable IMS, are being developed as a means of classifying buried or submerged objects as explosive ordnance.

  12. Novel solid-phase synthesis of thiol-terminated-poly(alpha-amino acid)-drug conjugate.

    PubMed

    Palacios, P; Bussat, P; Bichon, D

    1991-01-01

    A new method using a controlled pore glass solid support for the preparation of a thiol-terminated-polymerdrug, notably poly-L-glutamate-daunomycin having a terminal thiol group, is described. The method consists of first polymerizing an ester-protected glutamic acid onto an amino-disulfide functionalized controlled pore glass support. The ester protecting group is then removed, freeing the gamma-carboxyl groups of the grafted polymer which then allows it to react with daunomycin. Finally, the disulfide bond linking the conjugated polymer-drug to the solid support is broken by thiolysis, thus releasing the desired product. The final product consists of only polymer-drug conjugates with terminal thiol groups (global yield 26%). This novel method is much simpler and more elegant than more conventional preparation methods requiring solution phase techniques.

  13. A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics.

    PubMed

    Thiyagarajan, Shanmugam; Genuino, Homer C; van der Waal, Jan C; de Jong, Ed; Weckhuysen, Bert M; van Haveren, Jacco; Bruijnincx, Pieter C A; van Es, Daan S

    2016-01-22

    Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels-Alder (DA) aromatization route, to effectively block retro-DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal-based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80% selectivity in a solid-phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H-Y was found to perform the best and can be easily reused after calcination.

  14. Solid-phase synthesis of lidocaine and procainamide analogues using backbone amide linker (BAL) anchoring.

    PubMed

    Shannon, Simon K; Peacock, Mandy J; Kates, Steven A; Barany, George

    2003-01-01

    New solid-phase strategies have been developed for the synthesis of lidocaine (1) and procainamide (2) analogues, using backbone amide linker (BAL) anchoring. Both sets were prepared starting from a common resin-bound intermediate, followed by four general steps: (i) attachment of a primary aliphatic or aromatic amine to the solid support via reductive amination (as monitored by a novel test involving reaction of 2,4-dinitrophenylhydrazine with residual aldehyde groups); (ii) acylation of the resultant secondary amine; (iii) displacement of halide with an amine; and (iv) trifluoroacetic acid-mediated release from the support. A manual parallel strategy was followed to provide 60 novel compounds, of which two dozen have not been previously described. In most cases, initial crude purities were >80%, and overall isolated yields were in the 40-88% range.

  15. Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

    SciTech Connect

    Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

    2014-10-28

    Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H{sub 2} and D{sub 2} in an ∼85%-porous base-catalyzed silica aerogel. We find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ∼4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H{sub 2} and D{sub 2} confined inside the aerogel monolith. Results for H{sub 2} and D{sub 2} are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.

  16. C-104 Solid Phase Characterization of Sample 4C-13-1 From Tank 241-C-104 Closure Sampling Event

    SciTech Connect

    Cooke, Gary A.; Pestovich, John A.

    2013-06-12

    One solid grab sample from closure sampling in Riser 7 of tank 214-C-I04 (C-I04) was examined to determine the solid phases that were present. The sample was analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The purpose of this analysis was to see if the presence of hydrated phases could provide a possible explanation for the high moisture content obtained from thermogravimetric analysis (TGA).

  17. Mechanistic understanding of calcium-phosphonate solid dissolution and scale inhibitor return behavior in oilfield reservoir: formation of middle phase.

    PubMed

    Zhang, Ping; Shen, Dong; Ruan, Gedeng; Kan, Amy T; Tomson, Mason B

    2016-08-03

    Phosphonates are an important class of mineral scale inhibitors used for oilfield scale control. By injecting the phosphonate into an oilfield reservoir, calcium-phosphonate precipitate will form and subsequently release the phosphonate into produced water for scale control. In this study, a systematic procedure is developed to mechanistically characterize an acidic calcium-phosphonate amorphous material that is later developed into a middle phase and eventually a crystalline phase. The phosphonate used in this study is diethylenetriamine pentakis (methylene phosphonic acid) (DTPMP). An amorphous calcium-DTPMP solid is precipitated by mixing a calcium-containing solution with a DTPMP solution. The stoichiometry of this initially formed solid can be experimentally confirmed via a static dissolution test. Following another dynamic development test, two additional Ca-DTPMP solid phases, i.e., a middle phase and a crystalline phase have been observed. Electron microscopy and X-ray diffraction were employed to characterize the morphology and crystallinity of different Ca-DTPMP solids of interest. Evidently, the dynamic brine flushing of the Ca-DTPMP solid developed the initially amorphous material into a middle phase solid with an amorphous/microcrystalline structure and eventually into a crystalline material. Furthermore, a dissolution characterization study was carried out to determine the solubility product of the middle phase solid at different conditions. The obtained mechanistic understanding of the Ca-DTPMP solid related to precipitation chemistry, dissolution behavior and phase transition is critical to elucidate oilfield DTPMP return data and more importantly, can optimize the oilfield scale squeeze design to achieve an extended squeeze lifetime.

  18. Total enthalpy-based lattice Boltzmann method with adaptive mesh refinement for solid-liquid phase change

    NASA Astrophysics Data System (ADS)

    Huang, Rongzong; Wu, Huiying

    2016-06-01

    A total enthalpy-based lattice Boltzmann (LB) method with adaptive mesh refinement (AMR) is developed in this paper to efficiently simulate solid-liquid phase change problem where variables vary significantly near the phase interface and thus finer grid is required. For the total enthalpy-based LB method, the velocity field is solved by an incompressible LB model with multiple-relaxation-time (MRT) collision scheme, and the temperature field is solved by a total enthalpy-based MRT LB model with the phase interface effects considered and the deviation term eliminated. With a kinetic assumption that the density distribution function for solid phase is at equilibrium state, a volumetric LB scheme is proposed to accurately realize the nonslip velocity condition on the diffusive phase interface and in the solid phase. As compared with the previous schemes, this scheme can avoid nonphysical flow in the solid phase. As for the AMR approach, it is developed based on multiblock grids. An indicator function is introduced to control the adaptive generation of multiblock grids, which can guarantee the existence of overlap area between adjacent blocks for information exchange. Since MRT collision schemes are used, the information exchange is directly carried out in the moment space. Numerical tests are firstly performed to validate the strict satisfaction of the nonslip velocity condition, and then melting problems in a square cavity with different Prandtl numbers and Rayleigh numbers are simulated, which demonstrate that the present method can handle solid-liquid phase change problem with high efficiency and accuracy.

  19. Multivariate Quantification of the Solid State Phase Composition of Co-Amorphous Naproxen-Indomethacin.

    PubMed

    Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

    2015-10-27

    To benefit from the optimized dissolution properties of active pharmaceutical ingredients in their amorphous forms, co-amorphisation as a viable tool to stabilize these amorphous phases is of both academic and industrial interest. Reports dealing with the physical stability and recrystallization behavior of co-amorphous systems are however limited to qualitative evaluations based on the corresponding X-ray powder diffractograms. Therefore, the objective of the study was to develop a quantification model based on X-ray powder diffractometry (XRPD), followed by a multivariate partial least squares regression approach that enables the simultaneous determination of up to four solid state fractions: crystalline naproxen, γ-indomethacin, α-indomethacin as well as co-amorphous naproxen-indomethacin. For this purpose, a calibration set that covers the whole range of possible combinations of the four components was prepared and analyzed by XRPD. In order to test the model performances, leave-one-out cross validation was performed and revealed root mean square errors of validation between 3.11% and 3.45% for the crystalline molar fractions and 5.57% for the co-amorphous molar fraction. In summary, even four solid state phases, involving one co-amorphous phase, can be quantified with this XRPD data-based approach.

  20. Solid-phase control on lead bioaccessibility in smelter-impacted soils.

    PubMed

    Romero, F M; Villalobos, M; Aguirre, R; Gutiérrez, M E

    2008-11-01

    The goal of this work was to identify the solid-phase control on lead (Pb) bioaccessibility in soils impacted by smelter activities in the city of San Luis Potosi, in north-central Mexico. Total Pb concentrations in 30 ha of soil terrain from a residential area adjacent to the smelter showed levels above the 400-mg/kg intervention guideline dictated by Mexican Environmental regulations. These concentrations, although raising human health and environmental concerns, showed low water-soluble lead (<0.1 mg/L) and relatively low lead bioaccessibility (2.4-20.5%). X-ray diffraction and electron microscopy techniques showed, in addition to common Pb phases reported in similar contaminated environments [galena (PbS) and anglesite (PbSO(4))], the presence of a solid lead arsenate phase. The Pb solubility measured in soils agrees very well with the low solubility reported for the Pb minerals identified and explains the relatively low Pb bioaccessibility values measured, presumably from their low dissolution during passage through the gastrointestinal tract. The results reported are highly relevant for smelter-originated environmental contamination scenarios in general.

  1. Determination of amphetamines in hair by integrating sample disruption, clean-up and solid phase derivatization.

    PubMed

    Argente-García, A; Moliner-Martínez, Y; Campíns-Falcó, P; Verdú-Andrés, J; Herráez-Hernández, R

    2016-05-20

    The utility of matrix solid phase dispersion (MSPD) for the direct analysis of amphetamines in hair samples has been evaluated, using liquid chromatography (LC) with fluorescence detection and precolumn derivatization. The proposed approach is based on the employment of MSPD for matrix disruption and clean-up, followed by the derivatization of the analytes onto the dispersant-sample blend. The fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) has been used for derivatization. Different conditions for MSPD, analyte purification and solid phase derivatization have been tested, using amphetamine (AMP), methamphetamine (MET), ephedrine (EPE) and 3,4-methylenedioxymethamphetamine (MDMA) as model compounds. The results have been compared with those achieved by using ultrasound-assisted alkaline digestion and by MSPD combined with conventional solution derivatization. On the basis of the results obtained, a methodology is proposed for the analysis of amphetamines in hair which integrates sample disruption, clean-up and derivatization using a C18 phase. Improved sensitivity is achieved with respect to that obtained by the alkaline digestion or by the MSPD followed by solution derivatization methods. The method can be used for the quantification of the tested amphetamines within the 2.0-20.0ng/mg concentration interval, with limits of detection (LODs) of 0.25-0.75ng/mg. The methodology is very simple and rapid (the preparation of the sample takes less than 15min).

  2. Two-phase anaerobic digestion within a solid waste/wastewater integrated management system

    SciTech Connect

    De Gioannis, G.; Diaz, L.F.; Muntoni, A. Pisanu, A.

    2008-07-01

    A two-phase, wet anaerobic digestion process was tested at laboratory scale using mechanically pre-treated municipal solid waste (MSW) as the substrate. The proposed process scheme differs from others due to the integration of the MSW and wastewater treatment cycles, which makes it possible to avoid the recirculation of process effluent. The results obtained show that the supplying of facultative biomass, drawn from the wastewater aeration tank, to the solid waste acidogenic reactor allows an improvement of the performance of the first phase of the process which is positively reflected on the second one. The proposed process performed successfully, adopting mesophilic conditions and a relatively short hydraulic retention time in the methanogenic reactor, as well as high values of organic loading rate. Significant VS removal efficiency and biogas production were achieved. Moreover, the methanogenic reactor quickly reached optimal conditions for a stable methanogenic phase. Studies conducted elsewhere also confirm the feasibility of integrating the treatment of the organic fraction of MSW with that of wastewater.

  3. Solid state phase equilibria and intermetallic compounds of the Al-Cr-Ho system

    SciTech Connect

    Pang, Mingjun; Zhan, Yongzhong; Du, Yong

    2013-02-15

    The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C were experimentally investigated. The phase relations at 500 Degree-Sign C are governed by 14 three-phase regions, 29 two-phase regions and 15 single-phase regions. The existences of 10 binary compounds and 2 ternary phases have been confirmed. Al{sub 11}Cr{sub 2}, Al{sub 11}Cr{sub 4} and Al{sub 17}Ho{sub 2} were not found at 500 Degree-Sign C. Crystal structures of Al{sub 9}Cr{sub 4} and Al{sub 8}Cr{sub 4}Ho were determined by the Rietveld X-ray powder data refinement. Al{sub 9}Cr{sub 4} was found to exhibit cubic structure with space group I4-bar 3m (no. 217) and lattice parameters a=0.9107(5) nm. Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} structure type with space group I4/mmm (no. 139) and lattice parameters a=0.8909(4) nm, c=0.5120(5) nm. It is concluded that the obtained Al{sub 4}Cr phase in this work should be {mu}-Al{sub 4}Cr by comparing with XRD pattern of the hexagonal {mu}-Al{sub 4}Mn compound. - Graphical abstract: The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Al-Cr-Ho system has been investigated. Black-Right-Pointing-Pointer Al{sub 9}Cr{sub 4} has cubic structure with space group I4-bar 3m. Black-Right-Pointing-Pointer Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} type with space group I4/mmm. Black-Right-Pointing-Pointer Al{sub 4}Cr phase is {mu}-type at 500 Degree-Sign C.

  4. The effects of solid solution on the stability of the 10 Å phase

    NASA Astrophysics Data System (ADS)

    Howe, H.; Pawley, A. R.; Droop, G.

    2014-12-01

    Subduction of hydrous phases enables the transport of water into the typically anhydrous mantle. Dehydration of these phases has a dramatic expression at the Earth's surface in the form of earthquakes and arc volcanism. Within a subduction zone, talc (Mg3Si4O10(OH)2) is found within the hydrothermally altered oceanic crust and pelagic sediments of the subducting slab, as well as the metasomatised mantle wedge. The 10 Å phase (Mg3Si4O10(OH)2.H2O) forms from the breakdown of talc at low temperatures and pressures above 5 GPa, and is thought to be stable to depths up to 200 km1. Previous work has focused on the stability of Mg end-members of talc and the 10 Å phase. However, natural samples of talc show deviation from end member composition, most significantly in the substitution of iron for magnesium. It is likely that the stability of iron-bearing talc and its high pressure equivalent, the 10 Å phase, will differ from that of Mg end-member compositions, as demonstrated by previous studies examining the effect of solid solution in phyllosilicates such as antigorite. High pressure experiments using the multi-anvil press at the University of Manchester have bracketed the reaction talc + H2O = 10 Å phase for Mg end-member compositions. Samples of iron-bearing talc and the 10 Å phase have been synthesised at pressures of 2 GPa and 6.2 GPa, respectively. By performing phase equilibrium experiments on iron-bearing talc and 10 Å phase it is possible to quantify the effect of composition on the position of the reaction talc + H2O = 10 Å phase, as well the thermal breakdown of the 10 Å phase to enstatite and coesite. Univarient breakdown reactions assume that the 10 Å dehydrates at one discrete depth, where the thermal stability has been exceeded. The results are expected to show that instead, fluid release from 10 Å phase dehydration is more likely to occur over a range of depths during subduction, dependant on the bulk composition and the thermal regime of the

  5. Solid-phase immunoradiometric assay for serum amyloid A protein using magnetisable cellulose particles.

    PubMed

    De Beer, F C; Dyck, R F; Pepys, M B

    1982-10-29

    An immunoradiometric assay for human serum amyloid A protein (SAA) was developed using magnetisable cellulose particles as the solid phase. Rabbit antiserum to to SAA was raised by immunization with SAA isolated from acute-phase serum by gel filtration in formic acid. The antiserum was rendered monospecific for SAA by solid-phase immunoabsorption with normal human serum, which contains only traces of SAA, and some was coupled covalently to the cellulose particles. Immunopurified anti-SAA antibodies were isolated from the monospecific anti-SAA serum by binding to, and elution from insolubilized acute-phase serum and were radiolabelled with 125I. The assay was calibrated with an acute phase serum which contained 6000 times more SAA than normal sera with the lowest detectable level of SAA, and an arbitrary value of 6000 U/l was assigned to this standard. Sera were tested in the native, undenatured state and there was no increase in SAA immunoreactivity following alkali treatment or heating. The assay range was from 1-2000 U/l so that all SAA levels above 6 U/l could be measured on a single (1:6) dilution of serum. The intra- and interassay coefficients of variation were 11.7 and 15.0% respectively. Among 100 healthy normal subjects (50 male, 50 female) the median SAA level was 9 U/l, range less than 1-100, with 93% below 20 U/l and only 2% below the lower limit of sensitivity of the assay (1 U/l).

  6. Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies

    DOE PAGES

    Childs, Bradley C.; Braband, Henrik; Lawler, Keith; ...

    2016-10-04

    Here, ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), electron impact mass spectrometry (EI-MS) and theoretical methods. Refinement of the structure at 100 K indicates that Tc2O7 crystallizes as a molecular solid in the orthorhombic space group Pbca (a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, V = 557.5(3) Å3). The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedra (Tc---Tc = 3.698(1) Å and Tc-OBri-Tc = 180.0°). The EI-MS spectrum of Tc2O7 consists of both mononuclear and dinuclear species. The mainmore » dinuclear species in the gas-phase are Tc2O7 (100%) and Tc2O5 (56%), while the main mononuclear species are TcO3 (33.9%) and TcO2 (42.8%). The difference in the relative intensities of the M2O5 (M = Tc, Re) fragments (1.7% for Re) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc2O7 was investigated by density functional theory (DFT) methods. The optimized structure of the Tc2O7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc2O7 molecule in the gas-phase is bent (Tc-OBri-Tc = 156.5°), while linear (Tc-OBri-Tc = 180.0°) is favored in the solid state.« less

  7. Advanced Multi-phase Flow CFD Model Development for Solid Rocket Motor Flowfield Analysis

    NASA Technical Reports Server (NTRS)

    Liaw, Paul; Chen, Yen-Sen

    1995-01-01

    A Navier-Stokes code, finite difference Navier-Stokes (FDNS), is used to analyze the complicated internal flowfield of the SRM (solid rocket motor) to explore the impacts due to the effects of chemical reaction, particle dynamics, and slag accumulation on the solid rocket motor (SRM). The particulate multi-phase flowfield with chemical reaction, particle evaporation, combustion, breakup, and agglomeration models are included in present study to obtain a better understanding of the SRM design. Finite rate chemistry model is applied to simulate the chemical reaction effects. Hermsen correlation model is used for the combustion simulation. The evaporation model introduced by Spalding is utilized to include the heat transfer from the particulate phase to the gase phase due to the evaporation of the particles. A correlation of the minimum particle size for breakup expressed in terms of the Al/Al2O3 surface tension and shear force was employed to simulate the breakup of particles. It is assumed that the breakup occurs when the Weber number exceeds 6. A simple L agglomeration model is used to investigate the particle agglomeration. However, due to the large computer memory requirements for the agglomeration model, only 2D cases are tested with the agglomeration model. The VOF (Volume of Fluid) method is employed to simulate the slag buildup in the aft-end cavity of the redesigned solid rocket motor (RSRM). Monte Carlo method is employed to calculate the turbulent dispersion effect of the particles. The flowfield analysis obtained using the FDNS code in the present research with finite rate chemical reaction, particle evaporation, combustion, breakup, agglomeration, and VOG models will provide a design guide for the potential improvement of the SRM including the use of materials and the shape of nozzle geometry such that a better performance of the SRM can be achieved. The simulation of the slag buildup in the aft-end cavity can assist the designer to improve the design of

  8. Mechanisms and prevention of trifluoroacetylation in solid-phase peptide synthesis

    PubMed Central

    Kent, Stephen B. H.; Mitchell, Alexander R.; Engelhard, Martin; Merrifield, R. B.

    1979-01-01

    A novel mechanism for trifluoroacetylation in solid-phase peptide synthesis, independent of the coupling step, has been elucidated. It involves the presence of trifluoroacetoxymethyl groups on the resin support, which react with resin-bound amines by an intersite nucleophilic reaction. The trifluoroacetoxymethyl groups are generated from preexisting hydroxymethyl sites during treatment with trifluoroacetic acid in dichloromethane or by acidolysis of the benzyl ester bond between the peptide and the resin. The transfer of trifluoroacetyl from hydroxyl to amine occurs during the subsequent neutralization with tertiary amine. The mechanism was first elucidated by model studies with aminomethyl-resins. Then the expected transfer of trifluoroacetyl groups from trifluoroacetoxymethyl-resin to the α-amino group of Nε-benzyloxycarbonyllysine benzyl ester in solution was demonstrated; k2, 6 × 10-4 M-1. Lysine-resins were used to examine the extent of trifluoroacetylation under the conditions of solid-phase peptide synthesis. After a series of acid/base cycles simulating synthetic conditions but without coupling, the poorly nucleophilic α-amino group was approximately 1-2% trifluoroacetylated per cycle when attached to resins already containing hydroxymethyl groups. Standard benzyl ester resins without preexisting hydroxymethyl groups gave comparable levels of trifluoroacetylation after the first few synthetic cycles because of gradual acid cleavage of the ester and accumulation of trifluoroacetoxymethyl sites. Peptide chain termination resulting from trifluoroacetylation by this mechanism could be prevented (<0.02% per cycle) by the use of the aminoacyl-4-(oxymethyl)-phenylacetamidomethyl-resin support, which can be synthesized free from extraneous functionalities and which is stable to trifluoroacetic acid under the conditions of solid-phase peptide synthesis. PMID:287055

  9. Microcosm experiments to study the interaction of solid and solute phases during initial soil development

    NASA Astrophysics Data System (ADS)

    Zimmermann, C.; Chabbi, S.; Schaaf, W.

    2009-04-01

    During the initial phase of soil formation mineral weathering, interactions between the solid and liquid phases as well as accumulation of organic matter play an important role for the development of soil properties and for the establishment of vegetation and the colonization of soil biota. Our study is part of the Transregional Collaborative Research Centre (SFB/TRR 38) ‘Patterns and processes of initial ecosystem development in an artificial catchment' funded by the Deutsche Forschungsgemeinschaft (DFG). The catchment ´Chicken Creeḱ close to Cottbus (Germany) has a size of 6 ha and is composed of a 3-4 m layer of Quaternary loamy to sandy sediments overlying a 1-2 m clay layer. To connect interactions between the soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale we perform microcosm experiments with soil samples from the catchment under controlled laboratory conditions. The microcosm experiments are carried out in a climate chamber at constant 10 °C corresponding to the mean annual temperature of the region. In total 48 soil columns with a diameter of 14.4 cm and height of 30 cm were filled with substrates of two textural compositions reflecting the gradients observed at the catchment and a bulk density of 1.4-1.5 g*cm3. Within the microcosms it is possible to control the gaseous phase and the water fluxes by artificial irrigation. The irrigation runs automated and quasi-continuously four times a day with 6.6 ml each (in total 600 mm*yr-1). Irrigation amount and chemical composition of the artificial rainwater are based on the annual mean at the field site. Litter of two different plant species occurring at the catchment site (Lotus corniculatus, Calamagrostis epigejos) labelled with stable isotopes (δ13C; δ15N) is used for the experiments. All treatments including a control run with four replicates. The gaseous phase in the headspace of the microcosms is analysed continuously for CO2 and N2O contents

  10. Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

    PubMed

    Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

    2010-02-19

    The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition.

  11. Solid Phase Characterization of Tank 241-AY-102 Annulus Space Particulate

    SciTech Connect

    Cooke, G. A.

    2013-01-30

    The Special Analytical Studies Group at the 222-S Laboratory (222-S) examined the particulate recovered from a series of samples from the annular space of tank 241-AY-102 (AY-102) using solid phase characterization (SPC) methods. These include scanning electron microscopy (SEM) using the ASPEX®1 scanning electron microscope, X-ray diffraction (XRD) using the Rigaku®2 MiniFlex X-ray diffractometer, and polarized light microscopy (PLM) using the Nikon®3 Eclipse Pol optical microscope. The SEM is equipped with an energy dispersive X-ray spectrometer (EDS) to provide chemical information.

  12. Challenges of infrared reflective spectroscopy of solid-phase explosives and chemicals on surfaces

    SciTech Connect

    Phillips, Mark C.; Suter, Jonathan D.; Bernacki, Bruce E.; Johnson, Timothy J.

    2012-09-01

    Reliable active and passive hyperspectral imaging and detection of explosives and solid-phase chemical residue on surfaces remains a challenge and an active area of research and development. Both methods rely on reference libraries for material identification, but in many cases the reference spectra do not sufficiently resemble those instrumental signals scattered from real-world objects. We describe a physics-based model using the dispersive complex dielectric constant to explain what is often thought of as anomalous behavior of scattered or non-specular signatures encountered in active and passive sensing of explosives or chemicals on surfaces and show modeling and experimental results for RDX.

  13. Low-temperature solid-state phase transformations in 2H silicon carbide

    NASA Technical Reports Server (NTRS)

    Will, H. A.; Powell, J. A.

    1972-01-01

    Single crystals of 2H SiC were observed to undergo phase transformations at temperatures as low as 400 C. Some 2H crystals transformed to a structure with one-dimensional disorder along the crystal c axis. Others transformed to a faulted cubic/6H structure. The transformation is time and temperature dependent and is greatly enhanced by dislocations. Observations indicate that the transformation takes place by means of a slip process perpendicular to the c axis. Cubic SiC crystals were observed to undergo a solid state transformation above 1400 C.

  14. Click Reaction on Solid Phase Enables High Fidelity Synthesis of Nucleobase-Modified DNA.

    PubMed

    Tolle, Fabian; Rosenthal, Malte; Pfeiffer, Franziska; Mayer, Günter

    2016-03-16

    The post-synthetic functionalization of nucleic acids via click chemistry (CuAAC) has seen tremendous implementation, extending the applicability of nucleobase-modified nucleic acids in fields like fluorescent labeling, nanotechnology, and in vitro selection. However, the production of large quantities of high-density functionalized material via solid phase synthesis has been hampered by oxidative by-product formation associated with the alkaline workup conditions. Herein, we describe a rapid and cost-effective protocol for the high fidelity large-scale production of nucleobase-modified nucleic acids, exemplified with a recently described nucleobase-modified aptamer.

  15. Solid-phase synthesis of branched oligoribonucleotides related to messenger RNA splicing intermediates.

    PubMed Central

    Damha, M J; Ganeshan, K; Hudson, R H; Zabarylo, S V

    1992-01-01

    The chemical synthesis of oligoribonucleotides containing vicinal (2'-5')- and (3'-5')-phosphodiester linkages is described. The solid-phase method, based on silyl-phosphoramidite chemistry, was applied to the synthesis of a series of branched RNA [(Xp)nA2' (pN)n3'(pN)n] related to the splicing intermediates derived from Saccharomyces cerevisiae rp51a pre-messenger RNA. The branched oligonucleotides have been thoroughly characterized by nucleoside and branched nucleotide composition analysis. Branched oligoribonucleotides will be useful in the study of messenger RNA splicing and in determining the biological role of RNA 'lariats' and 'forks' in vivo. Images PMID:1480476

  16. An efficient protocol for the solid-phase synthesis of glycopeptides under microwave irradiation.

    PubMed

    Garcia-Martin, Fayna; Hinou, Hiroshi; Matsushita, Takahiko; Hayakawa, Shun; Nishimura, Shin-Ichiro

    2012-02-28

    A standardized and smooth protocol for solid-phase glycopeptides synthesis under microwave irradiation was developed. Double activation system was proved to allow for highly efficient coupling of Tn-Ser/Thr and bulky core 2-Ser/Thr derivatives. Versatility and robustness of the present strategy was demonstrated by constructing a Mucine-1 (MUC1) fragment and glycosylated fragments of tau protein. The success of this approach relies on the combination of microwave energy, a resin consisting totally of polyethylene glycol, a low excess of sugar amino acid and the "double activation" method.

  17. Diaminodiacid-based solid-phase synthesis of all-hydrocarbon stapled α-helical peptides.

    PubMed

    Wang, Feng-Liang; Guo, Ye; Li, Si-Jian; Guo, Qing-Xiang; Shi, Jing; Li, Yi-Ming

    2015-06-14

    An alternative stapling strategy is described herein using Fmoc-solid phase peptide synthesis (SPPS) that employed pre-prepared diaminodiacid building blocks to introduce all-hydrocarbon staples into peptides by on-resin cyclization. Compared to unstapled native peptides, diaminodiacid-based stapled peptides exhibited an increased α-helicity ratio and stability toward protease. Moreover, the linkage length was found to affect the bioactivity of the peptides and their ability to inhibit the Wnt pathway. Therefore, the new stapling method provides an alternative way to obtain stapled peptides with tunable linkers of diaminodiacids.

  18. [Anaerobic solid-phase fermentation of plant substrates by Bacillus subtilis].

    PubMed

    Ushakova, N A; Brodskiĭ, E S; Kozlova, A A; Nifatov, A V

    2009-01-01

    Solid-phase growth of Bacillus subtilis 8130 on cellulose-rich plant substrates (presscakes or pulp) under hypoxic conditions was accompanied by cellulose depolymerization, protein hydrolysis, and degradation of other plant components, including some processes of mixed-type carbohydrate fermentation. The bacterial fermentation yielded propionic, butyric, and hexanoic acids and butyric acid derivatives. The bacterial metabolism and fermentation degree can be characterized by the proportions of fatty acids in the reaction mixture. The product of sea buckthorn cake fermentation has a good sorption quality.

  19. Sequential, solid-phase assay for biotin in physiologic fluids that correlates with expected biotin status

    SciTech Connect

    Mock, D.M.; DuBois, D.B.

    1986-03-01

    Interest in accurate measurement of biotin concentrations in plasma and urine has been stimulated by recent advances in the understanding of biotin-responsive inborn errors of metabolism and by several reports describing acquired biotin deficiency during parenteral alimentation. This paper presents a biotin assay utilizing radiolabeled avidin in a sequential, solid-phase method; the assay has increased sensitivity compared to previous methods (greater than or equal to 10 fmol/tube), correlates with expected trends in biotin concentrations in blood and urine in a rat model of biotin deficiency, and can utilize commercially available radiolabeled avidin.

  20. Imaging time-of-flight secondary ion mass spectrometry of solid-phase peptide syntheses.

    PubMed

    Aubagnac, J L; Enjalbal, C; Drouot, C; Combarieu, R; Martinez, J

    1999-07-01

    Imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) of solid-phase peptide syntheses carried out by the Merrifield and Sheppard strategies is described. Mixtures of resin beads mixed at random from batch syntheses or obtained in combinatorial chemistry by the mix and split technique, where each bead is functionalized by a unique peptide, were analyzed directly without any chemical cleavage of the growing chains to assess the nature of the growing structure on any bead of the mixture without its isolation.

  1. Synthesis of graphene nanoribbons from amyloid templates by gallium vapor-assisted solid-phase graphitization

    SciTech Connect

    Murakami, Katsuhisa Dong, Tianchen; Kajiwara, Yuya; Takahashi, Teppei; Fujita, Jun-ichi; Hiyama, Takaki; Takai, Eisuke; Ohashi, Gai; Shiraki, Kentaro

    2014-06-16

    Single- and double-layer graphene nanoribbons (GNRs) with widths of around 10 nm were synthesized directly onto an insulating substrate by solid-phase graphitization using a gallium vapor catalyst and carbon templates made of amyloid fibrils. Subsequent investigation revealed that the crystallinity, conductivity, and carrier mobility were all improved by increasing the temperature of synthesis. The carrier mobility of the GNR synthesized at 1050 °C was 0.83 cm{sup 2}/V s, which is lower than that of mechanically exfoliated graphene. This is considered to be most likely due to electron scattering by the defects and edges of the GNRs.

  2. Reducing the sulfur-dioxide binding power of sweet white wines by solid-phase extraction.

    PubMed

    Saidane, Dorra; Barbe, Jean-Christophe; Birot, Marc; Deleuze, Hervé

    2013-11-01

    The high sulfur-dioxide binding power of sweet white wines may be reduced by extracting the naturally present carbonyl compounds from wine that are responsible for carbonyl bisulphites formation. The carbonyl compounds mainly responsible for trapping SO2 are acetaldehyde, pyruvic acid, and 2-oxoglutaric acid. The method employed was selective solid phase extraction, using phenylsulfonylhydrazine as a scavenging agent. The scavenging function was grafted onto a support prepared from raw materials derived from lignin. This approach is more acceptable to winemakers than the polymer media previously reported, as it reduces the possible contamination of wine to molecules already present in the wine making process.

  3. Automated solid-phase extraction of herbicides from water for gas chromatographic-mass spectrometric analysis

    USGS Publications Warehouse

    Meyer, M.T.; Mills, M.S.; Thurman, E.M.

    1993-01-01

    An automated solid-phase extraction (SPE) method was developed for the pre-concentration of chloroacetanilide and triazine herbicides, and two triazine metabolites from 100-ml water samples. Breakthrough experiments for the C18 SPE cartridge show that the two triazine metabolites are not fully retained and that increasing flow-rate decreases their retention. Standard curve r2 values of 0.998-1.000 for each compound were consistently obtained and a quantitation level of 0.05 ??g/l was achieved for each compound tested. More than 10,000 surface and ground water samples have been analyzed by this method.

  4. Mutual injection phase locking coherent combination of solid-state lasers based on corner cube.

    PubMed

    Cheng, Yong; Liu, Xu; Wan, Qiang; Zhu, Mengzhen; Mi, Chaowei; Tan, Chaoyong; Wei, Shangfang; Chen, Xia

    2013-12-01

    Coherent beam combination is an effective way to develop high-power lasers with high beam quality and high brightness. Coherent combination of six solid-state lasers based on the technique of mutual injection phase locking by using the natural coherent combination property of corner cube is first investigated. The coherent combination with 15.3 J of output energy, 1.7 mrad of divergent angle is obtained, and the combining efficiency is as high as 95.6% at 10 Hz and 85 A. The far-field profile is flattened protuberance.

  5. Facile synthesis of a 3-deazaadenosine phosphoramidite for RNA solid-phase synthesis

    PubMed Central

    2016-01-01

    Access to 3-deazaadenosine (c3A) building blocks for RNA solid-phase synthesis represents a severe bottleneck in modern RNA research, in particular for atomic mutagenesis experiments to explore mechanistic aspects of ribozyme catalysis. Here, we report the 5-step synthesis of a c3A phosphoramidite from cost-affordable starting materials. The key reaction is a silyl-Hilbert–Johnson nucleosidation using unprotected 6-amino-3-deazapurine and benzoyl-protected 1-O-acetylribose. The novel path is superior to previously described syntheses in terms of efficacy and ease of laboratory handling. PMID:28144324

  6. Different methods to select the best extraction system for solid-phase extraction.

    PubMed

    Bielicka-Daszkiewicz, Katarzyna

    2015-02-01

    The optimization methods for planning a solid-phase extraction experiment are presented. These methods are based on a study of interactions between different parts of an extraction system. Determination of the type and strength of interaction depends on the physicochemical properties of the individual components of the system. The main parameters that determine the extraction properties are described in this work. The influence of sorbents' and solvents' polarity on extraction efficiency, Hansen solubility parameters and breakthrough volume determination on sorption and desorption extraction step are discussed.

  7. Screening of Brazilian fruit aromas using solid-phase microextraction-gas chromatography-mass spectrometry.

    PubMed

    Augusto, F; Valente, A L; dos Santos Tada, E; Rivellino, S R

    2000-03-17

    Manual headspace solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) was used for the qualitative analysis of the aromas of four native Brazilian fruits: cupuassu (Theobroma grandiflorum, Spreng.), cajá (Spondias lutea. L.), siriguela (Spondias purpurea, L.) and graviola (Anona reticulata, L). Industrialized pulps of these fruits were used as samples, and extractions with SPME fibers coated with polydimethylsiloxane, polyacrylate, Carbowax and Carboxen were carried out. The analytes identified included several alcohols, esters, carbonyl compounds and terpernoids. The highest amounts extracted, evaluated from the sum of peak areas, were achieved using the Carboxen fiber.

  8. Novel nanoporous sorbent for solid-phase extraction in petroleum fingerprinting

    NASA Astrophysics Data System (ADS)

    Alayande, S. Oluwagbemiga; Hlengilizwe, Nyoni; Dare, E. Olugbenga; Msagati, Titus A. M.; Akinlabi, A. Kehinde; Aiyedun, P. O.

    2016-04-01

    Sample preparation is crucial in the analysis of petroleum and its derivatives. In this study, developing affordable sorbent for petroleum fingerprinting analysis using polymer waste such expanded polystyrene was explored. The potential of electrospun expanded polystyrene (EPS) as a sorbent for the solid-phase extraction (SPE) technique was investigated, and its efficiency was compared with commercial cartridges such as alumina, silica and alumina/silica hybrid commercial for petroleum fingerprinting analysis. The chromatograms showed that the packed electrospun EPS fibre demonstrated excellent properties for SPE applications relative to the hybrid cartridges.

  9. Rapid solid-phase peptide synthesis using thermal and controlled microwave irradiation.

    PubMed

    Bacsa, Bernadett; Desai, Bimbisar; Dibó, Gábor; Kappe, C Oliver

    2006-10-01

    A rapid and efficient microwave-assisted solid-phase synthesis method is described for the preparation of the nonapeptide WDTVRISFK, using conventional Fmoc/Bu(t) orthogonal protection strategy. The synthesis protocol is based on the use of cycles of pulsed microwave irradiation with intermittent cooling of the reaction during the removal of the Fmoc protecting group and during the coupling. The desired nonapeptide was obtained in highest yield and purity by employing MicroKan technology. The chemical reactions were carried out in a single-mode microwave reactor, equipped with a fiber-optic probe to monitor the reaction temperature continuously.

  10. Some applications of solid phase micro extraction (SPME) in the analysis of pesticide residues in food.

    PubMed

    Volante, M; Cattaneo, M; Bianchi, M; Zoccola, G

    1998-05-01

    The Solid Phase Micro-Extraction (SPME) technique was applied to analyze chlorpropham in potatoes and amitraz in honey. The homogenized sample, suspended in water and stirred, was extracted with a 100 microns thick polidimetylsiloxane fiber and desorbed into the injection port of a gas chromatograph/mass-spectrometer (quadrupole) operating in single ion monitoring. Sensitivities down to 0.01 mg/Kg and linear responses in the range of 0.01-0.1 mg/Kg were obtained. The results of SPME pesticide residue analysis in potatoes corresponded to those obtained with a traditional multiresidue method.

  11. The EPOS Implementation Phase: building thematic and integrated services for solid Earth sciences

    NASA Astrophysics Data System (ADS)

    Cocco, Massimo; Epos Consortium, the

    2015-04-01

    The European Plate Observing System (EPOS) has a scientific vision and approach aimed at creating a pan-European infrastructure for Earth sciences to support a safe and sustainable society. To follow this vision, the EPOS mission is integrating a suite of diverse and advanced Research Infrastructures (RIs) in Europe relying on new e-science opportunities to monitor and understand the dynamic and complex Earth system. To this goal, the EPOS Preparatory Phase has designed a long-term plan to facilitate integrated use of data and products as well as access to facilities from mainly distributed existing and new research infrastructures for solid Earth Science. EPOS will enable innovative multidisciplinary research for a better understanding of the Earth's physical processes that control earthquakes, volcanic eruptions, ground instability and tsunami as well as the processes driving tectonics and Earth surface dynamics. Through integration of data, models and facilities EPOS will allow the Earth Science community to make a step change in developing new concepts and tools for key answers to scientific and socio-economic questions concerning geo-hazards and geo-resources as well as Earth sciences applications to the environment and to human welfare. Since its conception EPOS has been built as "a single, Pan-European, sustainable and distributed infrastructure". EPOS is, indeed, the sole infrastructure for solid Earth Science in ESFRI and its pan-European dimension is demonstrated by the participation of 23 countries in its preparatory phase. EPOS is presently moving into its implementation phase further extending its pan-European dimension. The EPOS Implementation Phase project (EPOS IP) builds on the achievements of the successful EPOS preparatory phase project. The EPOS IP objectives are synergetic and coherent with the establishment of the new legal subject (the EPOS-ERIC in Italy). EPOS coordinates the existing and new solid Earth RIs within Europe and builds the

  12. Perovskite solid solutions with multiferroic morphotropic phase boundaries and property enhancement

    NASA Astrophysics Data System (ADS)

    Algueró, M.; Amorín, H.; Fernández-Posada, C. M.; Peña, O.; Ramos, P.; Vila, E.; Castro, A.

    2016-05-01

    Recently, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of phases in the BiFeO3-BiCoO3 perovskite binary system, associated with the existence of a discontinuous morphotropic phase boundary (MPB) between multiferroic polymorphs of rhombohedral and tetragonal symmetries. This might be a general property of multiferroic phase instabilities, and a novel promising approach for room temperature magnetoelectricity. We review here our current investigations on the identification and study of additional material systems, alternative to BiFeO3-BiCoO3 that has only been obtained by high pressure synthesis. Three systems, whose phase diagrams were, in principle, liable to show multiferroic MPBs have been addressed: the BiMnO3-PbTiO3 and BiFeO3-PbTiO3 binary systems, and the BiFeO3-BiMnO3-PbTiO3 ternary one. A comprehensive study of multiferroism across different solid solutions was carried out based on electrical and magnetic characterizations, complemented with mechanical and electromechanical measurements. An in-depth structural analysis was also accomplished when necessary.

  13. Manipulation and visualization of two-dimensional phase distribution of vibrational wave functions in solid parahydrogen crystal

    NASA Astrophysics Data System (ADS)

    Katsuki, Hiroyuki; Ohmori, Kenzo; Horie, Toru; Yanagi, Hisao; Ohmori, Kenji

    2015-09-01

    Solid parahydrogen, which is known to have an exceptionally long vibrational coherence lifetime as a molecular solid, offers an ideal testbed to perform coherent control experiments in the condensed phase. Here we demonstrate the spatial manipulation and visualization of the relative phase of vibrational wave functions in solid parahydrogen. Spatial distribution of vibrational excitation is generated by femtosecond impulsive Raman excitation. It is shown that the imprinted initial phase can be manipulated by wave-front modulation of the excitation laser pulses with a spatial light modulator. An interferometric measurement is used to convert the spatial phase distribution of the vibrational wave functions to the amplitude distribution. We have confirmed that the spatial profile of the scattered anti-Stokes pulse reveals the spatial phase distribution of the wave functions. The read-and-write scheme demonstrated in this experiment is applicable to a broad range of Raman memory systems accessible by Λ -type transitions.

  14. CRYOCHEM, Thermodynamic Model for Cryogenic Chemical Systems: Solid-Vapor and Solid-Liquid-Vapor Phase Equilibria Toward Applications on Titan and Pluto

    NASA Astrophysics Data System (ADS)

    Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.

    2014-12-01

    Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the

  15. Mechanical Yield in Amorphous Solids: A First-Order Phase Transition

    NASA Astrophysics Data System (ADS)

    Jaiswal, Prabhat K.; Procaccia, Itamar; Rainone, Corrado; Singh, Murari

    2016-02-01

    Amorphous solids yield at a critical value of the strain (in strain-controlled experiments); for larger strains, the average stress can no longer increase—the system displays an elastoplastic steady state. A long-standing riddle in the materials community is what the difference is between the microscopic states of the material before and after yield. Explanations in the literature are material specific, but the universality of the phenomenon begs a universal answer. We argue here that there is no fundamental difference in the states of matter before and after yield, but the yield is a bona fide first-order phase transition between a highly restricted set of possible configurations residing in a small region of phase space to a vastly rich set of configurations which include many marginally stable ones. To show this, we employ an order parameter of universal applicability, independent of the microscopic interactions, that is successful in quantifying the transition in an unambiguous manner.

  16. [Determination of histamine in fish and fish products by tandem solid-phase extraction].

    PubMed

    Awazu, Kaoru; Nomura, Chie; Yamaguchi, Mizuka; Obana, Hirotaka

    2011-01-01

    A simple and practical method was developed for the determination of histamine in fish and fish products by solid-phase extraction and fluorescence derivatization. Histamine was extracted with trichloroacetic acid. The extract was neutralized and diluted with phosphate buffer (pH 6.8), and cleaned up with a tandem-connected octadecyl silica (ODS) and strong cation exchange silica (SCX) cartridge. After removal of the solvent, histamine was derivatized with fluorescamine and analyzed by ion-paired reversed-phase high-performance liquid chromatography with fluorescence detection. Recovery tests of histamine from six kinds of fish and fish products showed acceptable recovery (83-92%) with low relative standard deviation (less than 5%). This method could be useful for determination of histamine in fish.

  17. "Reagentless" flow injection determination of ammonia and urea using membrane separation and solid phase basification.

    PubMed

    Akse, J R; Thompson, J O; Sauer, R L; Atwater, J E

    1998-07-01

    Flow injection analysis instrumentation and methodology for the determination of ammonia and ammonium ions in an aqueous solution are described. Using in-line solid phase basification beds containing crystalline media. the speciation of ammoniacal nitrogen is shifted toward the un-ionized form. which diffuses in the gas phase across a hydrophobic microporous hollow fiber membrane into a pure-water-containing analytical stream. The two streams flow in a countercurrent configuration on opposite sides of the membrane. The neutral pH of the analytical stream promotes the formation of ammonium cations, which are detected using specific conductance. The methodology provides a lower limit of detection of 10 microgram/L and a dynamic concentration range spanning three orders of magnitude using a 315-microliters sample injection volume. Using immobilized urease to enzymatically promote the hydrolysis of urea to produce ammonia and carbon dioxide, the technique has been extended to the determination of urea.

  18. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    PubMed

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

  19. Determination of chloroacetic acids in drinking water using suppressed ion chromatography with solid-phase extraction.

    PubMed

    Yoshikawa, Kenji; Soda, Yuko; Sakuragawa, Akio

    2009-12-01

    Suppressed ion chromatography with a conductivity detector was developed for the determination of trace amounts of underivatized chloroacetic acids (CAAs). When sodium carbonate and methanol were used as a mobile phase, the simultaneous determination of each CAA took approximately 25 min. The linearity, reproducibility and detection limits were determined for the proposed method. For the solid-phase extraction step, the effects of the pH of the sample solution, sample volume and the eluting agent were tested. Under the optimized extracting conditions, the average recoveries for CAAs spiked in tap water were 83-107%, with an optimal preconcentration factor of 20. The reproducibility of recovery rate for CAAs was 1.2-3.8%, based upon 6 repetitions of the recovery experiments.

  20. Static secondary ion mass spectrometry to monitor solid-phase peptide synthesis.

    PubMed

    Maux, D; Enjalbal, C; Martinez, J; Aubagnac, J L; Combarieu, R

    2001-10-01

    Insights into the direct monitoring of supported peptide synthesis were realized through the design of time of flight static secondary ion mass spectrometry (TOF-S-SIMS) experiments. The mass spectrometric method was carried out at the resin bead level and was found reproducible (intra- and inter-day assays), sensitive (femtomol level) and non-destructive (only 0.01% of the peptides were destroyed by the primary ion beam bombardment). The nature of the peptide-resin linkage governed the recovery of ions characterizing the whole peptide sequence. A S-SIMS cleavable bond was thus required solely in that position to achieve the release of the growing structures from the insoluble support into the gas phase without any fragmentation. Results are presented with standard solid-phase resins allowing linkage through an amide or an ester bond. The latter was orthogonally broken upon the bombardment and thus constituted a convenient S-SIMS cleavable bond.

  1. [Determination of organophosphorous pesticide residues in red wine by solid phase microextraction-gas chromatography].

    PubMed

    Hu, Yuan; Liu, Wenmin; Zhou, Yanming; Guan, Yafeng

    2006-05-01

    A method for the determination of 12 organophosphorus pesticide residues (OPs) in red wine by fiber solid phase microextraction (SPME) coupled with gas chromatography (GC) was developed and validated. The SPME phase was prepared by sol-gel technology of physical incorporation. The extraction conditions were optimized with the results of stirring rate of 1,250 r/min, NaCl mass concentration of 150 g/L, and extraction time of 30 min. With the sample volume of 25 mL, the relative standard deviations (RSD) of peak areas for most of OPs were below 5%, and the detection limits of OPs were in the range of 5 ng/L-0.38 microg/L. It can be seen from the results that this method has the potential to analyze OPs in other beverages and soft drinking materials.

  2. "Reagentless" flow injection determination of ammonia and urea using membrane separation and solid phase basification

    NASA Technical Reports Server (NTRS)

    Akse, J. R.; Thompson, J. O.; Sauer, R. L.; Atwater, J. E.

    1998-01-01

    Flow injection analysis instrumentation and methodology for the determination of ammonia and ammonium ions in an aqueous solution are described. Using in-line solid phase basification beds containing crystalline media. the speciation of ammoniacal nitrogen is shifted toward the un-ionized form. which diffuses in the gas phase across a hydrophobic microporous hollow fiber membrane into a pure-water-containing analytical stream. The two streams flow in a countercurrent configuration on opposite sides of the membrane. The neutral pH of the analytical stream promotes the formation of ammonium cations, which are detected using specific conductance. The methodology provides a lower limit of detection of 10 microgram/L and a dynamic concentration range spanning three orders of magnitude using a 315-microliters sample injection volume. Using immobilized urease to enzymatically promote the hydrolysis of urea to produce ammonia and carbon dioxide, the technique has been extended to the determination of urea.

  3. Solid-liquid phase coexistence of alkali nitrates from molecular dynamics simulations.

    SciTech Connect

    Jayaraman, Saivenkataraman

    2010-03-01

    Alkali nitrate eutectic mixtures are finding application as industrial heat transfer fluids in concentrated solar power generation systems. An important property for such applications is the melting point, or phase coexistence temperature. We have computed melting points for lithium, sodium and potassium nitrate from molecular dynamics simulations using a recently developed method, which uses thermodynamic integration to compute the free energy difference between the solid and liquid phases. The computed melting point for NaNO3 was within 15K of its experimental value, while for LiNO3 and KNO3, the computed melting points were within 100K of the experimental values [4]. We are currently extending the approach to calculate melting temperatures for binary mixtures of lithium and sodium nitrate.

  4. Solid-solid phase transformation via internal stress-induced virtual melting, significantly below the melting temperature. Application to HMX energetic crystal.

    PubMed

    Levitas, Valery I; Henson, Bryan F; Smilowitz, Laura B; Asay, Blaine W

    2006-05-25

    We theoretically predict a new phenomenon, namely, that a solid-solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid-solid transformation. Thus, virtual melting represents a new mechanism of solid-solid PT, stress relaxation, and loss of coherence at a moving solid-solid interface. It also removes the athermal interface friction and deletes the thermomechanical memory of preceding cycles of the direct-reverse transformation. It is also found that nonhydrostatic compressive internal stresses promote melting in contrast to hydrostatic pressure. Sixteen theoretical predictions are in qualitative and quantitative agreement with experiments conducted on the PTs in the energetic crystal HMX. In particular, (a) the energy of internal stresses is sufficient to reduce the melting temperature from 551 to 430 K for the delta phase during the beta --> delta PT and from 520 to 400 K for the beta phase during the delta --> beta PT; (b) predicted activation energies for direct and reverse PTs coincide with corresponding melting energies of the beta and delta phases and with the experimental values; (c) the temperature dependence of the rate constant is determined by the heat of fusion, for both direct and reverse PTs; results b and c are obtained both for overall kinetics and for interface propagation; (d) considerable nanocracking, homogeneously distributed in the transformed material, accompanies the PT, as predicted by theory; (e) the nanocracking does not

  5. Advanced Multi-Phase Flow CFD Model Development for Solid Rocket Motor Flowfield Analysis

    NASA Technical Reports Server (NTRS)

    Liaw, Paul; Chen, Y. S.; Shang, H. M.; Doran, Denise

    1993-01-01

    It is known that the simulations of solid rocket motor internal flow field with AL-based propellants require complex multi-phase turbulent flow model. The objective of this study is to develop an advanced particulate multi-phase flow model which includes the effects of particle dynamics, chemical reaction and hot gas flow turbulence. The inclusion of particle agglomeration, particle/gas reaction and mass transfer, particle collision, coalescence and breakup mechanisms in modeling the particle dynamics will allow the proposed model to realistically simulate the flowfield inside a solid rocket motor. The Finite Difference Navier-Stokes numerical code FDNS is used to simulate the steady-state multi-phase particulate flow field for a 3-zone 2-D axisymmetric ASRM model and a 6-zone 3-D ASRM model at launch conditions. The 2-D model includes aft-end cavity and submerged nozzle. The 3-D model represents the whole ASRM geometry, including additional grain port area in the gas cavity and two inhibitors. FDNS is a pressure based finite difference Navier-Stokes flow solver with time-accurate adaptive second-order upwind schemes, standard and extended k-epsilon models with compressibility corrections, multi zone body-fitted formulations, and turbulence particle interaction model. Eulerian/Lagrangian multi-phase solution method is applied for multi-zone mesh. To simulate the chemical reaction, penalty function corrected efficient finite-rate chemistry integration method is used in FDNS. For the AL particle combustion rate, the Hermsen correlation is employed. To simulate the turbulent dispersion of particles, the Gaussian probability distribution with standard deviation equal to (2k/3)(exp 1/2) is used for the random turbulent velocity components. The computational results reveal that the flow field near the juncture of aft-end cavity and the submerged nozzle is very complex. The effects of the turbulent particles affect the flow field significantly and provide better

  6. Aluminum effect on dissolution and precipitation under hyperalkaline conditions: II. Solid phase transformations.

    PubMed

    Qafoku, Nikolla P; Ainsworth, Calvin C; Szecsody, James E; Bish, David L; Young, James S; McCready, David E; Qafoku, Odeta S

    2003-01-01

    The high-level radioactive, Al-rich, concentrated alkaline and saline waste fluids stored in underground tanks have accidentally leaked into the vadose zone at the Hanford Site in Washington State. In addition to dissolution, precipitation is likely to occur when these waste fluids contact the sediments. The objective of this study was to investigate the solid phase transformations caused by dissolution and precipitation in the sediments treated with solutions similar to the waste fluids. Batch experiments at 323 K were conducted in metal- and glass-free systems under CO2 and O2 free conditions. Results from X-ray diffraction (XRD), quantitative X-ray diffraction (QXRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and energy dispersive X-ray fluorescence spectroscopy (EDXRF) indicated that significant solid phase transformations occurred in the sediments contacted with Al-rich, hyperalkaline, and saline solutions. The XRD and QXRD analyses confirmed that smectite and most likely biotite underwent dissolution. The SEM and the qualitative EDS analyses confirmed the formation of alumino-silicates in the groups of cancrinite and probably sodalite. The morphology of the alumino-silicates secondary phases changed in response to changes in the Si/Al aqueous molar ratio. The transformations in the sediments triggered by dissolution (weathering of soil minerals) and precipitation (formation of secondary phases with high specific surface area and probably high sorption capacities) may play a significant role in the immobilization and ultimate fate of radionuclides and contaminants such as Cs, Sr, and U in the Hanford vadose zone.

  7. Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid.

    PubMed

    Roux, María Victoria; Notario, Rafael; Foces-Foces, Concepción; Temprado, Manuel; Ros, Francisco; Emel'yanenko, Vladimir N; Verevkin, Sergey P

    2010-03-18

    This paper reports an experimental and computational thermochemical study on 5,5-dimethylbarbituric acid and the solid-phase structure of the compound. The value of the standard (p(o) = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -(706.4 +/- 2.2) kJ x mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated NB(2) stream, and a value of the enthalpy of sublimation at T = 298.15 K was derived as (115.8 +/- 0.5) kJ x mol(-1). From these results a value of -(590.6 +/- 2.3) kJ x mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 level were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in reasonable agreement with the experimental value. 5,5-Dimethylbarbituric acid was characterized by single crystal X-ray diffraction analysis. In the crystal structure, N-H...O=C hydrogen bonds lead to the formation of ribbons connected further by weak C-H...O=C hydrogen bonds into a three-dimensional network. The molecular and supramolecular structures observed in the solid state were also investigated in the gas phase by DFT calculations.

  8. Dipole-Oriented Molecular Solids Can Undergo a Phase Change and Still Maintain Electrical Polarization

    SciTech Connect

    Cassidy, Andrew; Jørgensen, Mads R. V.; Rosu-Finsen, Alexander; Lasne, Jérôme; Jørgensen, Jakob H.; Glavic, Artur; Lauter, Valeria; Iversen, Bo B.; McCoustra, Martin R. S.; Field, David

    2016-10-02

    It has recently been demonstrated that nanoscale molecular films can spontaneously assemble to self-generate intrinsic electric fields that can exceed 108 V/m. These electric fields originate from polarization charges in the material that arise because the films self-assemble to orient molecular dipole moments. This has been called the spontelectric effect. Such growth of spontaneously polarized layers of molecular solids has implications for our understanding of how intermolecular interactions dictate the structure of molecular materials used in a range of applications, for example, molecular semiconductors, sensors, and catalysts. In this paper, we present the first in situ structural characterization of a representative spontelectric solid, nitrous oxide. Infrared spectroscopy, temperature-programmed desorption, and neutron reflectivity measurements demonstrate that polarized films of nitrous oxide undergo a structural phase transformation upon heating above 48 K. A mean-field model can be used to describe quantitatively the magnitude of the spontaneously generated field as a function of film-growth temperature, and this model also recreates the phase change. Finally, this reinforces the spontelectric model as a means of describing long-range dipole–dipole interactions and points to a new type of ordering in molecular thin films.

  9. Solid-phase microextraction for the analysis of short-chain chlorinated paraffins in water samples.

    PubMed

    Castells, P; Santos, F J; Galceran, M T

    2003-01-10

    A novel solid-phase microextraction (SPME) method coupled to gas chromatography with electron capture detection (GC-ECD) was developed as an alternative to liquid-liquid and solid-phase extraction for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples. The extraction efficiency of five different commercially available fibres was evaluated and the 100-microm polydimethylsiloxane coating was the most suitable for the absorption of the SCCPs. Optimisation of several SPME parameters, such as extraction time and temperature, ionic strength and desorption time, was performed. Quality parameters were established using Milli-Q, tap water and river water. Linearity ranged between 0.06 and 6 microg l(-1) for spiked Milli-Q water and between 0.6 and 6 microg l(-1) for natural waters. The precision of the SPME-GC-ECD method for the three aqueous matrices was similar and gave relative standard deviations (RSD) between 12 and 14%. The limit of detection (LOD) was 0.02 microg l(-1) for Milli-Q water and 0.3 microg l(-1) for both tap water and river water. The optimised SPME-GC-ECD method was successfully applied to the determination of SCCPs in river water samples.

  10. Solid-phase microextraction-gas chromatographic determination of volatile monoaromatic hydrocarbons in soil.

    PubMed

    Zygmunt, B; Namiesnik, J

    2001-08-01

    Benzene, toluene, ethylbenzene, three isomers of xylene, and cumene have been isolated and enriched from soil samples by a combination of water extraction at room and elevated temperature and headspace-solid-phase microextraction before their gas chromatographic-mass spectrometric (GC-MS) determination. The conditions used for all stages of sample preparation and chromatographic analysis were optimized. Analytes sampled on a polydimethylsiloxane-coated solid-phase microextraction fiber were thermally desorbed in the split/splitless injector of a gas chromatograph (GC) coupled with a mass spectrometer (MS). The desorption temperature was optimized. The GC separation was performed in a capillary column. Detection limits were found to be of the order of ca. 1 ng g(-1). Relative recoveries of the analytes from soils were found to be highly dependent on soil organic-matter content and on compound identity; they ranged from ca 92 to 96% for sandy soil (extraction at room temperature) and from ca 27 to 55% for peaty soil (extraction at elevated temperature). A few real-world soil samples were analyzed; the individual monoaromatic hydrocarbon content ranged from below detection limits to 6.4 ng g(-1) for benzene and 8.1 for the total of p- + m-xylene.

  11. Carbon nanocones/disks as new coating for solid-phase microextraction.

    PubMed

    Jiménez-Soto, Juan Manuel; Cárdenas, Soledad; Valcárcel, Miguel

    2010-05-14

    In this article, the potential of carbon nanocones/disks as coating for solid-phase microextraction has been evaluated for the first time. The nanostructures were immobilized on a stainless steel needle by means of an organic binder. The fiber coating obtained was ca. 50 microm of thickness and 35 mm in length. The evaluation of the sorbent capacity was carried out through the determination of toluene, ethylbenzene, xylene isomers and styrene in water samples following the headspace sampling modality (15 min, 30 degrees C). The fiber was then transferred to a 10 mL vial which was sealed and heated at 110 degrees C for 15 min in the headspace module of the instrument to achieve the thermal desorption of the analytes. Then 2.5 mL of the headspace generated were injected in the gas chromatograph-mass spectrometer for analytes separation and quantitation. The detection and quantitation limits obtained for 10 mL of sample were 0.15 and 0.5 ng mL(-1) (0.6 and 2 ng mL(-1) for toluene). The optimized procedure was applied to the determination of the selected volatile compounds in waters collected from different locations. The recovery values obtained (average recovery ca. 92%) demonstrated the usefulness of the carbon nanocones/disks as sorbent material in solid-phase microextraction.

  12. Solid phase extraction and metabolic profiling of exudates from living copepods.

    PubMed

    Selander, Erik; Heuschele, Jan; Nylund, Göran M; Pohnert, Georg; Pavia, Henrik; Bjærke, Oda; Pender-Healy, Larisa A; Tiselius, Peter; Kiørboe, Thomas

    2016-01-01

    Copepods are ubiquitous in aquatic habitats. They exude bioactive compounds that mediate mate finding or induce defensive traits in prey organisms. However, little is known about the chemical nature of the copepod exometabolome that contributes to the chemical landscape in pelagic habitats. Here we describe the development of a closed loop solid phase extraction setup that allows for extraction of exuded metabolites from live copepods. We captured exudates from male and female Temora longicornis and analyzed the content with high resolution LC-MS. Chemometric methods revealed 87 compounds that constitute a specific chemical pattern either qualitatively or quantitatively indicating copepod presence. The majority of the compounds were present in both female and male exudates, but nine compounds were mainly or exclusively present in female exudates and hence potential pheromone candidates. Copepodamide G, known to induce defensive responses in phytoplankton, was among the ten compounds of highest relative abundance in both male and female extracts. The presence of copepodamide G shows that the method can be used to capture and analyze chemical signals from living source organisms. We conclude that solid phase extraction in combination with metabolic profiling of exudates is a useful tool to develop our understanding of the chemical interplay between pelagic organisms.

  13. Improvement of multilayer graphene crystallinity by solid-phase precipitation with current stress application during annealing

    NASA Astrophysics Data System (ADS)

    Sahab Uddin, Md.; Ichikawa, Hiroyasu; Sano, Shota; Ueno, Kazuyoshi

    2016-06-01

    To improve the crystallinity of multilayer graphene (MLG) films by solid-phase precipitation, a new method by which current stress is introduced during annealing of a carbon-doped cobalt (Co-C) layer using cobalt (Co) as the catalyst has been investigated. The effects of current stress on the formation and crystallinity of MLG films were investigated by comparing the characteristics of the films annealed at the same temperature with and without current by taking into account the temperature rise due to Joule heating. The characteristics obtained by Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) measurements revealed that the MLG films produced were crystalline in nature and their crystallinity increased with applied current stress at the same temperature. From SEM observations, beside Joule heating, enhancement of Co grain size by agglomeration induced by current stress may be the potential reason for the improvement of the crystallinity of MLG films. We have also improved the uniformity of MLG films by depositing an additional copper (Cu) capping layer over the Co-C layer. Current stress application can lead to low-temperature fabrication of MLG with higher crystallinity by solid-phase precipitation.

  14. Molecularly imprinted polymer microspheres for solid-phase extraction of protocatechuic acid in Rhizoma homalomenae.

    PubMed

    Chen, Fang-Fang; Wang, Guo-Ying; Shi, Yan-Ping

    2011-10-01

    Molecularly imprinted polymers (MIPs) had been prepared by precipitation polymerization method using acrylamide as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, acetonitrile as the porogen solvent and protocatechuic acid (PA), one of phenolic acids, as the template molecule. The MIPs were characterized by scanning electron microscopy and Fourier transform infrared, and their performance relative to non-imprinted polymers was assessed by equilibrium binding experiments. Six structurally similar phenolic acids, including p-hydroxybenzoic acid, gallic acid, salicylic acid, syringic acid, vanillic acid, ferulic acid were selected to assess the selectivity and recognition capability of the MIPs. The MIPs were applied to extract PA from the traditional Chinese medicines as a solid-phase extraction sorbent. The resultant cartridge showed that the MIPs have a good extraction performance and were able to selectively extract almost 82% of PA from the extract of Rhizoma homalomenae. Thus, the proposed molecularly imprinted-solid phase extraction-high performance liquid chromatography method can be successfully used to extract and analyse PA in traditional Chinese medicines.

  15. PEGylation of magnetic multi-walled carbon nanotubes for enhanced selectivity of dispersive solid phase extraction.

    PubMed

    Zeng, Qiong; Liu, Yi-Ming; Jia, Yan-Wei; Wan, Li-Hong; Liao, Xun

    2017-02-01

    Carbon nanotubes (CNTs) possess large potential as extraction absorbents in solid phase extraction. They have been widely applied in biomedicine research, while very rare application in natural product chemistry has been reported. In this work, methoxypolyethylene glycol amine (mPEG-NH2) is covalently coupled to CNTs-magnetic nanoparticles (CNTs-MNP) to prepare a novel magnetic nanocomposite (PEG-CNTs-MNP) for use as dispersive solid-phase extraction (DSPE) absorbent. The average particle size was 86nm, and the saturation magnetization was 52.30emu/g. This nanocomposite exhibits excellent dispersibility in aqueous systems, high selectivity and fast binding kinetics when used for extraction of Z-ligustilide, the characteristic bioactive compound from two popular Asian herbal plants, R. chuanxiong and R. ligusticum. HPLC quantification of Z-ligustilide extracted from the standard sample solution showed a high recovery of 98.9%, and the extraction rate from the extracts of the above two herbs are both around 70.0%. To our knowledge, this is the first report on using PEG-CNTs-MNP as DSPE nanosorbents for selective extraction of natural products. This nano-material has promising application in isolation and enrichment of targeted components from complex matrices.

  16. Automation of solid-phase microextraction in high-throughput format and applications to drug analysis.

    PubMed

    Vuckovic, Dajana; Cudjoe, Erasmus; Hein, Dietmar; Pawliszyn, Janusz

    2008-09-15

    The automation of solid-phase microextraction (SPME) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) was accomplished using a 96 multiwell plate format, a SPME multifiber device, two orbital shakers, and a three-arm robotic system. Extensive optimization of the proposed setup was performed including coating selection, optimization of the fiber coating procedure, confirmation of uniform agitation in all wells, and the selection of the optimal calibration method. The system allows the use of pre-equilibrium extraction times with no deterioration in method precision due to reproducible timing of extraction and desorption steps and reproducible positioning of all fibers within the wells. The applicability of the system for the extraction of several common drugs is demonstrated. The optimized multifiber SPME-LC-MS/MS was subsequently fully validated for the high-throughput analysis of diazepam, lorazepam, nordiazepam, and oxazepam in human whole blood. The proposed method allowed the automated sample preparation of 96 samples in 100 min, which represents the highest throughput of any SPME technique to date, while achieving excellent accuracy (87-113%), precision (solid-phase extraction (SPE) including lower cost, the ability to quantitatively determine free and total drug concentrations in a single biofluid sample, and the ability to directly process whole blood samples with absolutely no sample pretreatment required.

  17. Dipole-Oriented Molecular Solids Can Undergo a Phase Change and Still Maintain Electrical Polarization

    DOE PAGES

    Cassidy, Andrew; Jørgensen, Mads R. V.; Rosu-Finsen, Alexander; ...

    2016-10-02

    It has recently been demonstrated that nanoscale molecular films can spontaneously assemble to self-generate intrinsic electric fields that can exceed 108 V/m. These electric fields originate from polarization charges in the material that arise because the films self-assemble to orient molecular dipole moments. This has been called the spontelectric effect. Such growth of spontaneously polarized layers of molecular solids has implications for our understanding of how intermolecular interactions dictate the structure of molecular materials used in a range of applications, for example, molecular semiconductors, sensors, and catalysts. In this paper, we present the first in situ structural characterization of amore » representative spontelectric solid, nitrous oxide. Infrared spectroscopy, temperature-programmed desorption, and neutron reflectivity measurements demonstrate that polarized films of nitrous oxide undergo a structural phase transformation upon heating above 48 K. A mean-field model can be used to describe quantitatively the magnitude of the spontaneously generated field as a function of film-growth temperature, and this model also recreates the phase change. Finally, this reinforces the spontelectric model as a means of describing long-range dipole–dipole interactions and points to a new type of ordering in molecular thin films.« less

  18. Positional scanning for peptide secondary structure by systematic solid-phase synthesis of amino lactam peptides.

    PubMed

    Jamieson, Andrew G; Boutard, Nicolas; Beauregard, Kim; Bodas, Mandar S; Ong, Huy; Quiniou, Christiane; Chemtob, Sylvain; Lubell, William D

    2009-06-10

    Incorporation of amino lactams into biologically active peptides has been commonly used to restrict conformational mobility, enhance selectivity, and increase potency. A solid-phase method using a Fmoc-protection strategy has been developed for the systematic synthesis of peptides containing configurationally defined alpha- and beta-amino gamma-lactams. N-Alkylation of N-silyl peptides with five- and six-member cyclic sulfamidates 9 and 8 minimized bis-alkylation and provided N-alkyl peptides, which underwent lactam annulation under microwave heating. Employing this solid-phase protocol on the growth hormone secretagogue GHRP-6, as well as on the allosteric modulator of the IL-1 receptor 101.10, has furnished 16 lactam derivatives and validated the effectiveness of this approach on peptides bearing aliphatic, aromatic, branched, charged, and heteroatomic side chains. The binding affinity IC(50) values of the GHRP-6 lactam analogues on both the GHS-R1a and CD36 receptors are reported as well as inhibition of thymocyte proliferation measurements for the 101.10 lactam analogues. In these cases, lactam analogues were prepared exhibiting similar or improved properties compared with the parent peptide. Considering the potential for amino lactams to induce peptide turn conformations, the effective method described herein for their supported construction on growing peptides, and for the systematical amino lactam scan of peptides, has proven useful for the rapid identification of the secondary structure necessary for peptide biological activity.

  19. Introducing Freshmen Students to the Practice of Solid-Phase Synthesis

    NASA Astrophysics Data System (ADS)

    Taralp, Alpay; Hulusi Türkseven, Can; Özgür Çakmak, Atilla; Çengel, Ömer

    2002-01-01

    A one-semester laboratory project on solid-phase peptide chemistry was designed pedagogically to cater to freshman science students. The approach not only permitted multistep syntheses that would be considered impractical in solution, but also gave students insight into fundamental aspects of research at an early stage of development. Young scientists prepared Bz-Asn-Asn-Phe and Bz-Asn-Gln-Phe--peptides envisaged as potential competitive inhibitors of chymotrypsin. The synthesis, defined by an attachment-deprotection cycle, two elongation-deprotection cycles, and a benzoyl-capping protocol, was completed manually on Wang resin using Fmoc chemistry. Students quantified the yield of each condensation and deprotection reaction by measuring levels of dibenzylfulvene chromophore, a stoichiometrically afforded by-product. Benzoylation of the N-terminus was confirmed by employing a cadmium-ninhydrin reagent. The group also ascertained, through use of a chromogenic substrate, that chymotrypsin-catalyzed hydrolysis was impeded slightly when carried out in the presence of target peptides. Supplementary analyses supporting peptide purity and composition were given to students. Grading was based on laboratory participation, project proposals, reports, and a concluding slide-show presentation made to peers and colleagues. While the project was time-consuming overall, students acquired an impression of research work and an appreciation of the utility of solid-phase methods.

  20. Platform construction and extraction mechanism study of magnetic mixed hemimicelles solid-phase extraction

    PubMed Central

    Xiao, Deli; Zhang, Chan; He, Jia; Zeng, Rong; Chen, Rong; He, Hua

    2016-01-01

    Simple, accurate and high-throughput pretreatment method would facilitate large-scale studies of trace analysis in complex samples. Magnetic mixed hemimicelles solid-phase extraction has the power to become a key pretreatment method in biological, environmental and clinical research. However, lacking of experimental predictability and unsharpness of extraction mechanism limit the development of this promising method. Herein, this work tries to establish theoretical-based experimental designs for extraction of trace analytes from complex samples using magnetic mixed hemimicelles solid-phase extraction. We selected three categories and six sub-types of compounds for systematic comparative study of extraction mechanism, and comprehensively illustrated the roles of different force (hydrophobic interaction, π-π stacking interactions, hydrogen-bonding interaction, electrostatic interaction) for the first time. What’s more, the application guidelines for supporting materials, surfactants and sample matrix were also summarized. The extraction mechanism and platform established in the study render its future promising for foreseeable and efficient pretreatment under theoretical based experimental design for trace analytes from environmental, biological and clinical samples. PMID:27924944