Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 2. Application for the analysis of Loy Yang coal oxidation products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawamura, K.; Okuwaki, A.; Verheyen, T.V.

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt was optimized using the solvent gradient method. This method was applied for the analysis of Loy Yang coal oxidation products. It was confirmed that the analytical data using this method were consistent with those determined using gas chromatography.

Improved selectivity for high-performance liquid chromatographic determination of clonazepam in plasma of epileptic patients.

PubMed

Le Guellec, C; Gaudet, M L; Breteau, M

1998-11-20

We report a high-performance liquid chromatography method for clonazepam determination in plasma. The use of a synthetic silica-based stationary phase markedly improved clonazepam resolution compared to standard reversed-phase columns. A liquid-liquid extraction was used, associated with reversed-phase chromatography, gradient elution and ultraviolet detection. Accuracy and precision were satisfactory at therapeutic concentrations. Selectivity was studied for benzodiazepines or other antiepileptic drugs, with particular attention to newly marketed drugs i.e., gabapentine and vigabatrin. No interfering substance was evidenced. Under the conditions described, it was possible to quantify clonazepam at nanogram level even when carbamazepine was present at therapeutic concentrations.

Comprehensive analysis of pharmaceutical products using simultaneous mixed-mode (ion-exchange/reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Nesterenko, Pavel N; Soisungnoen, Phimpha; Burakham, Rodjana; Srijaranai, Supalax; Paull, Brett

2014-08-01

Liquid chromatographic assays were developed using a mixed-mode column coupled in sequence with a hydrophilic interaction liquid chromatography column to allow the simultaneous comprehensive analysis of inorganic/organic anions and cations, active pharmaceutical ingredients, and excipients (carbohydrates). The approach utilized dual sample injection and valve-mediated column switching and was based upon a single high-performance liquid chromatography gradient pump. The separation consisted of three distinct sequential separation mechanisms, namely, (i) ion-exchange, (ii) mixed-mode interactions under an applied dual gradient (reversed-phase/ion-exchange), and (iii) hydrophilic interaction chromatography. Upon first injection, the Scherzo SS C18 column (Imtakt) provided resolution of inorganic anions and cations under isocratic conditions, followed by a dual organic/salt gradient to elute active pharmaceutical ingredients and their respective organic counterions and potential degradants. At the top of the mixed-mode gradient (high acetonitrile content), the mobile phase flow was switched to a preconditioned hydrophilic interaction liquid chromatography column, and the standard/sample was reinjected for the separation of hydrophilic carbohydrates, some of which are commonly known excipients in drug formulations. The approach afforded reproducible separation and resolution of up to 23 chemically diverse solutes in a single run. The method was applied to investigate the composition of commercial cough syrups (Robitussin®), allowing resolution and determination of inorganic ions, active pharmaceutical ingredients, excipients, and numerous well-resolved unknown peaks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of low central fuelling on density and ion temperature profiles in reversed shear plasmas on JT-60U

NASA Astrophysics Data System (ADS)

Takenaga, H.; Ide, S.; Sakamoto, Y.; Fujita, T.; JT-60 Team

2008-07-01

Effects of low central fuelling on density and ion temperature profiles have been investigated using negative ion based neutral beam injection and electron cyclotron heating (ECH) in reversed shear plasmas on JT-60U. Strong internal transport barrier (ITB) was maintained in density and ion temperature profiles, when central fuelling was decreased by switching positive ion based neutral beam injection to ECH after the strong ITB formation. Similar density and ion temperature ITBs were formed for the low and high central fuelling cases during the plasma current ramp-up phase. Strong correlation between the density gradient and the ion temperature gradient was observed, indicating that particle transport and ion thermal transport are strongly coupled or the density gradient assists the ion temperature ITB formation through suppression of drift wave instabilities such as ion temperature gradient mode. These results support that the density and ion temperature ITBs can be formed under reactor relevant conditions.

Evaluation of comprehensive multidimensional separations using reversed-phase, reversed-phase liquid chromatography/mass spectrometry for shotgun proteomics.

PubMed

Nakamura, Tatsuji; Kuromitsu, Junro; Oda, Yoshiya

2008-03-01

Two-dimensional liquid-chromatographic (LC) separation followed by mass spectrometric (MS) analysis was examined for the identification of peptides in complex mixtures as an alternative to widely used two-dimensional gel electrophoresis followed by MS analysis for use in proteomics. The present method involves the off-line coupling of a narrow-bore, polymer-based, reversed-phase column using an acetonitrile gradient in an alkaline mobile phase in the first dimension with octadecylsilanized silica (ODS)-based nano-LC/MS in the second dimension. After the first separation, successive fractions were acidified and dried off-line, then loaded on the second dimension column. Both columns separate peptides according to hydrophobicity under different pH conditions, but more peptides were identified than with the conventional technique for shotgun proteomics, that is, the combination of a strong cation exchange column with an ODS column, and the system was robust because no salts were included in the mobile phases. The suitability of the method for proteomics measurements was evaluated.

Separation of Poly(styrene-block-t-butyl methacrylate) Copolymers by Various Liquid Chromatography Techniques

PubMed Central

Šmigovec Ljubič, Tina; Pahovnik, David; Žigon, Majda; Žagar, Ema

2012-01-01

The separation of a mixture of three poly(styrene-block-t-butyl methacrylate) copolymers (PS-b-PtBMA), consisting of polystyrene (PS) blocks of similar length and t-butyl methacrylate (PtBMA) blocks of different lengths, was performed using various chromatographic techniques, that is, a gradient liquid chromatography on reversed-phase (C18 and C8) and normal-phase columns, a liquid chromatography under critical conditions for polystyrene as well as a fully automated two-dimensional liquid chromatography that separates block copolymers by chemical composition in the first dimension and by molar mass in the second dimension. The results show that a partial separation of the mixture of PS-b-PtBMA copolymers can be achieved only by gradient liquid chromatography on reversed-phase columns. The coelution of the two block copolymers is ascribed to a much shorter PtBMA block length, compared to the PS block, as well as a small difference in the length of the PtBMA block in two of these copolymers, which was confirmed by SEC-MALS and NMR spectroscopy. PMID:22489207

Quantitative structure-retention relationship models for the prediction of the reversed-phase HPLC gradient retention based on the heuristic method and support vector machine.

PubMed

Du, Hongying; Wang, Jie; Yao, Xiaojun; Hu, Zhide

2009-01-01

The heuristic method (HM) and support vector machine (SVM) were used to construct quantitative structure-retention relationship models by a series of compounds to predict the gradient retention times of reversed-phase high-performance liquid chromatography (HPLC) in three different columns. The aims of this investigation were to predict the retention times of multifarious compounds, to find the main properties of the three columns, and to indicate the theory of separation procedures. In our method, we correlated the retention times of many diverse structural analytes in three columns (Symmetry C18, Chromolith, and SG-MIX) with their representative molecular descriptors, calculated from the molecular structures alone. HM was used to select the most important molecular descriptors and build linear regression models. Furthermore, non-linear regression models were built using the SVM method; the performance of the SVM models were better than that of the HM models, and the prediction results were in good agreement with the experimental values. This paper could give some insights into the factors that were likely to govern the gradient retention process of the three investigated HPLC columns, which could theoretically supervise the practical experiment.

Development of anion-exchange/reversed-phase high performance liquid chromatography-inductively coupled plasma-mass spectrometry methods for the speciation of bio-available iodine and bromine from edible seaweed.

PubMed

Romarís-Hortas, Vanessa; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

2012-05-04

Anion exchange high performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry has been novelly applied to assess inorganic (iodide and iodate) and organic (3-iodotyrosine - MIT, and 3,5-diiodotyrosine - DIT) iodine species in a single chromatographic run. The optimized operating conditions (Dionex IonPac AS7, gradient elution with 175 mM ammonium nitrate plus 15% (v/v) methanol, pH 3.8, as a mobile phase and flow rates within the 0.5-1.5 mL min(-1) range) have also been used to perform inorganic bromine speciation analysis (bromide and bromate). The developed method has been applied for determining the bio-available contents of iodine and bromine species in dialyzates from edible seaweed. Reverse phase high performance liquid chromatography (Zorbax Eclipse XDB-C8, gradient elution with 0.2% (m/m) acetic acid, and 0.2% (m/m) acetic acid in methanol, as mobile phases, and a constant flow rate of 0.75 mL min(-1)) also hyphenated with inductively coupled plasma-mass spectrometry was used to confirm the presence of organic iodine species (MIT and DIT) in the dialyzates. The verification of the presence of iodinated amino acids (MIT and DIT) in the extracts was also performed by reverse phase high performance liquid chromatography-electrospray ionization-mass spectrometry (LTQ Orbitrap). The developed methods have provided good repeatability (RSD values lower than 10% for both anion exchange and reverse phase separations) and analytical recoveries within the 90-105% range for all cases. The in vitro bio-availability method consisted of a simulated gastric and an intestinal digestion/dialysis (10 kDa molecular weight cut-off - MWCO) two-stage procedure. Iodide and MIT were the main bio-available species quantified, whereas bromide was the major bromine species found in the extracts. Copyright © 2012 Elsevier B.V. All rights reserved.

Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones.

PubMed

Aral, Hayriye; Aral, Tarık; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2013-11-15

A novel amide-bonded silica stationary phase was prepared starting from N-Boc-phenylalanine, cyclohexylamine and spherical silica gel (4 µm, 60 Å). The amide ligand was synthesised with high yield. The resulting amide bonded stationary phase was characterised by SEM, IR and elemental analysis. The resulting selector bearing a polar amide group is used for the reversed-phase chromatography separation of different classes of thirteen phytohormones (plant hormones). The chromatographic behaviours of these analytes on the amide-silica stationary phase were compared with those of RP-C18 column under same conditions. The effects of different separation conditions, such as mobile phase, pH value, flow rate and temperature, on the separation and retention behaviours of the 13 phytohormones in this system were studied. The optimum separation was achieved using reversed-phase HPLC gradient elution with an aqueous mobile phase containing pH=6.85 potassium phosphate buffer (20 mM) and acetonitrile with a 22 °C column temperature. Under these experimental conditions, the 12 phytohormones could be separated and detected at 230 or 270 nm within 26 min. Copyright © 2013 Elsevier B.V. All rights reserved.

Dopexamine reverses colonic but not gastric mucosal perfusion defects in lethal endotoxin shock.

PubMed

Tenhunen, J J; Martikainen, T J; Uusaro, A; Ruokonen, E

2003-12-01

Whilst dopexamine appears to increase overall splanchnic blood flow in postoperative and septic patients, the effects on gastric mucosal perfusion are controversial and based on concomitantly increasing mucosal to arterial PCO(2) gradients (PdCO(2)). We hypothesized that dopexamine alters splanchnic blood flow distribution and metabolism during experimental endotoxin shock and modifies the inflammatory response induced by endotoxin. In an experiment with anaesthetized normovolaemic, normoventilated pigs, 21 animals were randomized into: (i). subacute lethal endotoxin shock for 14 h (n=7 at baseline); (ii). endotoxin shock with dopexamine infusion (aiming to exceed baseline cardiac output, n=7); or (iii). controls (n=7). Regional blood flow and metabolism were monitored. Endotoxin produced a hypodynamic phase followed by a normo/hyperdynamic, hypotensive phase. Despite increasing systemic blood flow in response to dopexamine, proportional splanchnic blood flow decreased during the hypodynamic phase. Dopexamine gradually decreased fractional coeliac trunk flow, while fractional superior mesenteric arterial flow increased. Dopexamine induced early arterial hyperlactataemia and augmented the gastric PdCO(2) gradient while colonic luminal lactate release and colonic PdCO(2) gradient were reversed. Dopexamine did not modify the inflammatory response as evaluated by arterial IL-1beta and IL-6 concentrations. Dopexamine protects colonic, but not gastric mucosal epithelium in experimental endotoxin shock. This may be related to redistribution of blood flow within the splanchnic circulation.

Separation of cannabinoids on three different mixed-mode columns containing carbon/nanodiamond/amine-polymer superficially porous particles.

PubMed

Hung, Chuan-Hsi; Zukowski, Janusz; Jensen, David S; Miles, Andrew J; Sulak, Clayton; Dadson, Andrew E; Linford, Matthew R

2015-09-01

Three mixed-mode high-performance liquid chromatography columns packed with superficially porous carbon/nanodiamond/amine-polymer particles were used to separate mixtures of cannabinoids. Columns evaluated included: (i) reversed phase (C18 ), weak anion exchange, 4.6 × 33 mm, 3.6 μm, and 4.6 × 100 mm, 3.6 μm, (ii) reversed phase, strong anion exchange (quaternary amine), 4.6×33 mm, 3.6 μm, and (iii) hydrophilic interaction liquid chromatography, 4.6 × 150 mm, 3.6 μm. Different selectivities were achieved under various mobile phase and stationary phase conditions. Efficiencies and peak capacities were as high as 54 000 N/m and 56, respectively. The reversed phase mixed-mode column (C18 ) retained tetrahydrocannabinolic acid strongly under acidic conditions and weakly under basic conditions. Tetrahydrocannabinolic acid was retained strongly on the reversed phase, strong anion exchange mixed-mode column under basic polar organic mobile phase conditions. The hydrophilic interaction liquid chromatography column retained polar cannabinoids better than the (more) neutral ones under basic conditions. A longer reversed phase (C18 ) mixed-mode column (4.6 × 100 mm) showed better resolution for analytes (and a contaminant) than a shorter column. Fast separations were achieved in less than 5 min and sometimes 2 min. A real world sample (bubble hash extract) was also analyzed by gradient elution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ferroic Shape Memory Materials & Piezo:Pyro-Electric Oriented Recrystallized Glasses.

DTIC Science & Technology

1986-07-01

microcope hot stage. The direction of crystallization was parallel to the direction of temperature gradient. The crystalline phases in the glass...may increase or decrease with temperature. Several compounds show a sign reversal in the pyroelectric coefficients, going from positive to negative

Development and validation of reversed-phase HPLC gradient method for the estimation of efavirenz in plasma.

PubMed

Gupta, Shweta; Kesarla, Rajesh; Chotai, Narendra; Omri, Abdelwahab

2017-01-01

Efavirenz is an anti-viral agent of non-nucleoside reverse transcriptase inhibitor category used as a part of highly active retroviral therapy for the treatment of infections of human immune deficiency virus type-1. A simple, sensitive and rapid reversed-phase high performance liquid chromatographic gradient method was developed and validated for the determination of efavirenz in plasma. The method was developed with high performance liquid chromatography using Waters X-Terra Shield, RP18 50 x 4.6 mm, 3.5 μm column and a mobile phase consisting of phosphate buffer pH 3.5 and Acetonitrile. The elute was monitored with the UV-Visible detector at 260 nm with a flow rate of 1.5 mL/min. Tenofovir disoproxil fumarate was used as internal standard. The method was validated for linearity, precision, accuracy, specificity, robustness and data obtained were statistically analyzed. Calibration curve was found to be linear over the concentration range of 1-300 μg/mL. The retention times of efavirenz and tenofovir disoproxil fumarate (internal standard) were 5.941 min and 4.356 min respectively. The regression coefficient value was found to be 0.999. The limit of detection and the limit of quantification obtained were 0.03 and 0.1 μg/mL respectively. The developed HPLC method can be useful for quantitative pharmacokinetic parameters determination of efavirenz in plasma.

Monitoring gradient profile on-line in micro- and nano-high performance liquid chromatography using conductivity detection.

PubMed

Zhang, Min; Chen, Apeng; Lu, Joann J; Cao, Chengxi; Liu, Shaorong

2016-08-19

In micro- or nano-flow high performance liquid chromatography (HPLC), flow-splitters and gradient elutions are commonly used for reverse phase HPLC separations. When a flow splitter was used at a high split-ratio (e.g., 1000:1 or higher), the actual gradient may deviate away from the programmed gradient. Sometimes, mobile phase concentrations can deviate by as much as 5%. In this work, we noticed that the conductivity (σ) of a gradient decreased with the increasing organic-solvent fraction (φ). Based on the relationship between σ and φ, a method was developed for monitoring gradient profile on-line to record any deviations in these HPLC systems. The conductivity could be measured by a traditional conductivity detector or a capacitively coupled contactless conductivity detector (C(4)D). The method was applied for assessing the performance of an electroosmotic pump (EOP) based nano-HPLC. We also observed that σ value of the gradient changed with system pressure; a=0.0175ΔP (R(2)=0.964), where a is the percentage of the conductivity increase and ΔP is the system pressure in bar. This effect was also investigated. Copyright © 2016. Published by Elsevier B.V.

A RP-LC method with evaporative light scattering detection for the assay of simethicone in pharmaceutical formulations.

PubMed

Moore, Douglas E; Liu, Tina X; Miao, William G; Edwards, Alison; Elliss, Russell

2002-09-05

A reversed-phase liquid chromatographic method has been developed and validated for the determination of the polydimethylsiloxane (PDMS) component of Simethicone, which is used as an anti-foaming agent in pharmaceutical formulations. The method involves acidification to neutralise antacid components of the formulation, then a single extraction of the PDMS with dichloromethane. This is followed by separation with a reversed-phase column using an acetonitrile-chloroform solvent gradient, and quantification by an evaporative light scattering detector. An assay precision of 3% was achieved in intraday and interday determinations. No interference was found from the aluminium and magnesium hydroxide components of antacid formulations.

HPLC Characterization of Phenol-Formaldehyde Resole Resin Used in Fabrication of Shuttle Booster Nozzles

NASA Technical Reports Server (NTRS)

Young, Philip R.

1999-01-01

A reverse phase High Performance Liquid Chromatographic method was developed to rapidly fingerprint a phenol-formaldehyde resole resin similar to Durite(R) SC-1008. This resin is used in the fabrication of carbon-carbon composite materials from which Space Shuttle Solid Rocket Booster nozzles are manufactured. A knowledge of resin chemistry is essential to successful composite processing and performance. The results indicate that a high quality separation of over 35 peaks in 25 minutes were obtained using a 15 cm Phenomenex LUNA C8 bonded reverse phase column, a three-way water-acetonitrile-methanol nonlinear gradient, and LTV detection at 280 nm.

Mobile phase effects on the retention on polar columns with special attention to the dual hydrophilic interaction-reversed-phase liquid chromatography mechanism, a review.

PubMed

Jandera, Pavel; Hájek, Tomáš

2018-01-01

Hydrophilic interaction liquid chromatography on polar columns in aqueous-organic mobile phases has become increasingly popular for the separation of many biologically important compounds in chemical, environmental, food, toxicological, and other samples. In spite of many new applications appearing in literature, the retention mechanism is still controversial. This review addresses recent progress in understanding of the retention models in hydrophilic interaction liquid chromatography. The main attention is focused on the role of water, both adsorbed by the column and contained in the bulk mobile phase. Further, the theoretical retention models in the isocratic and gradient elution modes are discussed. The dual hydrophilic interaction liquid chromatography reversed-phase retention mechanism on polar columns is treated in detail, especially with respect to the practical use in one- and two-dimensional liquid chromatography separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization and screening of pyrrolizidine alkaloids and N-oxides from various parts of many botanicals and dietary supplements using liquid chromatography high resolution mass spectrometry

USDA-ARS?s Scientific Manuscript database

The UHPLC-QToF-MS analysis of pyrrolizidine alkaloids from various parts of 37 botanicals and 7 dietary supplements was performed. A separation by LC was achieved using a reversed-phase column and a gradient of water/acetonitrile each containing formic acid as the mobile phase. MS-MS detection was u...

A validated LC method for determination of 2,3-dichlorobenzoic acid and its associated regio isomers.

PubMed

Krishnaiah, Ch; Sri, Khagga Bhavya

2012-05-01

A simple, selective and sensitive gradient reversed-phase liquid chromatography method has been developed for the separation and determination of 2,3-dichlorobenzoic acid, which is an intermediate of the lamotrizine drug substance, and its regio isomers. The separation was achieved on a reversed-phase United States Pharmacopeia L1 (C-18) column using 0.01 M ammonium acetate buffer at pH 2.5 and methanol (50:50 v/v) mixture as mobile phase A and a methanol and water mixture (80:20 v/v) as mobile phase B in a gradient elution at flow rate 1.2 mL/min with ultraviolet detection at 210 nm. The method is found to be selective, precise, linear, accurate and robust. It was used for quality assurance and monitoring the synthetic reactions involved in the process development of lamotrizine. The method is found to be simple, rapid, specific and reliable for the determination of unreacted levels of raw materials and isomers in reaction mixtures and finished product lamotrizine. The method was fully validated as per International Conference of Harmonization guidelines and results from validation confirm that the method is highly suitable for its intended purpose. © The Author [2012]. Published by Oxford University Press. All rights reserved.

Reversed-phase thin-layer chromatography of homologs of Antimycin-A and related derivatives

USGS Publications Warehouse

Abidi, Sharon L.

1989-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

High Performance Liquid Chromatography of Some Analgesic Compounds: An Instrumental Analysis Experiment.

ERIC Educational Resources Information Center

Haddad, Paul; And Others

1983-01-01

Background information, procedures, and results are provided for an experiment demonstrating techniques of solvent selection, gradient elution, pH control, and ion-pairing in the analysis of an analgesic mixture using reversed-phase liquid chromatography on an octadecylsilane column. Although developed using sophisticated/expensive equipment, less…

Simultaneous separation by reversed-phase high-performance liquid chromatography and mass spectral identification of anthocyanins and flavonols in Shiraz grape skin.

PubMed

Downey, Mark O; Rochfort, Simone

2008-08-01

A limitation of large-scale viticultural trials is the time and cost of comprehensive compositional analysis of the fruit by high-performance liquid chromatography (HPLC). In addition, separate methods have generally been required to identify and quantify different classes of metabolites. To address these shortcomings a reversed-phase HPLC method was developed to simultaneously separate the anthocyanins and flavonols present in grape skins. The method employs a methanol and water gradient acidified with 10% formic acid with a run-time of 48 min including re-equilibration. Identity of anthocyanins and flavonols in Shiraz (Vitis vinifera L.) skin was confirmed by mass spectral analysis.

Ability of polymorphonuclear leukocytes to orient in gradients of chemotactic factors

PubMed Central

1977-01-01

Polymorphonuclear leukocyte (PMN) chemotaxis has been examined under conditions which allow phase microscope observations of cells responding to controlled gradients of chemotactic factors. With this visual assay, PMNs can be seen to orient rapidly and reversibly to gradients of N-formylmethionyl peptides. The level of orientation depends upon the mean concentration of peptide present as well as the concentration gradient. The response allows an estimation of the binding constant of the peptide to the cell. In optimal gradients, PMNs can detect a 1% difference in the concentration of peptide. At high cell densities, PMNs incubated with active peptides orient their locomotion away from the center of the cell population. This orientation appears to be due to inactivation of the peptides by the cells. Such inactivation in vivo could help to limit an inflammatory response. PMID:264125

A NEW HPLC METHOD FOR SEPARATION OF PHYTOPLANKTON PIGMENTS IN NATURAL SAMPLES

EPA Science Inventory

A new high-performance liquid chromatographic (HPLC) method was developed to analyze, in a single run, most polar and non-polar chlorophylls and carotenoids from marine phytoplankton. The method is based on a reverse-phase amide C16 (RP-amide C16) column and an elution gradient o...

High Performance Liquid Chromatographic Analysis of Phytoplankton Pigments Using a C16-Amide Column

EPA Science Inventory

A reverse-phase high performance liquid chromatographic (RP-HPLC) method was developed to analyze in a single run, most polar and non-polar chlorophylls and carotenoids from marine phytoplankton. The method is based on a RP-C16-Amide column and a ternary gradient system consistin...

Microfluidic chip for peptide analysis with an integrated HPLC column, sample enrichment column, and nanoelectrospray tip.

PubMed

Yin, Hongfeng; Killeen, Kevin; Brennen, Reid; Sobek, Dan; Werlich, Mark; van de Goor, Tom

2005-01-15

Current nano-LC/MS systems require the use of an enrichment column, a separation column, a nanospray tip, and the fittings needed to connect these parts together. In this paper, we present a microfabricated approach to nano-LC, which integrates these components on a single LC chip, eliminating the need for conventional LC connections. The chip was fabricated by laminating polyimide films with laser-ablated channels, ports, and frit structures. The enrichment and separation columns were packed using conventional reversed-phase chromatography particles. A face-seal rotary valve provided a means for switching between sample loading and separation configurations with minimum dead and delay volumes while allowing high-pressure operation. The LC chip and valve assembly were mounted within a custom electrospray source on an ion-trap mass spectrometer. The overall system performance was demonstrated through reversed-phase gradient separations of tryptic protein digests at flow rates between 100 and 400 nL/min. Microfluidic integration of the nano-LC components enabled separations with subfemtomole detection sensitivity, minimal carryover, and robust and stable electrospray throughout the LC solvent gradient.

Mixed-bed ion exchange chromatography employing a salt-free pH gradient for improved sensitivity and compatibility in MudPIT.

PubMed

Mommen, Geert P M; Meiring, Hugo D; Heck, Albert J R; de Jong, Ad P J M

2013-07-16

In proteomics, comprehensive analysis of peptides mixtures necessitates multiple dimensions of separation prior to mass spectrometry analysis to reduce sample complexity and increase the dynamic range of analysis. The main goal of this work was to improve the performance of (online) multidimensional protein identification technology (MudPIT) in terms of sensitivity, compatibility and recovery. The method employs weak anion and strong cation mixed-bed ion exchange chromatography (ACE) in the first separation dimension and reversed phase chromatography (RP) in the second separation dimension (Motoyama et.al. Anal. Chem 2007, 79, 3623-34.). We demonstrated that the chromatographic behavior of peptides in ACE chromatography depends on both the WAX/SCX mixing ratio as the ionic strength of the mobile phase system. This property allowed us to replace the conventional salt gradient by a (discontinuous) salt-free, pH gradient. First dimensional separation of peptides was accomplished with mixtures of aqueous formic acid and dimethylsulfoxide with increasing concentrations. The overall performance of this mobile phase system was found comparable to ammonium acetate buffers in application to ACE chromatography, but clearly outperformed strong cation exchange for use in first dimensional peptide separation. The dramatically improved compatibility between (salt-free) ion exchange chromatography and reversed phase chromatography-mass spectrometry allowed us to downscale the dimensions of the RP analytical column down to 25 μm i.d. for an additional 2- to 3-fold improvement in performance compared to current technology. The achieved levels of sensitivity, orthogonality, and compatibility demonstrates the potential of salt-free ACE MudPIT for the ultrasensitive, multidimensional analysis of very modest amounts of sample material.

Effect of pressure gradient and new phases for 1,3,5-trinitrohexahydro-s-triazine (RDX) under high pressures.

PubMed

Gao, Chan; Zhang, Xueyong; Zhang, Chuanchao; Sui, Zhilei; Hou, Meng; Dai, Rucheng; Wang, Zhongping; Zheng, Xianxu; Zhang, Zengming

2018-05-17

Herein, pressure-induced phase transitions of RDX up to 50 GPa were systematically studied under different compression conditions. Precise phase transition points were obtained based on high-quality Raman spectra with small pressure intervals. This favors the correctness of the theoretical formula for detonation and the design of a precision weapon. The experimental results indicated that α-RDX immediately transformed to γ-RDX at 3.5 GPa due to hydrostatic conditions and possible interaction between the penetrating helium and RDX, with helium gas as the pressure-transmitting medium (PTM). Mapping of pressure distribution in samples demonstrates that the pressure gradient is generated in the chamber and independent of other PTMs. The gradient induced the first phase transition starts at 2.3 GPa and completed at 4.1 GPa. The larger pressure gradient promoted phase transition in advance under higher pressures. Experimental results supported that there existed two conformers of AAI and AAE for γ-RDX, as proposed by another group. δ-RDX was considered to only occur in a hydrostatic environment around 18 GPa using helium as the PTM. This study confirms that δ-RDX is independent of PTM and exists under non-hydrostatic conditions. Evidence for a new phase (ζ) was found at about 28 GPa. These 4 phases have also been verified via XRD under high pressures. In addition to this, another new phase (η) may exist above 38 GPa, and it needs to be further confirmed in the future. Moreover, all the phase transitions were reversible after the pressure was released, and original α-RDX was always obtained at ambient pressure.

Development of an on-line mixed-mode gel liquid chromatography×reversed phase liquid chromatography method for separation of water extract from Flos Carthami.

PubMed

Wang, Yu-Qing; Tang, Xu; Li, Jia-Fu; Wu, Yun-Long; Sun, Yu-Ying; Fang, Mei-Juan; Wu, Zhen; Wang, Xiu-Min; Qiu, Ying-Kun

2017-10-13

A novel on-line comprehensive two-dimensional liquid chromatography (2D-LC) method by coupling mixed-mode gel liquid chromatography (MMG-LC) with reversed phase liquid chromatography (RPLC) was developed. A mixture of 17 reference compounds was used to study the separation mechanism. A crude water extract of Flos Carthami was applied to evaluate the performance of the novel 2D-LC system. In the first dimension, the extract was eluted with a gradient of water/methanol over a cross-linked dextran gel Sephadex LH-20 column. Meanwhile, the advantages of size exclusion, reversed phase partition and adsorption separation mechanism were exploited before further on-line reversed phase purification on the second dimension. This novel on-line mixed-mode Sephadex LH-20×RPLC method provided higher peak resolution, sample processing ability (2.5mg) and better orthogonality (72.9%) versus RPLC×RPLC and hydrophilic interaction liquid chromatography (HILIC)×RPLC. To the best of our knowledge, this is the first report of a mixed-mode Sephadex LH-20×RPLC separation method with successful applications in on-line mode, which might be beneficial for harvesting targets from complicated medicinal plants. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of a mixed-model stationary phase derived from glutamine for HPLC separation of structurally different biologically active compounds: HILIC and reversed-phase applications.

PubMed

Aral, Tarık; Aral, Hayriye; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2015-01-01

A novel mixed-mode stationary phase was synthesised starting from N-Boc-glutamine, aniline and spherical silica gel (4 µm, 60 Å). The prepared stationary phase was characterized by IR and elemental analysis. The new stationary phase bears an embedded amide group into phenyl ring, highly polar a terminal amide group and non-polar groups (phenyl and alkyl groups). At first, this new mixed-mode stationary phase was used for HILIC separation of four nucleotides and five nucleosides. The effects of different separation conditions, such as pH value, mobile phase and temperature, on the separation process were investigated. The optimum separation for nucleotides was achieved using HILIC isocratic elution with aqueous mobile phase and acetonitrile with 20°C column temperature. Under these conditions, the four nucleotides could be separated and detected at 265 nm within 14 min. Five nucleosides were separated under HILIC isocratic elution with aqueous mobile phase containing pH=3.25 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 265 nm within 14 min. Chromatographic parameters as retention factor, selectivity, theoretical plate number and peak asymmetry factor were calculated for the effect of temperature and water content in mobile phase on the separation process. The new column was also tested for nucleotides and nucleosides mixture and six analytes were separated in 10min. The chromatographic behaviours of these polar analytes on the new mixed-model stationary phase were compared with those of HILIC columns under similar conditions. Further, phytohormones and phenolic compounds were separated in order to see influence of the new stationary phase in reverse phase conditions. Eleven plant phytohormones were separated within 13 min using RP-HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 230 or 278 nm. The best separation conditions for seven phenolic compounds was also achieved using reversed-phase HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and seven phenolic compounds could be separated and detected at 230 nm within 16 min. Copyright © 2014 Elsevier B.V. All rights reserved.

Rheological Properties of Quasi-2D Fluids in Microgravity

NASA Technical Reports Server (NTRS)

Trittel, Torsten; Stannarius, Ralf; Eremin, Alexey; Harth, Kirsten; Clark, Noel A.; Maclennan, Joseph; Glaser, Matthew; Park, Cheol; Hall, Nancy; Tin, Padetha

2016-01-01

Freely suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters are used to study thermally driven convection and diffusion in the film plane. The experiments were performed during a six minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). The project served as a preliminary test for a planned ISS Experiment with liquid crystal films (OASIS), and in addition it provided new experimental data on smectic films exposed to in-plane thermal gradients.We find an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to a Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 Kmm, thermally driven convection sets in when the hot post reaches the transition temperature to the nematic phase.An additional experiment was performed under microgravity conditions to test the stability of liquid crystal bridges in different smectic phases.

Applications of the solvation parameter model in reversed-phase liquid chromatography.

PubMed

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Cyclohexylamine additives for enhanced peptide separations in reversed phase liquid chromatography.

PubMed

Cole, S R; Dorsey, J G

1997-01-01

While the choice of stationary phase, organic modifier, and gradient strength can have significant effects on biomolecule separations, mobile phase additives can also have a significant effect on the chromatographic selectivity, recovery, efficiency and resolution. Given the importance of stationary phase coverage, the beneficial, silanol-masking properties of amines, and the potential for selectivity modification through ion-pair interactions, cyclohexylamine was examined as a mobile phase additive and compared with triethylamine and trifluoroacetic acid. Greatly improved separation was possible when cyclohexylamine was used as compared with phosphate buffer, and cyclohexylamine did not require purification before use, while triethylamine required distillation before 'clean' chromatograms were obtained.

Liquid chromatographic determination of sennosides in Cassia angustifolia leaves.

PubMed

Srivastava, Alpuna; Pandey, Richa; Verma, Ram K; Gupta, Madan M

2006-01-01

A simple liquid chromatographic method was developed for the determination of sennosides B and A in leaves of Cassia angustifolia. These compounds were extracted from leaves with a mixture of methanol-water (70 + 30, v/v) after defatting with hexane. Analyte separation and quantitation were achieved by gradient reversed-phase liquid chromatography and UV absorbance at 270 nm using a photodiode array detector. The method involves the use of an RP-18 Lichrocart reversed-phase column (5 microm, 125 x 4.0 mm id) and a binary gradient mobile-phase profile. The various other aspects of analysis, namely, peak purity, similarity, recovery, repeatability, and robustness, were validated. Average recoveries of 98.5 and 98.6%, with a coefficient of variation of 0.8 and 0.3%, were obtained by spiking sample solution with 3 different concentration solutions of standards (60, 100, and 200 microg/mL). Detection limits were 10 microg/mL for sennoside B and 35 microg/mL for sennoside A, present in the sample solution. The quantitation limits were 28 and 100 microg/mL. The analytical method was applied to a large number of senna leaf samples. The new method provides a reliable tool for rapid screening of C. angustifolia samples in large numbers, which is needed in breeding/genetic engineering and genetic mapping experiments.

Characterization of Jamaican agro-industrial wastes. Part II, fatty acid profiling using HPLC: precolumn derivatization with phenacyl bromide.

PubMed

Bailey-Shaw, Y A; Golden, K D; Pearson, A G M; Porter, R B R

2012-09-01

This paper describes the determination of fatty acid composition of coffee, citrus and rum distillery wastes using reversed-phase high-performance liquid chromatography (RP-HPLC). Lipid extracts of the waste samples are derivatized with phenacyl bromide and their phenacyl esters are separated on a C8 reversed-phase column by using continuous gradient elution with water and acetonitrile. The presence of saturated and unsaturated fatty acids in quantifiable amounts in the examined wastes, as well as the high percentage recoveries, are clear indications that these wastes have potential value as inexpensive sources of lipids. The HPLC procedures described here could be adopted for further analysis of materials of this nature.

Highly efficient monolithic silica capillary columns modified with poly(acrylic acid) for hydrophilic interaction chromatography.

PubMed

Horie, Kanta; Ikegami, Tohru; Hosoya, Ken; Saad, Nabil; Fiehn, Oliver; Tanaka, Nobuo

2007-09-14

Monolithic silica capillary columns for hydrophilic interaction liquid chromatography (HILIC) were prepared by on-column polymerization of acrylic acid on monolithic silica in a fused silica capillary modified with anchor groups. The products maintained the high permeability (K=5 x 10(-14)m(2)) and provided a plate height (H) of less than 10 microm at optimum linear velocity (u) and H below 20 microm at u=6mm/s for polar solutes including nucleosides and carbohydrates. The HILIC mode monolithic silica capillary column was able to produce 10000 theoretical plates (N) with column dead time (t(0)) of 20s at a pressure drop of 20 MPa or lower. The total performance was much higher than conventional particle-packed HILIC columns currently available. The gradient separations of peptides by a capillary LC-electrospray mass spectrometry system resulted in very different retention selectivity between reversed-phase mode separations and the HILIC mode separations with a peak capacity of ca. 100 in a 10 min gradient time in either mode. The high performance observed with the monolithic silica capillary column modified with poly(acrylic acid) suggests that the HILIC mode can be an alternative to the reversed-phase mode for a wide range of compounds, especially for those of high polarity in isocratic as well as gradient elution.

On the development and benchmarking of an approach to model gas transport in fractured media with immobile water storage

NASA Astrophysics Data System (ADS)

Harp, D. R.; Ortiz, J. P.; Pandey, S.; Karra, S.; Viswanathan, H. S.; Stauffer, P. H.; Anderson, D. N.; Bradley, C. R.

2017-12-01

In unsaturated fractured media, the rate of gas transport is much greater than liquid transport in many applications (e.g., soil vapor extraction operations, methane leaks from hydraulic fracking, shallow CO2 transport from geologic sequestration operations, and later-time radionuclide gas transport from underground nuclear explosions). However, the relatively immobile pore water can inhibit or promote gas transport for soluble constituents by providing storage. In scenarios with constant pressure gradients, the gas transport will be retarded. In scenarios with reversing pressure gradients (i.e. barometric pressure variations) pore water storage can enhance gas transport by providing a ratcheting mechanism. Recognizing the computational efficiency that can be gained using a single-phase model and the necessity of considering pore water storage, we develop a Richard's solution approach that includes kinetic dissolution/volatilization of constituents. Henry's Law governs the equilibrium gaseous/aqueous phase partitioning in the approach. The approach is implemented in a development branch of the PFLOTRAN simulator. We verify the approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) sinusoidal barometric pumping of a fracture, and (4) gas transport along a fracture with uniform flow and diffusive walls. We demonstrate the retardation of gas transport in cases with constant pressure gradients and the enhancement of gas transport with reversing pressure gradients. The figure presents the verification of our approach to the analytical solution of barometric pumping of a fracture from Nilson et al (1991) where the x-axis "Horizontal axis" is the distance into the matrix block from the fracture.

On the development and benchmarking of an approach to model gas transport in fractured media with immobile water storage

NASA Astrophysics Data System (ADS)

Harp, D. R.; Ortiz, J. P.; Pandey, S.; Karra, S.; Viswanathan, H. S.; Stauffer, P. H.; Anderson, D. N.; Bradley, C. R.

2016-12-01

In unsaturated fractured media, the rate of gas transport is much greater than liquid transport in many applications (e.g., soil vapor extraction operations, methane leaks from hydraulic fracking, shallow CO2 transport from geologic sequestration operations, and later-time radionuclide gas transport from underground nuclear explosions). However, the relatively immobile pore water can inhibit or promote gas transport for soluble constituents by providing storage. In scenarios with constant pressure gradients, the gas transport will be retarded. In scenarios with reversing pressure gradients (i.e. barometric pressure variations) pore water storage can enhance gas transport by providing a ratcheting mechanism. Recognizing the computational efficiency that can be gained using a single-phase model and the necessity of considering pore water storage, we develop a Richard's solution approach that includes kinetic dissolution/volatilization of constituents. Henry's Law governs the equilibrium gaseous/aqueous phase partitioning in the approach. The approach is implemented in a development branch of the PFLOTRAN simulator. We verify the approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) sinusoidal barometric pumping of a fracture, and (4) gas transport along a fracture with uniform flow and diffusive walls. We demonstrate the retardation of gas transport in cases with constant pressure gradients and the enhancement of gas transport with reversing pressure gradients. The figure presents the verification of our approach to the analytical solution of barometric pumping of a fracture from Nilson et al (1991) where the x-axis "Horizontal axis" is the distance into the matrix block from the fracture.

Gradient retention prediction of acid-base analytes in reversed phase liquid chromatography: a simplified approach for acetonitrile-water mobile phases.

PubMed

Andrés, Axel; Rosés, Martí; Bosch, Elisabeth

2014-11-28

In previous work, a two-parameter model to predict chromatographic retention of ionizable analytes in gradient mode was proposed. However, the procedure required some previous experimental work to get a suitable description of the pKa change with the mobile phase composition. In the present study this previous experimental work has been simplified. The analyte pKa values have been calculated through equations whose coefficients vary depending on their functional group. Forced by this new approach, other simplifications regarding the retention of the totally neutral and totally ionized species also had to be performed. After the simplifications were applied, new prediction values were obtained and compared with the previously acquired experimental data. The simplified model gave pretty good predictions while saving a significant amount of time and resources. Copyright © 2014 Elsevier B.V. All rights reserved.

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves

NASA Astrophysics Data System (ADS)

Zeb, Alam; Ullah, Fareed

2017-04-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins and two chlorophylls. Lutein (806.0 µg/g), chlorophyll b' (410.0 µg/g), chlorophyll a (162.4 µg/g), 9'-Z-neoxanthin (142.8 µg/g) and all-E-violaxanthin (82.2 µg/g)) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of thirteen compounds, namely p-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5-O-caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g) and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for possible medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a potential source of nutraceuticals or as a functional food ingredient.

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves

PubMed Central

Zeb, Alam; Ullah, Fareed

2017-01-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins, and two chlorophylls. Lutein (806.0 μg/g), chlorophyll b′ (410.0 μg/g), chlorophyll a (162.4 μg/g), 9′-Z-neoxanthin (142.8 μg/g) and all-E-violaxanthin (82.2 μg/g) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of 13 compounds, namely 4-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5-O-caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g), and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of Adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for the potential medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a possible source of nutraceuticals or as a functional food ingredient. PMID:28497036

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves.

PubMed

Zeb, Alam; Ullah, Fareed

2017-01-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins, and two chlorophylls. Lutein (806.0 μg/g), chlorophyll b ' (410.0 μg/g), chlorophyll a (162.4 μg/g), 9'- Z -neoxanthin (142.8 μg/g) and all- E -violaxanthin (82.2 μg/g) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of 13 compounds, namely 4-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5- O -caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g), and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of Adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for the potential medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a possible source of nutraceuticals or as a functional food ingredient.

Evolution of a Planar Wake in Adverse Pressure Gradient

NASA Technical Reports Server (NTRS)

Driver, David M.; Mateer, George G.

2016-01-01

In the interest of improving the predictability of high-lift systems at maximum lift conditions, a series of fundamental experiments were conducted to study the effects of adverse pressure gradient on a wake flow. Mean and fluctuating velocities were measured with a two-component laser-Doppler velocimeter. Data were obtained for several cases of adverse pressure gradient, producing flows ranging from no reversed flow to massively reversed flow. While the turbulent Reynolds stresses increase with increasing size of the reversed flow region, the gradient of Reynolds stress does not. Computations using various turbulence models were unable to reproduce the reversed flow.

Improved optimization of polycyclic aromatic hydrocarbons (PAHs) mixtures resolution in reversed-phase high-performance liquid chromatography by using factorial design and response surface methodology.

PubMed

Andrade-Eiroa, Auréa; Diévart, Pascal; Dagaut, Philippe

2010-04-15

A new procedure for optimizing PAHs separation in very complex mixtures by reverse phase high performance (RPLC) is proposed. It is based on changing gradually the experimental conditions all along the chromatographic procedure as a function of the physical properties of the compounds eluted. The temperature and speed flow gradients allowed obtaining the optimum resolution in large chromatographic determinations where PAHs with very different medium polarizability have to be separated. Whereas optimization procedures of RPLC methodologies had always been accomplished regardless of the physico-chemical properties of the target analytes, we found that resolution is highly dependent on the physico-chemical properties of the target analytes. Based on resolution criterion, optimization process for a 16 EPA PAHs mixture was performed on three sets of difficult-to-separate PAHs pairs: acenaphthene-fluorene (for the optimization procedure in the first part of the chromatogram where light PAHs elute), benzo[g,h,i]perylene-dibenzo[a,h]anthracene and benzo[g,h,i]perylene-indeno[1,2,3-cd]pyrene (for the optimization procedure of the second part of the chromatogram where the heavier PAHs elute). Two-level full factorial designs were applied to detect interactions among variables to be optimized: speed flow, temperature of column oven and mobile-phase gradient in the two parts of the studied chromatogram. Experimental data were fitted by multivariate nonlinear regression models and optimum values of speed flow and temperature were obtained through mathematical analysis of the constructed models. An HPLC system equipped with a reversed phase 5 microm C18, 250 mm x 4.6mm column (with acetonitrile/water mobile phase), a column oven, a binary pump, a photodiode array detector (PDA), and a fluorimetric detector were used in this work. Optimum resolution was achieved operating at 1.0 mL/min in the first part of the chromatogram (until 45 min) and 0.5 mL/min in the second one (from 45 min to the end) and by applying programmed temperature gradient (15 degrees C until 30 min and progressively increasing temperature until reaching 40 degrees C at 45 min). (c) 2009 Elsevier B.V. All rights reserved.

Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

PubMed

Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

2015-07-07

The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

Direct measurement of the glucuronide conjugate of 1-hydroxypyrene in human urine by using liquid chromatography with tandem mass spectrometry.

PubMed

Kakimoto, Kensaku; Toriba, Akira; Ohno, Takanori; Ueno, Mariko; Kameda, Takayuki; Tang, Ning; Hayakawa, Kazuichi

2008-05-15

To evaluate human exposure to polycyclic aromatic hydrocarbons (PAHs), we developed a rapid, simple and sensitive method for determining 1-hydroxypyrene-glucuronide (1-OHP-G) in human urine. To improve precision, a deuterated glucuronide was used as an internal standard. The method requires only 1 mL of urine. The urine was treated with a mixed-mode anion-exchange and reversed-phase solid-phase extraction cartridge (Oasis MAX). The analytes were analyzed with a C(18) reversed-phase column with a gradient elution, followed by tandem mass spectrometry with electrospray ionization in negative ion mode. The detection limit of 1-OHP-G (corresponding to a signal-to-noise ratio of 3) was 0.13 fmol/injection. Urinary concentrations of 1-OHP-G determined by this method were strongly correlated (r(2)=0.961) with concentrations of 1-hydroxypyrene by conventional HPLC with fluorescence detection.

Reversible beam heater for suppression of microbunching instability by transverse gradient undulators

NASA Astrophysics Data System (ADS)

Liu, Tao; Qin, Weilun; Wang, Dong; Huang, Zhirong

2017-08-01

The microbunching instability driven by beam collective effects in a linear accelerator of a free-electron laser (FEL) facility significantly degrades the electron beam quality and FEL performance. A conventional method to suppress this instability is to introduce an additional uncorrelated energy spread by laser-electron interaction, which has been successfully operated in the Linac Coherent Light Source and Fermi@Elettra, etc. Some other ideas are recently proposed to suppress the instability without increasing energy spread, which could benefit the seeded FEL schemes. In this paper, we propose a reversible electron beam heater using two transverse gradient undulators to suppress the microbunching instability. This scheme introduces both an energy spread increase and a transverse-to-longitudinal phase space coupling, which suppress the microbunching instabilities driven by both longitudinal space charge and coherent synchrotron radiation before and within the system. Finally the induced energy spread increase and emittance growth are reversed. Theoretical analysis and numerical simulations are presented to verify the feasibility of the scheme and indicate the capability to improve the seeded FEL radiation performance.

Reversible beam heater for suppression of microbunching instability by transverse gradient undulators

DOE PAGES

Liu, Tao; Qin, Weilun; Wang, Dong; ...

2017-08-02

The microbunching instability driven by beam collective effects in a linear accelerator of a free-electron laser (FEL) facility significantly degrades the electron beam quality and FEL performance. A conventional method to suppress this instability is to introduce an additional uncorrelated energy spread by laser-electron interaction, which has been successfully operated in the Linac Coherent Light Source and Fermi@Elettra, etc. Some other ideas are recently proposed to suppress the instability without increasing energy spread, which could benefit the seeded FEL schemes. In this paper, we propose a reversible electron beam heater using two transverse gradient undulators to suppress the microbunching instability.more » This scheme introduces both an energy spread increase and a transverse-to-longitudinal phase space coupling, which suppress the microbunching instabilities driven by both longitudinal space charge and coherent synchrotron radiation before and within the system. Finally the induced energy spread increase and emittance growth are reversed. In conclusion, theoretical analysis and numerical simulations are presented to verify the feasibility of the scheme and indicate the capability to improve the seeded FEL radiation performance.« less

High-performance liquid chromatographic method for the determination of dansyl-polyamines

Treesearch

Subhash C. Minocha; Rakesh Minocha; Cheryl A. Robie

1990-01-01

This paper describes a fast reliable, and a sensitive technique for the separation and quantification of dansylated polyamines by high-performance liquid chromatography. Using a small 33 x 4.6 mm I.D., 3 ?m particle size, C18 reversed-phase cartridge column and a linear gradient of acetonitrile-heptanesulfonate (10 mM, pH 3.4...

ANALYSIS OF PROTEIN DIGESTS BY nano- SCX/RP/MSMS WITH pH SALT GRADIENT SCX ELUTION

EPA Science Inventory

The objective of this study was to optimize chromatographic parameters for complex peptide mixture analyses using two dimensional nano-LC/MSMS system. It used a strong cation exchange (SCX) and reversed phase chromatography (RP). The SCX solvent system was designed to promote pep...

NOVEL CONTINUOUS PH/SALT GRADIENT AND PEPTIDE SCORE FOR STRONG CATION EXCHANGE CHROMATOGRAPHY IN 2D-NANO-LC/MSMS PEPTIDE IDENTIFICATION FOR PROTEOMICS

EPA Science Inventory

Tryptic digests of human serum albumin (HSA) and human lung epithelial cell lysates were used as test samples in a novel proteomics study. Peptides were separated and analyzed using 2D-nano-LC/MSMS with strong cation exchange (SCX) and reverse phase (RP) chromatography and contin...

Separation and quantitation of colour pigments of chili powder (Capsicum frutescens) by high-performance liquid chromatography-diode array detection.

PubMed

Cserháti, T; Forgács, E; Morais, M H; Mota, T; Ramos, A

2000-10-27

The performance of reversed-phase thin-layer (RP-TLC) and reversed-phase high-performance liquid chromatography (RP-HPLC) was compared for the separation and determination of the colour pigments of chili (Capsicum frutescens) powder using a wide variety of eluent systems. No separation of pigments was achieved in RP-TLC, however, it was established that tetrahydrofuran shows an unusually high solvent strength. RP-HPLC using water-methanol-acetonitrile gradient elution separated the chili pigments in many fractions. Diode array detection (DAD) indicated that yellow pigments are eluted earlier than the red ones and chili powder contains more yellow pigments than common paprika powders. It was established that the very different absorption spectra of pigments make the use of DAD necessary.

Flow convergence caused by a salinity minimum in a tidal channel

USGS Publications Warehouse

Warner, John C.; Schoellhamer, David H.; Burau, Jon R.; Schladow, S. Geoffrey

2006-01-01

Residence times of dissolved substances and sedimentation rates in tidal channels are affected by residual (tidally averaged) circulation patterns. One influence on these circulation patterns is the longitudinal density gradient. In most estuaries the longitudinal density gradient typically maintains a constant direction. However, a junction of tidal channels can create a local reversal (change in sign) of the density gradient. This can occur due to a difference in the phase of tidal currents in each channel. In San Francisco Bay, the phasing of the currents at the junction of Mare Island Strait and Carquinez Strait produces a local salinity minimum in Mare Island Strait. At the location of a local salinity minimum the longitudinal density gradient reverses direction. This paper presents four numerical models that were used to investigate the circulation caused by the salinity minimum: (1) A simple one-dimensional (1D) finite difference model demonstrates that a local salinity minimum is advected into Mare Island Strait from the junction with Carquinez Strait during flood tide. (2) A three-dimensional (3D) hydrodynamic finite element model is used to compute the tidally averaged circulation in a channel that contains a salinity minimum (a change in the sign of the longitudinal density gradient) and compares that to a channel that contains a longitudinal density gradient in a constant direction. The tidally averaged circulation produced by the salinity minimum is characterized by converging flow at the bed and diverging flow at the surface, whereas the circulation produced by the constant direction gradient is characterized by converging flow at the bed and downstream surface currents. These velocity fields are used to drive both a particle tracking and a sediment transport model. (3) A particle tracking model demonstrates a 30 percent increase in the residence time of neutrally buoyant particles transported through the salinity minimum, as compared to transport through a constant direction density gradient. (4) A sediment transport model demonstrates increased deposition at the near-bed null point of the salinity minimum, as compared to the constant direction gradient null point. These results are corroborated by historically noted large sedimentation rates and a local maximum of selenium accumulation in clams at the null point in Mare Island Strait.

[Fast optimization of stepwise gradient conditions for ternary mobile phase in reversed-phase high performance liquid chromatography].

PubMed

Shan, Yi-chu; Zhang, Yu-kui; Zhao, Rui-huan

2002-07-01

In high performance liquid chromatography, it is necessary to apply multi-composition gradient elution for the separation of complex samples such as environmental and biological samples. Multivariate stepwise gradient elution is one of the most efficient elution modes, because it combines the high selectivity of multi-composition mobile phase and shorter analysis time of gradient elution. In practical separations, the separation selectivity of samples can be effectively adjusted by using ternary mobile phase. For the optimization of these parameters, the retention equation of samples must be obtained at first. Traditionally, several isocratic experiments are used to get the retention equation of solute. However, it is time consuming especially for the separation of complex samples with a wide range of polarity. A new method for the fast optimization of ternary stepwise gradient elution was proposed based on the migration rule of solute in column. First, the coefficients of retention equation of solute are obtained by running several linear gradient experiments, then the optimal separation conditions are searched according to the hierarchical chromatography response function which acts as the optimization criterion. For each kind of organic modifier, two initial linear gradient experiments are used to obtain the primary coefficients of retention equation of each solute. For ternary mobile phase, only four linear gradient runs are needed to get the coefficients of retention equation. Then the retention times of solutes under arbitrary mobile phase composition can be predicted. The initial optimal mobile phase composition is obtained by resolution mapping for all of the solutes. A hierarchical chromatography response function is used to evaluate the separation efficiencies and search the optimal elution conditions. In subsequent optimization, the migrating distance of solute in the column is considered to decide the mobile phase composition and sustaining time of the latter steps until all the solutes are eluted out. Thus the first stepwise gradient elution conditions are predicted. If the resolution of samples under the predicted optimal separation conditions is satisfactory, the optimization procedure is stopped; otherwise, the coefficients of retention equation are adjusted according to the experimental results under the previously predicted elution conditions. Then the new stepwise gradient elution conditions are predicted repeatedly until satisfactory resolution is obtained. Normally, the satisfactory separation conditions can be found only after six experiments by using the proposed method. In comparison with the traditional optimization method, the time needed to finish the optimization procedure can be greatly reduced. The method has been validated by its application to the separation of several samples such as amino acid derivatives, aromatic amines, in which satisfactory separations were obtained with predicted resolution.

Recursion equations in predicting band width under gradient elution.

PubMed

Liang, Heng; Liu, Ying

2004-06-18

The evolution of solute zone under gradient elution is a typical problem of non-linear continuity equation since the local diffusion coefficient and local migration velocity of the mass cells of solute zones are the functions of position and time due to space- and time-variable mobile phase composition. In this paper, based on the mesoscopic approaches (Lagrangian description, the continuity theory and the local equilibrium assumption), the evolution of solute zones in space- and time-dependent fields is described by the iterative addition of local probability density of the mass cells of solute zones. Furthermore, on macroscopic levels, the recursion equations have been proposed to simulate zone migration and spreading in reversed-phase high-performance liquid chromatography (RP-HPLC) through directly relating local retention factor and local diffusion coefficient to local mobile phase concentration. This new approach differs entirely from the traditional theories on plate concept with Eulerian description, since band width recursion equation is actually the accumulation of local diffusion coefficients of solute zones to discrete-time slices. Recursion equations and literature equations were used in dealing with same experimental data in RP-HPLC, and the comparison results show that the recursion equations can accurately predict band width under gradient elution.

Single-shot EPI with Nyquist ghost compensation: Interleaved Dual-Echo with Acceleration (IDEA) EPI

PubMed Central

Poser, Benedikt A; Barth, Markus; Goa, Pål-Erik; Deng, Weiran; Stenger, V Andrew

2012-01-01

Echo planar imaging is most commonly used for BOLD fMRI, owing to its sensitivity and acquisition speed. A major problem with EPI is Nyquist (N/2) ghosting, most notably at high field. EPI data are acquired under an oscillating readout gradient and hence vulnerable to gradient imperfections such as eddy current delays and off-resonance effects, as these cause inconsistencies between odd and even k-space lines after time reversal. We propose a straightforward and pragmatic method herein termed Interleaved Dual Echo with Acceleration (IDEA) EPI: Two k-spaces (echoes) are acquired under the positive and negative readout lobes, respectively, by performing phase blips only before alternate readout gradients. From these two k-spaces, two almost entirely ghost free images per shot can be constructed, without need for phase correction. The doubled echo train length can be compensated by parallel imaging and/or partial Fourier acquisition. The two k-spaces can either be complex-averaged during reconstruction, which results in near-perfect cancellation of residual phase errors, or reconstructed into separate images. We demonstrate the efficacy of IDEA EPI and show phantom and in vivo images at both 3 and 7 Tesla. PMID:22411762

High-performance liquid-chromatographic separation of subcomponents of antimycin-A

USGS Publications Warehouse

Abidi, S.L.

1988-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Single column comprehensive analysis of pharmaceutical preparations using dual-injection mixed-mode (ion-exchange and reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Taylor, Mark R; Haddad, Paul R; Nesterenko, Pavel N; Paull, Brett

2013-12-01

The comprehensive separation and detection of hydrophobic and hydrophilic active pharmaceutical ingredients (APIs), their counter-ions (organic, inorganic) and excipients, using a single mixed-mode chromatographic column, and a dual injection approach is presented. Using a mixed-mode Thermo Fisher Acclaim Trinity P1 column, APIs, their counter-ions and possible degradants were first separated using a combination of anion-exchange, cation-exchange and hydrophobic interactions, using a mobile phase consisting of a dual organic modifier/salt concentration gradient. A complementary method was also developed using the same column for the separation of hydrophilic bulk excipients, using hydrophilic interaction liquid chromatography (HILIC) under high organic solvent mobile phase conditions. These two methods were then combined within a single gradient run using dual sample injection, with the first injection at the start of the applied gradient (mixed-mode retention of solutes), followed by a second sample injection at the end of the gradient (HILIC retention of solutes). Detection using both ultraviolet absorbance and refractive index enabled the sensitive detection of APIs and UV-absorbing counter-ions, together with quantitative determination of bulk excipients. The developed approach was applied successfully to the analysis of a dry powder inhalers (Flixotide(®), Spiriva(®)), enabling comprehensive quantification of all APIs and excipients in the sample. Copyright © 2013 Elsevier B.V. All rights reserved.

Simultaneous determination of azathioprine and 6-mercaptopurine by high-performance liquid chromatography.

PubMed

Van Os, E C; McKinney, J A; Zins, B J; Mays, D C; Schriver, Z H; Sandborn, W J; Lipsky, J J

1996-04-26

A specific, sensitive, single-step solid-phase extraction and reversed-phase high-performance liquid chromatographic method for the simultaneous determination of plasma 6-mercaptopurine and azathioprine concentrations is reported. Following solid-phase extraction, analytes are separated on a C18 column with mobile phase consisting of 0.8% acetonitrile in 1 mM triethylamine, pH 3.2, run on a gradient system. Quantitation limits were 5 ng/ml and 2 ng/ml for azathioprine and 6-mercaptopurine, respectively. Peak heights correlated linearly to known extracted standards for 6-mercaptopurine and azathioprine (r = 0.999) over a range of 2-200 ng/ml. No chromatographic interferences were detected.

Determination of preservatives in cosmetics, cleaning agents and pharmaceuticals using fast liquid chromatography.

PubMed

Baranowska, Irena; Wojciechowska, Iwona; Solarz, Natalia; Krutysza, Ewa

2014-01-01

This paper reports the development of a method for simultaneously determining five preservatives in cosmetics, cleaning agents and pharmaceuticals by fast liquid chromatography. Methylisothiazolinone, methylchloroisothiazolinone, benzyl alcohol, sodium benzoate and methylparaben were separated on a Chromolith Fast Gradient reversed-phase 18e column using gradient elution with acetonitrile and a 0.1% aqueous solution of formic acid, with a run time of 3 min. The preparation of solid and liquid samples included ultrasonic extraction with methanol with recoveries ranging from 69 to 119%. The developed method was used to analyze samples of cosmetics (66 samples), cleaning agents (five samples) and pharmaceutical industry products (17 samples).

Development of a perfusion reversed-phase high performance liquid chromatography method for the characterisation of maize products using multivariate analysis.

PubMed

Rodriguez-Nogales, J M; Garcia, M C; Marina, M L

2006-02-03

A perfusion reversed-phase high performance liquid chromatography (RP-HPLC) method has been designed to allow rapid (3.4 min) separations of maize proteins with high resolution. Several factors, such as extraction conditions, temperature, detection wavelength and type and concentration of ion-pairing agent were optimised. A fine optimisation of the gradient elution was also performed by applying experimental design. Commercial maize products for human consumption (flours, precocked flours, fried snacks and extruded snacks) were characterised for the first time by perfusion RP-HPLC and their chromatographic profiles allowed a differentiation among products relating the different technological process used for their preparation. Furthermore, applying discriminant analysis makes it possible to group the samples according with the technological process suffered by maize products, obtaining a good prediction in 92% of the samples.

In vivo biosynthesis of L-(/sup 35/S)Cys-arginine vasopressin, -oxytocin, and -somatostatin: rapid estimation using reversed phase high pressure liquid chromatography. [Rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franco-Bourland, R.E.; Fernstrom, J.D.

1981-01-01

L(/sup 35/S)Cys-arginine vasopressin, -oxytocin, and -somatostatin were purified from hypothalami and neurohypophyses 4 h after rats received L(/sup 35/S)Cys via the third ventricle. After acetic acid extraction, Sephadex G-25 filtration, and chemoadsorption to C18-silica (Sep-Pak cartridges), the labeled peptides were rapidly separated by gradient elution, reversed phase, high pressure liquid chromatography (HPLC). The identity and isotopic purity of the labeled peptides were determined by several reversed phase HPLC procedures in conjunction with chemical modification. The labeled peptide fractions were at least 50% radiochemically pure. Using this HPLC isolation procedure, incorporation of L-(/sup 35/S)Cys into each peptide was determined in hydratedmore » and dehydrated rats. Label incorporation into arginine vasopressin and oxytocin in the hypothalamus and the neurohypophysis of dehydrated rats was 2-3 times greater than that in hydrated rats. Incorporation of label into hypothalamic and neurohypophyseal somatostatin was unaffected by the hydration state of the animal. This procedure thus provides a very rapid, but sensitive, set of techniques for studying the control of small peptide biosynthesis in the brain.« less

Retention modeling under organic modifier gradient conditions in ion-pair reversed-phase chromatography. Application to the separation of a set of underivatized amino acids.

PubMed

Pappa-Louisi, A; Agrafiotou, P; Papachristos, K

2010-07-01

The combined effect of the ion-pairing reagent concentration, C(ipr), and organic modifier content, phi, on the retention under phi-gradient conditions at different constant C(ipr) was treated in this study by using two approaches. In the first approach, the prediction of the retention time of a sample solute is based on a direct fitting procedure of a proper retention model to 3-D phi-gradient retention data obtained under the same phi-linear variation but with different slope and time duration of the initial isocratic part and in the presence of various constant C(ipr) values in the eluent. The second approach is based on a retention model describing the combined effect of C(ipr) and phi on the retention of solutes in isocratic mode and consequently analyzes isocratic data obtained in mobile phases containing different C(ipr) values. The effectiveness of the above approaches was tested in the retention prediction of a mixture of 16 underivatized amino acids using mobile phases containing acetonitrile as organic modifier and sodium dodecyl sulfate as ion-pairing reagent. From these approaches, only the first one gives satisfactory predictions and can be successfully used in optimization of ion-pair chromatographic separations under gradient conditions. The failure of the second approach to predict the retention of solutes in the gradient elution mode in the presence of different C(ipr) values was attributed to slow changes in the distribution equilibrium of ion-pairing reagents caused by phi-variation.

Rapid and accurate reversed-phase high-performance liquid chromatographic determination of conjugated bile acids in human bile for routine clinical applications. Therapeutic control during gallstone dissolution therapy.

PubMed

Swobodnik, W; Klüppelberg, U; Wechsler, J G; Volz, M; Normandin, G; Ditschuneit, H

1985-05-03

This paper introduces a new method to detect the taurine and glycine conjugates of five different bile acids (cholic acid, deoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid and lithocholic acid) in human bile. Advantages of this method are sufficient separation of compounds within a short period of time and a high rate of reproducibility. Using a mobile phase gradient of acetonitrile and water, modified with tetrabutylammonium hydrogen sulphate (0.0075 mol/l), we were able to maximize the differentiation between ursodeoxycholic acid and lithocholic acid, which is of primary interest during conservative gallstone dissolution therapy. Use of this gradient reduced analysis time to less than 0.5 h. Recovery rates for this modified method ranged from 94% to 100%, and reproducibility was 98%, sufficient for routine clinical applications.

Determination of pentachlorophenol in water and aquifer sediments by high-performance liquid chromatography

USGS Publications Warehouse

Goerlitz, D.F.

1981-01-01

Methods for the determination of pentachlorophenol (PCP) in water and aquifer sediments are presented. Reverse-phase high-performance liquid chromotography employing ion suppression and gradient elution is used. PCP can be determined directly in water at a lower limit of detection Of 0.2 micrograms per liter. For extracts of sediment, PCP can be determined to a lower limit of 1.0 micrograms per kilogram.

Simultaneous determination of 16 purine derivatives in urinary calculi by gradient reversed-phase high-performance liquid chromatography with UV detection.

PubMed

Safranow, Krzysztof; Machoy, Zygmunt

2005-05-25

A reversed-phase high-performance liquid chromatography (HPLC) method with ultraviolet detection has been developed for the analysis of purines in urinary calculi. The method using gradient of methanol concentration and pH was able to separate 16 compounds: uric acid, 2,8-dihydroxyadenine, xanthine, hypoxanthine, allopurinol and oxypurinol as well as 10 methyl derivatives of uric acid or xanthine (1-, 3-, 7- and 9-methyluric acid, 1,3-, 1,7- and 3,7-dimethyluric acid, 1-, 3- and 7-methylxanthine). Limits of detection for individual compounds ranged from 0.006 to 0.035 mg purine/g of the stone weight and precision (CV%) was 0.5-2.4%. The method enabled us to detect in human uric acid stones admixtures of nine other purine derivatives: natural metabolites (hypoxanthine, xanthine, 2,8-dihydroxyadenine) and methylated purines (1-, 3- and 7-methyluric acid, 1,3-dimethyluric acid, 3- and 7-methylxanthine) originating from the metabolism of methylxanthines (caffeine, theophylline and theobromine). The method allows simultaneous quantitation of all known purine constituents of urinary stones, including methylated purines, and may be used as a reference one for diagnosing disorders of purine metabolism and research on the pathogenesis of urolithiasis.

Thresholds and gradients in a semi-arid grassland: long-term grazing treatments induce slow, continuous, and reversible vegetation change

USDA-ARS?s Scientific Manuscript database

Semiarid ecosystems can exhibit non-reversible shifts among alternative stable ecosystem states (thresholds and hysteresis), but can also be characterized by slow, continuous, and reversible changes in plant composition (successional gradients). Conceptual state-and-transition models (STMs) attempt ...

Suppressing Electron Turbulence and Triggering Internal Transport Barriers with Reversed Magnetic Shear in the National Spherical Torus Experiment

NASA Astrophysics Data System (ADS)

Peterson, Jayson Luc

2011-10-01

Observations in the National Spherical Torus Experiment (NSTX) have found electron temperature gradients that greatly exceed the linear threshold for the onset for electron temperature gradient-driven (ETG) turbulence. These discharges, deemed electron internal transport barriers (e-ITBs), coincide with a reversal in the shear of the magnetic field and with a reduction in electron-scale density fluctuations, qualitatively consistent with earlier gyrokinetic predictions. To investigate this phenomenon further, we numerically model electron turbulence in NSTX reversed-shear plasmas using the gyrokinetic turbulence code GYRO. These first-of-a-kind nonlinear gyrokinetic simulations of NSTX e-ITBs confirm that reversing the magnetic shear can allow the plasma to reach electron temperature gradients well beyond the critical gradient for the linear onset of instability. This effect is very strong, with the nonlinear threshold for significant transport approaching three times the linear critical gradient in some cases, in contrast with moderate shear cases, which can drive significant ETG turbulence at much lower gradients. In addition to the experimental implications of this upshifted nonlinear critical gradient, we explore the behavior of ETG turbulence during reversed shear discharges. This work is supported by the SciDAC Center for the Study of Plasma Microturbulence, DOE Contract DE-AC02-09CH11466, and used the resources of NCCS at ORNL and NERSC at LBNL. M. Ono et al., Nucl. Fusion 40, 557 (2000).

A low-cost gradient system for high-performance liquid chromatography. Quantitation of complex pharmaceutical raw materials.

PubMed

Erni, F; Frei, R W

1976-09-29

A device is described that makes use of an eight-port motor valve to generate step gradients on the low-pressure side of a piston pump with a low dead volume. Such a gradient device with an automatic control unit, which also permits repetition of previous steps, can be built for about half the cost of a gradient system with two pumps. Applications of this gradient unit to the separation of complex mixtures of glycosides and alkaloids are discussed and compared with separations systems using two high-pressure pumps. The gradients that are used on reversed-phase material with solvent mixtures of water and completely miscible organic solvents are suitable for quantitative routine control of pharmaceutical products. The reproducibility of retention data is excellent over several months and, with the use of loop injectors, major components can be determined quantitatively with a reproducibility of better than 2% (relative standard deviation). The step gradient selector valve can also be used as an introduction system for very large sample volumes. Up to 11 can be injected and samples with concentrations of less than 1 ppb can be determined with good reproducibilities.

3D printed titanium micro-bore columns containing polymer monoliths for reversed-phase liquid chromatography.

PubMed

Gupta, Vipul; Talebi, Mohammad; Deverell, Jeremy; Sandron, Sara; Nesterenko, Pavel N; Heery, Brendan; Thompson, Fletcher; Beirne, Stephen; Wallace, Gordon G; Paull, Brett

2016-03-03

The potential of 3D selective laser melting (SLM) technology to produce compact, temperature and pressure stable titanium alloy chromatographic columns is explored. A micro bore channel (0.9 mm I.D. × 600 mm long) was produced within a 5 × 30 × 30 mm titanium alloy (Ti-6Al-4V) cuboid, in form of a double handed spiral. A poly(butyl methacrylate-co-ethyleneglycoldimethacrylate) (BuMA-co-EDMA) monolithic stationary phase was thermally polymerised within the channel for application in reversed-phase high-performance liquid chromatography. The prepared monolithic column was applied to the liquid chromatographic separation of intact proteins and peptides. Peak capacities of 69-76 (for 6-8 proteins respectively) were observed during isothermal separation of proteins at 44 °C which were further increased to 73-77 using a thermal step gradient with programmed temperature from 60 °C to 35 °C using an in-house built direct-contact heater/cooler platform based upon matching sized Peltier thermoelectric modules. Rapid temperature gradients were possible due to direct-contact between the planar metal column and the Peltier module, and the high thermal conductivity of the titanium column as compared to a similar stainless steel printed column. The separation of peptides released from a digestion of E.coli was also achieved in less than 35 min with ca. 40 distinguishable peaks at 210 nm. Copyright © 2016 Elsevier B.V. All rights reserved.

Wide-Band Spatially Tunable Photonic Bandgap in Visible Spectral Range and Laser based on a Polymer Stabilized Blue Phase

PubMed Central

Lin, Jia-De; Wang, Tsai-Yen; Mo, Ting-Shan; Huang, Shuan-Yu; Lee, Chia-Rong

2016-01-01

This work successfully develops a largely-gradient-pitched polymer-stabilized blue phase (PSBP) photonic bandgap (PBG) device with a wide-band spatial tunability in nearly entire visible region within a wide blue phase (BP) temperature range including room temperature. The device is fabricated based on the reverse diffusion of two injected BP-monomer mixtures with a low and a high chiral concentrations and afterwards through UV-curing. This gradient-pitched PSBP can show a rainbow-like reflection appearance in which the peak wavelength of the PBG can be spatially tuned from the blue to the red regions at room temperature. The total tuning spectral range for the cell is as broad as 165 nm and covers almost the entire visible region. Based on the gradient-pitched PSBP, a spatially tunable laser is also demonstrated in this work. The temperature sensitivity of the lasing wavelength for the laser is negatively linear and approximately −0.26 nm/°C. The two devices have a great potential for use in applications of photonic devices and displays because of their multiple advantages, such as wide-band tunability, wide operated temperature range, high stability and reliability, no issue of hysteresis, no need of external controlling sources, and not slow tuning speed (mechanically). PMID:27456475

Simultaneous liquid chromatography/mass spectrometry determination of both polar and "multiresidue" pesticides in food using parallel hydrophilic interaction/reversed-phase liquid chromatography and a hybrid sample preparation approach.

PubMed

Robles-Molina, José; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

2017-09-29

Pesticide testing of foodstuffs is usually accomplished with generic wide-scope multi-residue methods based on liquid chromatography tandem mass spectrometry (LC-MS/MS). However, this approach does not cover some special pesticides, the so called "single-residue method" compounds, that are hardly compatible with standard reversed-phase (RP) separations due to their specific properties. In this article, we propose a comprehensive strategy for the integration of single residue method compounds and standard multiresidue pesticides within a single run. It is based on the use of a parallel LC column assembly with two different LC gradients performing orthogonal hydrophilic interaction chromatography (HILIC) and reversed-phase (RPLC) chromatography within one analytical run. Two sample aliquots were simultaneously injected on each column, using different gradients, being the eluents merged post-column prior to mass spectrometry detection. The approach was tested with 41 multiclass pesticides covering a wide range of physicochemical properties across several orders of log K ow (from -4 to +5.5). With this assembly, distinct separation from the void was attained for all the pesticides studied, keeping similar performance in terms of sensitivity, peak area reproducibility (<6 RSD% in most cases) and retention time stability of standard single column approaches (better than±0.1min). The application of the proposed approach using parallel HILIC/RPLC and RPLC/aqueous normal phase (Obelisc) were assessed in leek using LC-MS/MS. For this purpose, a hybrid QuEChERS (Quick, easy, cheap, effective, rugged and safe)/QuPPe (quick method for polar pesticides) method was evaluated based on solvent extraction with MeOH and acetonitrile followed by dispersive solid-phase extraction, delivering appropriate recoveries for most of the pesticides included in the study within the log K ow in the range from -4 to +5.5. The proposed strategy may be extended to other fields such as sport drug testing or environmental analysis, where the same type of variety of analytes featuring poor retention within a single chromatographic separation occurs. Copyright © 2017 Elsevier B.V. All rights reserved.

Anomalous magnon Nernst effect of topological magnonic materials

NASA Astrophysics Data System (ADS)

Wang, X. S.; Wang, X. R.

2018-05-01

The magnon transport driven by a thermal gradient in a perpendicularly magnetized honeycomb lattice is studied. The system with the nearest-neighbor pseudodipolar interaction and the next-nearest-neighbor Dzyaloshinskii–Moriya interaction has various topologically nontrivial phases. When an in-plane thermal gradient is applied, a transverse in-plane magnon current is generated. This phenomenon is termed as the anomalous magnon Nernst effect that closely resembles the anomalous Nernst effect for an electronic system. The anomalous magnon Nernst coefficient and its sign are determined by the magnon Berry curvature distributions in the momentum space and magnon populations in the magnon bands. We predict a temperature-induced sign reversal in anomalous magnon Nernst effect under certain conditions.

The Role of Transmural Repolarization Gradient in the Inversion of Cardiac Electric Field: Model Study of ECG in Hypothermia.

PubMed

Arteyeva, Natalia V; Azarov, Jan E

2017-01-01

The changes in ventricular repolarization gradients lead to significant alterations of the electrocardiographic body surface T waves up to the T wave inversion. However, the contribution of a specific gradient remains to be elucidated. The objective of the present investigation was to study the role of the transmural repolarization gradient in the inversion of the body surface T wave with a mathematical model of the hypothermia-induced changes of ventricular repolarization. By means of mathematical simulation, we set the hypothermic action potential duration (APD) distribution on the rabbit ventricular epicardium as it was previously experimentally documented. Then the parameters of the body surface potential distribution were tested with the introduction of different scenarios of the endocardial and epicardial APD behavior in hypothermia resulting in the unchanged, reversed or enlarged transmural repolarization gradient. The reversal of epicardial repolarization gradients (apicobasal, anterior-posterior and interventricular) caused the inversion of the T waves regardless of the direction of the transmural repolarization gradient. However, the most realistic body surface potentials were obtained when the endocardial APDs were not changed under hypothermia while the epicardial APDs prolonged. This produced the reversed and increased transmural repolarization gradient in absolute magnitude. The body surface potentials simulated under the unchanged transmural gradient were reduced in comparison to those simulated under the reversed transmural gradient. The simulations demonstrated that the transmural repolarization gradient did not play a crucial role in the cardiac electric field inversion under hypothermia, but its magnitude and direction contribute to the T wave amplitude. © 2016 Wiley Periodicals, Inc.

Finite-frequency tomography using adjoint methods-Methodology and examples using membrane surface waves

NASA Astrophysics Data System (ADS)

Tape, Carl; Liu, Qinya; Tromp, Jeroen

2007-03-01

We employ adjoint methods in a series of synthetic seismic tomography experiments to recover surface wave phase-speed models of southern California. Our approach involves computing the Fréchet derivative for tomographic inversions via the interaction between a forward wavefield, propagating from the source to the receivers, and an `adjoint' wavefield, propagating from the receivers back to the source. The forward wavefield is computed using a 2-D spectral-element method (SEM) and a phase-speed model for southern California. A `target' phase-speed model is used to generate the `data' at the receivers. We specify an objective or misfit function that defines a measure of misfit between data and synthetics. For a given receiver, the remaining differences between data and synthetics are time-reversed and used as the source of the adjoint wavefield. For each earthquake, the interaction between the regular and adjoint wavefields is used to construct finite-frequency sensitivity kernels, which we call event kernels. An event kernel may be thought of as a weighted sum of phase-specific (e.g. P) banana-doughnut kernels, with weights determined by the measurements. The overall sensitivity is simply the sum of event kernels, which defines the misfit kernel. The misfit kernel is multiplied by convenient orthonormal basis functions that are embedded in the SEM code, resulting in the gradient of the misfit function, that is, the Fréchet derivative. A non-linear conjugate gradient algorithm is used to iteratively improve the model while reducing the misfit function. We illustrate the construction of the gradient and the minimization algorithm, and consider various tomographic experiments, including source inversions, structural inversions and joint source-structure inversions. Finally, we draw connections between classical Hessian-based tomography and gradient-based adjoint tomography.

Retention and effective diffusion of model metabolites on porous graphitic carbon.

PubMed

Lunn, Daniel B; Yun, Young J; Jorgenson, James W

2017-12-29

The study of metabolites in biological samples is of high interest for a wide range of biological and pharmaceutical applications. Reversed phase liquid chromatography is a common technique used for the separation of metabolites, but it provides little retention for polar metabolites. An alternative to C18 bonded phases, porous graphitic carbon has the ability to provide significant retention for both non-polar and polar analytes. The goal of this work is to study the retention and effective diffusion properties of porous graphitic carbon, to see if it is suitable for the wide injection bands and long run times associated with long, packed capillary-scale separations. The retention of a set of standard metabolites was studied for both stationary phases over a wide range of mobile phase conditions. This data showed that porous graphitic carbon benefits from significantly increased retention (often >100 fold) under initial gradient conditions for these metabolites, suggesting much improved ability to focus a wide injection band at the column inlet. The effective diffusion properties of these columns were studied using peak-parking experiments with the standard metabolites under a wide range of retention conditions. Under the high retention conditions, which can be associated with retention after injection loading for gradient separations, D eff /D m ∼0.1 for both the C18-bonded and porous graphitic carbon columns. As C18 bonded particles are widely, and successfully utilized for long gradient separations without issue of increasing peak width from longitudinal diffusion, this suggests that porous graphitic carbon should be amenable for long runtime gradient separations as well. Copyright © 2017 Elsevier B.V. All rights reserved.

Probing the regional distribution of pulmonary gas exchange through single-breath gas- and dissolved-phase 129Xe MR imaging.

PubMed

Kaushik, S Sivaram; Freeman, Matthew S; Cleveland, Zackary I; Davies, John; Stiles, Jane; Virgincar, Rohan S; Robertson, Scott H; He, Mu; Kelly, Kevin T; Foster, W Michael; McAdams, H Page; Driehuys, Bastiaan

2013-09-01

Although some central aspects of pulmonary function (ventilation and perfusion) are known to be heterogeneous, the distribution of diffusive gas exchange remains poorly characterized. A solution is offered by hyperpolarized 129Xe magnetic resonance (MR) imaging, because this gas can be separately detected in the lung's air spaces and dissolved in its tissues. Early dissolved-phase 129Xe images exhibited intensity gradients that favored the dependent lung. To quantitatively corroborate this finding, we developed an interleaved, three-dimensional radial sequence to image the gaseous and dissolved 129Xe distributions in the same breath. These images were normalized and divided to calculate "129Xe gas-transfer" maps. We hypothesized that, for healthy volunteers, 129Xe gas-transfer maps would retain the previously observed posture-dependent gradients. This was tested in nine subjects: when the subjects were supine, 129Xe gas transfer exhibited a posterior-anterior gradient of -2.00 ± 0.74%/cm; when the subjects were prone, the gradient reversed to 1.94 ± 1.14%/cm (P < 0.001). The 129Xe gas-transfer maps also exhibited significant heterogeneity, as measured by the coefficient of variation, that correlated with subject total lung capacity (r = 0.77, P = 0.015). Gas-transfer intensity varied nonmonotonically with slice position and increased in slices proximal to the main pulmonary arteries. Despite substantial heterogeneity, the mean gas transfer for all subjects was 1.00 ± 0.01 while supine and 1.01 ± 0.01 while prone (P = 0.25), indicating good "matching" between gas- and dissolved-phase distributions. This study demonstrates that single-breath gas- and dissolved-phase 129Xe MR imaging yields 129Xe gas-transfer maps that are sensitive to altered gas exchange caused by differences in lung inflation and posture.

Development of a sensitive and rapid method for rifampicin impurity analysis using supercritical fluid chromatography.

PubMed

Li, Wei; Wang, Jun; Yan, Zheng-Yu

2015-10-10

A novel simple, fast and efficient supercritical fluid chromatography (SFC) method was developed and compared with RPLC method for the separation and determination of impurities in rifampicin. The separation was performed using a packed diol column and a mobile phase B (modifier) consisting of methanol with 0.1% ammonium formate (w/v) and 2% water (v/v). Overall satisfactory resolutions and peak shapes for rifampicin quinone (RQ), rifampicin (RF), rifamycin SV (RSV), rifampicin N-oxide (RNO) and 3-formylrifamycinSV (3-FR) were obtained by optimization of the chromatography system. With gradient elution of mobile phase, all of the impurities and the active were separated within 4 min. Taking full advantage of features of SFC (such as particular selectivity, non-sloping baseline in gradient elution, and without injection solvent effects), the method was successfully used for determination of impurities in rifampicin, with more impurity peaks detected, better resolution achieved and much less analysis time needed compared with conventional reversed-phase liquid chromatography (RPLC) methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Basilar-membrane interference patterns from multiple internal reflection of cochlear traveling waves.

PubMed

Shera, Christopher A; Cooper, Nigel P

2013-04-01

At low stimulus levels, basilar-membrane (BM) mechanical transfer functions in sensitive cochleae manifest a quasiperiodic rippling pattern in both amplitude and phase. Analysis of the responses of active cochlear models suggests that the rippling is a mechanical interference pattern created by multiple internal reflection within the cochlea. In models, the interference arises when reverse-traveling waves responsible for stimulus-frequency otoacoustic emissions (SFOAEs) reflect off the stapes on their way to the ear canal, launching a secondary forward-traveling wave that combines with the primary wave produced by the stimulus. Frequency-dependent phase differences between the two waves then create the rippling pattern measurable on the BM. Measurements of BM ripples and SFOAEs in individual chinchilla ears demonstrate that the ripples are strongly correlated with the acoustic interference pattern measured in ear-canal pressure, consistent with a common origin involving the generation of SFOAEs. In BM responses to clicks, the ripples appear as temporal fine structure in the response envelope (multiple lobes, waxing and waning). Analysis of the ripple spacing and response phase gradients provides a test for the role of fast- and slow-wave modes of reverse energy propagation within the cochlea. The data indicate that SFOAE delays are consistent with reverse slow-wave propagation but much too long to be explained by fast waves.

Development and validation of stability indicating the RP-HPLC method for the estimation of related compounds of guaifenesin in pharmaceutical dosage forms.

PubMed

Reddy, Sunil Pingili; Babu, K Sudhakar; Kumar, Navneet; Sekhar, Y V V Sasi

2011-10-01

A stability-indicating gradient reverse phase liquid chromatographic (RP-LC) method was developed for the quantitative determination of related substances of guaifenesin in pharmaceutical formulations. The baseline separation for guaifenesin and all impurities was achieved by utilizing a Water Symmetry C18 (150 mm × 4.6 mm) 5 μm column particle size and a gradient elution method. The mobile phase A contains a mixture of 0.02 M KH2PO4 (pH 3.2) and methanol in the ratio of 90:10 v/v, while the mobile phase B contains 0.02 M KH2PO4 (pH 3.2) and methanol in the ratio of 10:90 v/v, respectively. The flow rate of the mobile phase was 0.8 ml/min with a column temperature of 25°C and detection wavelength at 273 nm. Guaifenesin was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal, and photolytic degradation. The developed method was validated as per ICH guidelines with respect to specificity, linearity, limit of detection and quantification, accuracy, precision, and robustness.

Development and validation of stability indicating the RP-HPLC method for the estimation of related compounds of guaifenesin in pharmaceutical dosage forms

PubMed Central

Reddy, Sunil Pingili; Babu, K. Sudhakar; Kumar, Navneet; Sekhar, Y. V. V. Sasi

2011-01-01

Aim and background: A stability-indicating gradient reverse phase liquid chromatographic (RP-LC) method was developed for the quantitative determination of related substances of guaifenesin in pharmaceutical formulations. Materials and methods: The baseline separation for guaifenesin and all impurities was achieved by utilizing a Water Symmetry C18 (150 mm × 4.6 mm) 5 μm column particle size and a gradient elution method. The mobile phase A contains a mixture of 0.02 M KH2PO4 (pH 3.2) and methanol in the ratio of 90:10 v/v, while the mobile phase B contains 0.02 M KH2PO4 (pH 3.2) and methanol in the ratio of 10:90 v/v, respectively. The flow rate of the mobile phase was 0.8 ml/min with a column temperature of 25°C and detection wavelength at 273 nm. Results: Guaifenesin was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal, and photolytic degradation. Conclusion: The developed method was validated as per ICH guidelines with respect to specificity, linearity, limit of detection and quantification, accuracy, precision, and robustness. PMID:23781462

Thermal transport dynamics in the quasi-single helicity state

NASA Astrophysics Data System (ADS)

McKinney, I. J.; Terry, P. W.

2017-06-01

A dynamical model describing oscillations between multiple and single helicity configurations in the quasi-single helicity (QSH) state of the reversed field pinch [P. W. Terry and G. G. Whelan, Plasma Phys. Controlled Fusion 56, 094003 (2014)] is extended to include electron temperature profile dynamics. It is shown that QSH dynamics is linked to the electron temperature profile because the suppression of mode coupling between tearing modes proposed to underlie QSH also suppresses magnetic-fluctuation-induced thermal transport. Above the threshold of dominant-mode shear that marks the transition to QSH, the model produces temperature-gradient steepening in the strong shear region. Oscillations of the dominant and secondary mode amplitudes give rise to oscillations of the temperature gradient. The phasing and amplitude of temperature gradient oscillations relative to those of the dominant mode are in agreement with experiment. This provides further evidence that the model, while heuristic, captures key physical aspects of the QSH state.

Thermal gradients for the stabilization of a single domain wall in magnetic nanowires.

PubMed

Mejía-López, J; Velásquez, E A; Mazo-Zuluaga, J; Altbir, D

2018-08-24

By means of Monte Carlo simulations we studied field driven nucleation and propagation of transverse domain walls (DWs) in magnetic nanowires subjected to temperature gradients. Simulations identified the existence of critical thermal gradients that allow the existence of reversal processes driven by a single DW. Critical thermal gradients depend on external parameters such as temperature, magnetic field and wire length, and can be experimentally obtained through the measurement of the mean velocity of the magnetization reversal as a function of the temperature gradient. Our results show that temperature gradients provide a high degree of control over DW propagation, which is of great importance for technological applications.

Comparison of various second-dimension gradient types in comprehensive two-dimensional liquid chromatography.

PubMed

Jandera, Pavel; Hájek, Tomás; Cesla, Petr

2010-06-01

Gradient elution provides significant improvement in peak capacity with respect to isocratic conditions. In the second dimension, gradients are limited to a short-time period available for separation. Various types of second-dimension gradients in comprehensive LC x LC are compared: (i) "full in fraction", (ii) "segment in fraction" and (iii) "continuously shifting" gradients, applied in orthogonal LC x LC separations of phenolic acids and flavones on a polyethylene glycol column in the first dimension and two types of porous shell fused-core C18 columns in the second dimension (Ascentis Express and Kinetex). The porous shell columns provide narrow bandwidths and fast second-dimension separations at moderate operating pressure that allows important savings of the overall separation time in comprehensive LC x LC separations. The effects of the gradient type on the bandwidths, theoretical peak capacity, separation time and column pressure in the second dimension were investigated. The type of gradient program controls the range of lipophilicity of sample compounds that can be separated in the second-dimension reversed-phase time period. This range can be calibrated using alkylbenzene standards, to design the separation conditions for complete sample separation, avoiding harmful wrap around of non-eluted compounds to the subsequent second-dimension fractions.

Unexpected retention behavior of baicalin: Hydrophilic interaction like properties of a reversed-phase column.

PubMed

Magda, Balázs; Márta, Zoltán; Imre, Tímea; Kalapos-Kovács, Bernadett; Klebovich, Imre; Fekete, Jenő; Szabó, Pál T

2015-01-01

The original aim of this study was to develop a method for the determination of baicalin from membrane vesicles. The unconventional chromatographic separation ("inverse gradient elution" on a reversed phase column) was due to a lucky chance, which is detailed and discussed in this study. The validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) method is proved to be sensitive, rapid and selective. Chromatographic separation was performed on a Zorbax SB-C8 column (250 mm × 4.6 mm, i.d.; 5 μm) with 0.1% formic acid in water and methanol by linear gradient elution. Quantification of baicalin was determined by multiple reaction monitoring (MRM) mode using electrospray ionization (ESI). The calibration curve was linear (r = 0.9987) over the concentration range from 1 to 1000 nM. The coefficient of variation and relative error of baicalin for intra- and inter-assay at three quality control (QC) levels were 2.0-10.2% and -6.1 to 6.7%, respectively. The lower limit of quantification (LLOQ) for baicalin was 1 nM (0.446 ng/ml), without preconcentration of the sample. This method was subsequently applied to vesicular transport assays of baicalin in membrane vesicles successfully. The developed method can open up new area of research in the chromatographic separation of flavonoids and their glucuronides. Copyright © 2015. Published by Elsevier B.V.

Systematical Optimization of Reverse-phase Chromatography for Shotgun Proteomics

PubMed Central

Xu, Ping; Duong, Duc M.; Peng, Junmin

2009-01-01

Summary We report the optimization of a common LC/MS/MS platform to maximize the number of proteins identified from a complex biological sample. The platform uses digested yeast lysate on a 75 μm internal diameter × 12 cm reverse-phase column that is combined with an LTQ-Orbitrap mass spectrometer. We first generated a yeast peptide mix that was quantified by multiple methods including the strategy of stable isotope labeling with amino acids in cell culture (SILAC). The peptide mix was analyzed on a highly reproducible, automated nanoLC/MS/MS system with systematic adjustment of loading amount, flow rate, elution gradient range and length. Interestingly, the column was found to be almost saturated by loading ~1 μg of the sample. Whereas the optimal flow rate (~0.2 μl/min) and elution buffer range (13–32% of acetonitrile) appeared to be independent of the loading amount, the best gradient length varied according to the amount of samples: 160 min for 1 μg of the peptide mix, but 40 min for 10 ng of the same sample. The effect of these parameters on elution peptide peak width is evaluated. After full optimization, 1,012 proteins (clustered in 806 groups) with an estimated protein false discovery rate of ~3% were identified in 1 μg of yeast lysate in a single 160-min LC/MS/MS run. PMID:19566079

pH Gradient Reversal: An Emerging Hallmark of Cancers.

PubMed

Sharma, Mohit; Astekar, Madhusudan; Soi, Sonal; Manjunatha, Bhari S; Shetty, Devi C; Radhakrishnan, Raghu

2015-01-01

Several tumors exhibit pH gradient reversal, with acidification of extracellular pH (pHe) and alkalinization of intracellular pH (pHi). The pH gradient reversal is evident even during the preliminary stages of tumorigenesis and is crucial for survival and propagation of tumors, irrespective of their pathology, genetics and origins. Moreover, this hallmark seems to be present ubiquitously in all malignant tumors. Based on these facts, we propose a new emerging hallmark of cancer "pH gradient reversal". Normalizing pH gradient reversal through inhibition of various proton transporters such as Na(+)-H(+) exchanger (NHE), Vacuolar-type H(+)-ATPase (V-ATPase), H(+)/K(+)-ATPases and carbonic anhydrases (CAs) has demonstrated substantial therapeutic benefits. Indeed, inhibition of NHE1 is now being regarded as the latest concept in cancer treatment. A recent patent deals with the utilization of cis-Urocanic acid to acidify the pHi and induce apoptosis in tumors. Another patent reports therapeutic benefit by inhibiting Lactate Dehydrogenase - 5 (LDH-5) in various cancers. Several patents have been formulated by designing drugs activated through acidic pHe providing a cancer specific action. The purpose of this review is to analyze the available literature and help design selective therapies that could be a valuable adjunct to the conventional therapies or even replace them.

Simultaneous quantification of flavonoids and triterpenoids in licorice using HPLC.

PubMed

Wang, Yuan-Chuen; Yang, Yi-Shan

2007-05-01

Numerous bioactive compounds are present in licorice (Glycyrrhizae Radix), including flavonoids and triterpenoids. In this study, a reversed-phase high-performance liquid chromatography (HPLC) method for simultaneous quantification of three flavonoids (liquiritin, liquiritigenin and isoliquiritigenin) and four triterpenoids (glycyrrhizin, 18alpha-glycyrrhetinic acid, 18beta-glycyrrhetinic acid and 18beta-glycyrrhetinic acid methyl ester) from licorice was developed, and further, to quantify these 7 compounds from 20 different licorice samples. Specifically, the reverse-phase HPLC was performed with a gradient mobile phase composed of 25 mM phosphate buffer (pH 2.5)-acetonitrile featuring gradient elution steps as follows: 0 min, 100:0; 10 min, 80:20; 50 min, 70:30; 73 min, 50:50; 110 min, 50:50; 125 min, 20:80; 140 min, 20:80, and peaks were detected at 254 nm. By using our technique, a rather good specificity was obtained regarding to the separation of these seven compounds. The regression coefficient for the linear equations for the seven compounds lay between 0.9978 and 0.9992. The limits of detection and quantification lay in the range of 0.044-0.084 and 0.13-0.25 microg/ml, respectively. The relative recovery rates for the seven compounds lay between 96.63+/-2.43 and 103.55+/-2.77%. Coefficient variation for intra-day and inter-day precisions lay in the range of 0.20-1.84 and 0.28-1.86%, respectively. Based upon our validation results, this analytical technique is a convenient method to simultaneous quantify numerous bioactive compounds derived from licorice, featuring good quantification parameters, accuracy and precision.

High-performance liquid chromatography with nuclear magnetic resonance detection applied to organosilicon polymers. Part 2. Comparison with other methods.

PubMed

Blechta, Vratislav; Kurfürst, Milan; Sýkora, Jan; Schraml, Jan

2007-03-23

LC-NMR utilizing (1)H and (29)Si NMR spectroscopy is ideally suited for the analysis of silicones. It is shown that reversed phase gradient LC-NMR surpasses standard gel permeation chromatography (GPC) and diffusion ordered spectroscopy (DOSY) in the analysis of model hydride terminated polydimethylsiloxane. (1)H and (29)Si NMR in the stopped-flow arrangement leads to full identification of the components. Concentration gradient introduces a dependence of the (29)Si shifts on solvent composition, this dependence can be substantially reduced by a proposed method of referencing. It is shown that the ADEQUATE version of powerful but insensitive 2D INADEQUATE experiment can be used for complete line assignment.

Determination of adrenaline, noradrenaline and corticosterone in rodent blood by ion pair reversed phase UHPLC-MS/MS.

PubMed

Bergh, Marianne Skov-Skov; Bogen, Inger Lise; Andersen, Jannike Mørch; Øiestad, Åse Marit Leere; Berg, Thomas

2018-01-01

A novel ion pair reversed phase ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of the stress hormones adrenaline, noradrenaline and corticosterone in rodent blood was developed and fully validated. Separations were performed on an Acquity HSS T3 column (2.1mm i.d.×100mm, 1.8μm) with gradient elution and a runtime of 5.5min. The retention of adrenaline and noradrenaline was substantially increased by employing the ion pair reagent heptafluorobutyric acid (HFBA). Ion pair reagents are usually added to the mobile phase only, but we demonstrate for the first time that including HFBA to the sample reconstitution solvent as well, has a major impact on the chromatography of these compounds. The stability of adrenaline and corticosterone in rodent blood was investigated using the surrogate analytes adrenaline-d 3 and corticosterone-d 8 . The applicability of the described method was demonstrated by measuring the concentration of stress hormones in rodent blood samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Expanding the term "Design Space" in high performance liquid chromatography (I).

PubMed

Monks, K E; Rieger, H-J; Molnár, I

2011-12-15

The current article presents a novel approach to applying Quality by Design (QbD) principles to the development of high pressure reversed phase liquid chromatography (HPLC) methods. Four common critical parameters in HPLC--gradient time, temperature, pH of the aqueous eluent, and stationary phase--are evaluated within the Quality by Design framework by the means of computer modeling software and a column database, to a satisfactory degree. This work proposes the establishment of two mutually complimentary Design Spaces to fully depict a chromatographic method; one Column Design Space (CDS) and one Eluent Design Space (EDS) to describe the influence of the stationary phase and of the mobile phase on the separation selectivity, respectively. The merge of both Design Spaces into one is founded on the continuous nature of the mobile phase influence on retention and the great variety of the stationary phases available. Copyright © 2011 Elsevier B.V. All rights reserved.

Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, Patrick Allen

2005-12-17

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity ofmore » the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5%-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.« less

Temperature-gradient-induced

NASA Astrophysics Data System (ADS)

Park, Cheol; Glaser, Matt; Maclennan, Joe; Clark, Noel; Trittel, Torsten; Stannarius, Ralf

Freely-suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters were used to study thermally driven migration and convection in the film plane. Film experiments were performed during the 6 minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). We have found an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to the Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 K/mm, with thermally driven convection only setting in when the hot post reaches the transition temperature to the nematic phase. The Observation and Analysis of Smectic Islands in Space (OASIS) flight hardware was launched on SpaceX-6 in April 2015 and experiments on smectic bubbles were carried out on the International Space Station using four different smectic A and C liquid crystal materials in separate sample chambers. We observed that smectic islands on the surface of the bubbles migrated towards the colder part of the bubble in a temperature gradient. This work was supported by NASA Grant No. NNX-13AQ81G, by the Soft Materials Research Center under NSF MRSEC Grants No. DMR-0820579 and No. DMR-1420736, and by DLR Grants 50WM1127 and 50WM1430.

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

PubMed Central

Manahan, G. G.; Habib, A. F.; Scherkl, P.; Delinikolas, P.; Beaton, A.; Knetsch, A.; Karger, O.; Wittig, G.; Heinemann, T.; Sheng, Z. M.; Cary, J. R.; Bruhwiler, D. L.; Rosenzweig, J. B.; Hidding, B.

2017-01-01

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m−1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread—an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wave can be locally overloaded without compromising the witness bunch normalized emittance. This reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams. PMID:28580954

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

NASA Astrophysics Data System (ADS)

Manahan, G. G.; Habib, A. F.; Scherkl, P.; Delinikolas, P.; Beaton, A.; Knetsch, A.; Karger, O.; Wittig, G.; Heinemann, T.; Sheng, Z. M.; Cary, J. R.; Bruhwiler, D. L.; Rosenzweig, J. B.; Hidding, B.

2017-06-01

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m-1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread--an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wave can be locally overloaded without compromising the witness bunch normalized emittance. This reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams.

Affinity-reversed-phase liquid chromatography assay to quantitate recombinant antibodies and antibody fragments in fermentation broth.

PubMed

Battersby, J E; Snedecor, B; Chen, C; Champion, K M; Riddle, L; Vanderlaan, M

2001-08-24

An automated dual-column liquid chromatography assay comprised of affinity and reversed-phase separations that quantifies the majority of antibody-related protein species found in crude cell extracts of recombinant origin is described. Although potentially applicable to any antibody preparation, we here use samples of anti-CD18 (Fab'2LZ) and a full-length antibody, anti-tissue factor (anti-TF), from various stages throughout a biopharmaceutical production process to describe the assay details. The targeted proteins were captured on an affinity column containing an anti-light-chain (kappa) Fab antibody (AME5) immobilized on controlled pore glass. The affinity column was placed in-line with a reversed-phase column and the captured components were transferred by elution with dilute acid and subsequently resolved by eluting the reversed-phase column with a shallow acetonitrile gradient. Characterization of the resolved components showed that most antibody fragment preparations contained a light-chain fragment, free light chain, light-chain dimer and multiple forms of Fab'. Analysis of full-length antibody preparations also resolved these fragments as well as a completely assembled form. Co-eluting with the full-length antibody were high-molecular-mass variants that were missing one or both light chains. Resolved components were quantified by comparison with peak areas of similarly treated standards. By comparing the two-dimensional polyacrylamide gel electrophoresis patterns of an Escherichia coli blank run, a production run and the material affinity captured (AME5) from a production run, it was determined that the AME5 antibody captured isoforms of light chain, light chain covalently attached to heavy chain, and truncated light chain isoforms. These forms comprise the bulk of the soluble product-related fragments found in E. coli cell extracts of recombinantly produced antibody fragments.

Repeated nitrous oxide exposure in rats causes a thermoregulatory sign-reversal with concurrent activation of opposing thermoregulatory effectors

PubMed Central

Ramsay, Douglas S; Woods, Stephen C; Kaiyala, Karl J

2014-01-01

Initial administration of 60% nitrous oxide (N2O) to rats at an ambient temperature of 21°C decreases core temperature (Tc), primarily via increased heat loss (HL). Over repeated N2O administrations, rats first develop tolerance to this hypothermia and subsequently exhibit hyperthermia (a sign-reversal) due primarily to progressive increases in heat production (HP). When rats initially receive 60% N2O in a thermal gradient, they become hypothermic while selecting cooler ambient temperatures that facilitate HL. This study investigated whether rats repeatedly administered 60% N2O in a thermal gradient would use the gradient to behaviorally facilitate, or oppose, the development of chronic tolerance and a hyperthermic sign-reversal. Male Long-Evans rats (N = 16) received twelve 3-h administrations of 60% N2O in a gas-tight, live-in thermal gradient. Hypothermia (Sessions 1–3), complete chronic tolerance (Sessions 4–6), and a subsequent transient hyperthermic sign-reversal (Sessions 7–12) sequentially developed. Despite the progressive recovery and eventual hyperthermic sign-reversal of Tc, rats consistently selected cooler ambient temperatures during all N2O administrations. A final 60% N2O administration in a total calorimeter indicated that the hyperthermic sign-reversal resulted primarily from increased HP. Thus, rats did not facilitate chronic tolerance development by moving to warmer locations in the gradient, and instead selected cooler ambient temperatures while simultaneously increasing autonomic HP. The inefficient concurrent activation of opposing effectors and the development of a sign-reversal are incompatible with homeostatic models of drug-adaptation and may be better interpreted using a model of drug-induced allostasis. PMID:25938127

Rapid dark-blood carotid vessel-wall imaging with random bipolar gradients in a radial SSFP acquisition.

PubMed

Lin, Hung-Yu; Flask, Chris A; Dale, Brian M; Duerk, Jeffrey L

2007-06-01

To investigate and evaluate a new rapid dark-blood vessel-wall imaging method using random bipolar gradients with a radial steady-state free precession (SSFP) acquisition in carotid applications. The carotid artery bifurcations of four asymptomatic volunteers (28-37 years old, mean age = 31 years) were included in this study. Dark-blood contrast was achieved through the use of random bipolar gradients applied prior to the signal acquisition of each radial projection in a balanced SSFP acquisition. The resulting phase variation for moving spins established significant destructive interference in the low-frequency region of k-space. This phase variation resulted in a net nulling of the signal from flowing spins, while the bipolar gradients had a minimal effect on the static spins. The net effect was that the regular SSFP signal amplitude (SA) in stationary tissues was preserved while dark-blood contrast was achieved for moving spins. In this implementation, application of the random bipolar gradient pulses along all three spatial directions nulled the signal from both in-plane and through-plane flow in phantom and in vivo studies. In vivo imaging trials confirmed that dark-blood contrast can be achieved with the radial random bipolar SSFP method, thereby substantially reversing the vessel-to-lumen contrast-to-noise ratio (CNR) of a conventional rectilinear SSFP "bright-blood" acquisition from bright blood to dark blood with only a modest increase in TR (approximately 4 msec) to accommodate the additional bipolar gradients. Overall, this sequence offers a simple and effective dark-blood contrast mechanism for high-SNR SSFP acquisitions in vessel wall imaging within a short acquisition time.

Simultaneous analysis of insect repellent DEET, sunscreen oxybenzone and five relevant metabolites by reversed-phase HPLC with UV detection: application to an in vivo study in a piglet model.

PubMed

Kasichayanula, Sreeneeranj; House, James D; Wang, Tao; Gu, Xiaochen

2005-08-05

N,N-Diethyl-m-toluamide (DEET) and oxybenzone are two essential active ingredients in insect repellent and sunscreen preparations. We developed and validated a simple, sensitive, and selective HPLC assay to simultaneously measure DEET, oxybenzone and five primary metabolites of DEET and oxybenzone in biological samples including plasma, urine and skin strips. The compounds were separated on a reversed-phase C18 column using three-stage gradient steps with methanol and water. DEET and two relevant metabolites were detected at 254 nm, while oxybenzone and three relevant metabolites were detected at 289 nm. The limit of detection was 0.6 ng for DEET and 0.5 ng for oxybenzone, respectively. The developed method was further applied to analyze various biological samples from an in vivo animal study that evaluated concurrent use of commercially available insect repellent and sunscreen preparations.

Simultaneous determination of diclofenac potassium and methocarbamol in ternary mixture with guaifenesin by reversed phase liquid chromatography.

PubMed

Elkady, Ehab F

2010-09-15

New, simple, rapid and precise reversed phase liquid chromatographic (RP-LC) method has been developed for the simultaneous determination of diclofenac potassium (DP) and methocarbamol (MT) in ternary mixture with guaifenesin (GF), degradation product of methocarbamol. Chromatographic separation was achieved on a Symmetry Waters C18 column (150 mm x 4. 6mm, 5 microm). Gradient elution based on phosphate buffer pH (8)-acetonitrile at a flow rate of 1 mL min(-1) was applied. The UV detector was operated at 282 nm for DP and 274 nm for MT and GF. Linearity, accuracy and precision were found to be acceptable over the concentration ranges of 0.05-16, 0.5-160 and 0.5-160 microg mL(-1) for DP, MT and GF, respectively. The optimized method proved to be specific, robust and accurate for the quality control of the cited drugs in pharmaceutical preparation. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Fast Gradient Elution Reversed-Phase HPLC with Diode-Array Detection as a High Throughput Screening Method for Drugs of Abuse

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peter W. Carr; K.M. Fuller; D.R. Stoll

A new approach has been developed by modifying a conventional gradient elution liquid chromatograph for the high throughput screening of biological samples to detect the presence of regulated intoxicants. The goal of this work was to improve the speed of a gradient elution screening method over current approaches by optimizing the operational parameters of both the column and the instrument without compromising the reproducibility of the retention times, which are the basis for the identification. Most importantly, the novel instrument configuration substantially reduces the time needed to re-equilibrate the column between gradient runs, thereby reducing the total time for eachmore » analysis. The total analysis time for each gradient elution run is only 2.8 minutes, including 0.3 minutes for column reequilibration between analyses. Retention times standard calibration solutes are reproducible to better than 0.002 minutes in consecutive runs. A corrected retention index was adopted to account for day-to-day and column-to-column variations in retention time. The discriminating power and mean list length were calculated for a library of 47 intoxicants and compared with previous work from other laboratories to evaluate fast gradient elution HPLC as a screening tool.« less

[Separation and determination of eight plant hormones by reversed-phase high performance liquid chromatography].

PubMed

Fang, N; Hou, S; Shao, X; He, Y; Zhao, G

1998-09-01

In this paper, reversed-phase high performance liquid chromatographic technique was used for the separation and determination of eight plant hormones. Methanol-water-acetic acid system was chosen as the mobile phase. The effects of different separation conditions, such as the methanol and acetic acid concentrations in mobile phase, on the retention behaviours of eight plant hormones in this system were studied. The general trends in retention behaviours could be correlated to the methanol concentration in mobile phase. The experimental results showed that the optimum separation was achieved with following gradient elution condition: 0-3 minutes, 70% (water percentage in mobile phase), 3-13 minutes, 70%-20%, 13-48 minutes, 20%. Benzene was added to be as the internal standard. Under this experimental condition, the eight plant hormones could be separated completely and detected quantitatively at 260 nm within 16 minutes. The calibration curves for the eight compounds gave linearity over a wide range. The correlation coefficients of each components were r(ZT) = 0.9971, r(GAs) = 0.9999, r(K) = 0.9997, r(BA) = 0.9995, r(IAA) = 0.9998, r(IPA) = 0.9982, r(IBA) = 0.9995 and r(NAA) = 0.9995. The method is rapid, simple and efficient. It is a suitable method for the accurate determination of gibberellic acid (GA) and alpha-naphthaleneacetic acid (alpha-NAA) in products for agricultural use.

Application of the artificial neural network in quantitative structure-gradient elution retention relationship of phenylthiocarbamyl amino acids derivatives.

PubMed

Tham, S Y; Agatonovic-Kustrin, S

2002-05-15

Quantitative structure-retention relationship(QSRR) method was used to model reversed-phase high-performance liquid chromatography (RP-HPLC) separation of 18 selected amino acids. Retention data for phenylthiocarbamyl (PTC) amino acids derivatives were obtained using gradient elution on ODS column with mobile phase of varying acetonitrile, acetate buffer and containing 0.5 ml/l of triethylamine (TEA). Molecular structure of each amino acid was encoded with 36 calculated molecular descriptors. The correlation between the molecular descriptors and the retention time of the compounds in the calibration set was established using the genetic neural network method. A genetic algorithm (GA) was used to select important molecular descriptors and supervised artificial neural network (ANN) was used to correlate mobile phase composition and selected descriptors with the experimentally derived retention times. Retention time values were used as the network's output and calculated molecular descriptors and mobile phase composition as the inputs. The best model with five input descriptors was chosen, and the significance of the selected descriptors for amino acid separation was examined. Results confirmed the dominant role of the organic modifier in such chromatographic systems in addition to lipophilicity (log P) and molecular size and shape (topological indices) of investigated solutes.

Analysis of iodinated quorum sensing peptides by LC-UV/ESI ion trap mass spectrometry.

PubMed

Janssens, Yorick; Verbeke, Frederick; Debunne, Nathan; Wynendaele, Evelien; Peremans, Kathelijne; De Spiegeleer, Bart

2018-02-01

Five different quorum sensing peptides (QSP) were iodinated using different iodination techniques. These iodinated peptides were analyzed using a C 18 reversed phase HPLC system, applying a linear gradient of water and acetonitrile containing 0.1% (m/v) formic acid as mobile phase. Electrospray ionization (ESI) ion trap mass spectrometry was used for the identification of the modified peptides, while semi-quantification was performed using total ion current (TIC) spectra. Non-iodinated peptides and mono- and di-iodinated peptides (NIP, MIP and DIP respectively) were well separated and eluted in that order. Depending on the used iodination method, iodination yields varied from low (2%) to high (57%).

A comprehensive study on rotation reversal in KSTAR: experimental observations and modelling

NASA Astrophysics Data System (ADS)

Na, D. H.; Na, Yong-Su; Angioni, C.; Yang, S. M.; Kwon, J. M.; Jhang, Hogun; Camenen, Y.; Lee, S. G.; Shi, Y. J.; Ko, W. H.; Lee, J. A.; Hahm, T. S.; KSTAR Team

2017-12-01

Dedicated experiments have been performed in KSTAR Ohmic plasmas to investigate the detailed physics of the rotation reversal phenomena. Here we adapt the more general definition of rotation reversal, a large change of the intrinsic toroidal rotation gradient produced by minor changes in the control parameters (Camenen et al 2017 Plasma Phys. Control. Fusion 59 034001), which is commonly observed in KSTAR regardless of the operating conditions. The two main phenomenological features of the rotation reversal are the normalized toroidal rotation gradient ({{u}\\prime} ) change in the gradient region and the existence of an anchor point. For the KSTAR Ohmic plasma database including the experiment results up to the 2016 experimental campaign, both features were investigated. First, the observations show that the locations of the gradient and the anchor point region are dependent on {{q}95} . Second, a strong dependence of {{u}\\prime} on {νeff} is clearly observed in the gradient region, whereas the dependence on R/{{L}{{Ti}}} , R/{{L}{{Te}}} , and R/{{L}{{ne}}} is unclear considering the usual variation of the normalized gradient length in KSTAR. The experimental observations were compared against several theoretical models. The rotation reversal might not occur due to the transition of the dominant turbulence from the trapped electron mode to the ion temperature gradient mode or the neoclassical equilibrium effect in KSTAR. Instead, it seems that the profile shearing effects associated with a finite ballooning tilting well reproduce the experimental observations of both the gradient region and the anchor point; the difference seems to be related to the magnetic shear and the q value. Further analysis implies that the increase of {{u}\\prime} in the gradient region with the increase of the collisionality would occur when the reduction of the momentum diffusivity is comparatively larger than the reduction of the residual stress. It is supported by the perturbative analysis of the experiments and the nonlinear gyrokinetic simulations. The absence of the sign change of {{u}\\prime} even when a much lower collisionality is produced by additional electron cyclotron heating brings further experimental support to this interpretation.

Suppression/Reversal of Natural Convection by Exploiting the Temperature/Composition Dependence of Magnetic Susceptibility

NASA Technical Reports Server (NTRS)

Seybert, C. D.; Evans, J. W.; Leslie, F.; Jones, W. K., Jr.

2000-01-01

Natural convection, driven by temperature-or concentration gradients or both, is an inherent phenomenon during solidification of materials on Earth. This convection has practical consequences (e.g effecting macrosegregation) but also renders difficult the scientific examination of diffusive/conductive phenomena during solidification. It is possible to halt, or even reverse, natural convection by exploiting the variation (with temperature, for example) of the susceptibility of a material. If the material is placed in a vertical magnetic field gradient, a buoyancy force of magnetic origin arises and, at a critical field gradient, can balance the normal buoyancy forces to halt convection. At higher field gradients the convection can be reversed. The effect has been demonstrated in experiments at Marshall Space Flight Center where flow was measured by PIV in MnCl2 solution in a superconducting magnet. In auxiliary experiments the field in the magnet and the properties of the solution were measured. Computations of the natural convection, its halting and reversal, using the commercial software FLUENT were in good agreement with the measurements.

Performance of the reverse Helmbold universal portfolio

NASA Astrophysics Data System (ADS)

Tan, Choon Peng; Kuang, Kee Seng; Lee, Yap Jia

2017-04-01

The universal portfolio is an important investment strategy in a stock market where no stochastic model is assumed for the stock prices. The zero-gradient set of the objective function estimating the next-day portfolio which contains the reverse Kullback-Leibler order-alpha divergence is considered. From the zero-gradient set, the explicit, reverse Helmbold universal portfolio is obtained. The performance of the explicit, reverse Helmbold universal portfolio is studied by running them on some stock-price data sets from the local stock exchange. It is possible to increase the wealth of the investor by using these portfolios in investment.

Validation of an electrospray ionisation LC-MS/MS method for quantitative analysis of telaprevir and its R-diastereomer.

PubMed

Penchala, Sujan Dilly; Tjia, John; El Sherif, Omar; Back, David J; Khoo, Saye H; Else, Laura J

2013-08-01

A sensitive high-performance reverse phase liquid chromatography-positive ion electrospray tandem mass spectrometry method was developed and validated for the quantification of telaprevir and its inactive R-diastereomer (VRT-127394) in human plasma. The analytes and the internal standard (telaprevir-d11) were extracted from plasma by liquid-liquid extraction using tert-Butyl methyl ether (TBME). Chromatographic separation was achieved on a reversed-phase Accucore C18 column with a gradient programme consisting of water:ammonia (25%), 100:0.01 (v/v) (mobile phase A) and ACN:MeOH:ammonia (25%), 15:85:0.01 (v/v/v) (mobile phase B). The MS acquisition was performed with selective reaction monitoring mode using the respective [M+H](+) ions, m/z 680.59→322.42 for telaprevir and VRT-127394, and 691.15→110.13 for telaprevir-d11. The assay exhibited a linear dynamic range of 5-5000ng/mL for telaprevir and VRT-127394. Acceptable precision (%RSD<6.5%) and accuracy (94-108%) were obtained for concentrations over the range of the standard curve. A procedure was established to stabilise the plasma to prevent ex vivo interconversion of the isomers. Copyright © 2013 Elsevier B.V. All rights reserved.

Sudden motility reversal indicates sensing of magnetic field gradients in Magnetospirillum magneticum AMB-1 strain

PubMed Central

González, Lina M; Ruder, Warren C; Mitchell, Aaron P; Messner, William C; LeDuc, Philip R

2015-01-01

Many motile unicellular organisms have evolved specialized behaviors for detecting and responding to environmental cues such as chemical gradients (chemotaxis) and oxygen gradients (aerotaxis). Magnetotaxis is found in magnetotactic bacteria and it is defined as the passive alignment of these cells to the geomagnetic field along with active swimming. Herein we show that Magnetospirillum magneticum (AMB-1) show a unique set of responses that indicates they sense and respond not only to the direction of magnetic fields by aligning and swimming, but also to changes in the magnetic field or magnetic field gradients. We present data showing that AMB-1 cells exhibit sudden motility reversals when we impose them to local magnetic field gradients. Our system employs permalloy (Ni80Fe20) islands to curve and diverge the magnetic field lines emanating from our custom-designed Helmholtz coils in the vicinity of the islands (creating a drop in the field across the islands). The three distinct movements we have observed as they approach the permalloy islands are: unidirectional, single reverse and double reverse. Our findings indicate that these reverse movements occur in response to magnetic field gradients. In addition, using a permanent magnet we found further evidence that supports this claim. Motile AMB-1 cells swim away from the north and south poles of a permanent magnet when the magnet is positioned less than ∼30 mm from the droplet of cells. All together, these results indicate previously unknown response capabilities arising from the magnetic sensing systems of AMB-1 cells. These responses could enable them to cope with magnetic disturbances that could in turn potentially inhibit their efficient search for nutrients. PMID:25478682

Sudden motility reversal indicates sensing of magnetic field gradients in Magnetospirillum magneticum AMB-1 strain.

PubMed

González, Lina M; Ruder, Warren C; Mitchell, Aaron P; Messner, William C; LeDuc, Philip R

2015-06-01

Many motile unicellular organisms have evolved specialized behaviors for detecting and responding to environmental cues such as chemical gradients (chemotaxis) and oxygen gradients (aerotaxis). Magnetotaxis is found in magnetotactic bacteria and it is defined as the passive alignment of these cells to the geomagnetic field along with active swimming. Herein we show that Magnetospirillum magneticum (AMB-1) show a unique set of responses that indicates they sense and respond not only to the direction of magnetic fields by aligning and swimming, but also to changes in the magnetic field or magnetic field gradients. We present data showing that AMB-1 cells exhibit sudden motility reversals when we impose them to local magnetic field gradients. Our system employs permalloy (Ni(80)Fe(20)) islands to curve and diverge the magnetic field lines emanating from our custom-designed Helmholtz coils in the vicinity of the islands (creating a drop in the field across the islands). The three distinct movements we have observed as they approach the permalloy islands are: unidirectional, single reverse and double reverse. Our findings indicate that these reverse movements occur in response to magnetic field gradients. In addition, using a permanent magnet we found further evidence that supports this claim. Motile AMB-1 cells swim away from the north and south poles of a permanent magnet when the magnet is positioned less than ∼30 mm from the droplet of cells. All together, these results indicate previously unknown response capabilities arising from the magnetic sensing systems of AMB-1 cells. These responses could enable them to cope with magnetic disturbances that could in turn potentially inhibit their efficient search for nutrients.

Characterization of Rare Reverse Flow Events in Adverse Pressure Gradient Turbulent Boundary Layers

NASA Astrophysics Data System (ADS)

Kaehler, Christian J.; Bross, Matthew; Fuchs, Thomas

2017-11-01

Time-resolved tomographic flow fields measured in the viscous sublayer region of a turbulent boundary layer subjected to an adverse pressure gradient (APG) are examined with the aim to resolve and characterize reverse flow events at Reτ = 5000. The fields were measured using a novel high resolution tomographic particle tracking technique. It is shown that this technique is able to fully resolve mean and time dependent features of the complex three-dimensional flow with high accuracy down to very near-wall distances ( 10 μm). From time resolved Lagrangian particle trajectories, statistical information as well as instantaneous topological features of near-wall flow events are deduced. Similar to the zero pressure gradient case (ZPG), it was found that individual events with reverse flow components still occur relatively rarely under the action of the pressure gradient investigated here. However, reverse flow events comprised of many individual events, are shown to appear in relatively organized groupings in both spanwise and streamise directions. Furthermore, instantaneous measurements of reverse flow events show that these events are associated with the motion of low-momentum streaks in the near-wall region. This work is supported by the Priority Programme SPP 1881 Turbulent Superstructures and the individual project Grant KA1808/8-2 of the Deutsche Forschungsgemeinschaft.

Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend.

PubMed

Jiang, Hua; Dou, Nannan; Fan, Guoqiang; Yang, Zhaohui; Zhang, Xiaohua

2013-09-28

We have investigated experimentally the structure formation processes during phase separation via spinodal decomposition above and below the spinodal line in a binary polymer blend system exposed to in-plane stationary thermal gradients using phase contrast optical microscopy and temperature gradient hot stage. Below the spinodal line there is a coupling of concentration fluctuations and thermal gradient imposed by the temperature gradient hot stage. Also under the thermal gradient annealing phase-separated domains grow faster compared with the system under homogeneous temperature annealing on a zero-gradient or a conventional hot stage. We suggest that the in-plane thermal gradient accelerates phase separation through the enhancement in concentration fluctuations in the early and intermediate stages of spinodal decomposition. In a thermal gradient field, the strength of concentration fluctuation close to the critical point (above the spinodal line) is strong enough to induce phase separation even in one-phase regime of the phase diagram. In the presence of a temperature gradient the equilibrium phase diagrams are no longer valid, and the systems with an upper critical solution temperature can be quenched into phase separation by applying the stationary temperature gradient. The in-plane temperature gradient drives enhanced concentration fluctuations in a binary polymer blend system above and below the spinodal line.

Metabolism studies of benzbromarone in rats by high performance liquid chromatography-quadrupole time of flight mass spectrometry.

PubMed

Wu, Haiqing; Peng, Ying; Wang, Shaojie; Wang, Kai; Zhao, Xunchen; Jiang, Fan

2012-12-12

A high performance liquid chromatography-quadrupole time of flight mass spectrometry (HPLC-QTOF-MS) method was employed in investigation of benzbromarone metabolites in rat plasma, urine, feces and bile samples. Meanwhile, the metabolic pathways of benzbromarone in rats were discussed. The identification was achieved on a reversed-phase C(18) column with mobile phase gradient method. The QTOF-MS was operated under full scan of MS or MS/MS in negative mode. The fragments were acquired by raising collision induced dissociation (CID) energy for speculating the structures of parent ions. According to the information from the chromatograms and mass spectra, 17 metabolites were obtained. Among them, the deoxidized phase I metabolites and an array of phase II metabolites-sulfate conjugates detected in the biological samples made the work more significant. Copyright © 2012 Elsevier B.V. All rights reserved.

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations.

PubMed

Schicks, J M; Luzi, M; Beeskow-Strauch, B

2011-11-24

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Arsenic-containing fatty acids and hydrocarbons in marine oils - determination using reversed-phase HPLC-ICP-MS and HPLC-qTOF-MS.

PubMed

Sele, Veronika; Sloth, Jens J; Holmelid, Bjarte; Valdersnes, Stig; Skov, Kasper; Amlund, Heidi

2014-04-01

Arsenolipids are the major arsenic species present in marine oils. Several structures of arsenolipids have been elucidated the last 5 years, demonstrating the chemical complexity of this trace element in the marine environment. Several commercial fish oils and marine oils, ranging in total arsenic concentrations from 1.6 to 12.5 mg kg(-1) oil, were analyzed for arsenolipids using reversed-phase high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The arsenolipids were quantified using three different arsenic-containing calibration standards; dimethylarsinate (DMA), triphenylarsinoxide (Ph₃AsO) and a synthesized arsenic-containing hydrocarbon (AsHC) (dimethylarsinoyl nonadecane; C₂₁H₄₃AsO). The observed variation in signal intensity for arsenic during the gradient elution profile in reversed-phase HPLC was compensated for by determining the time-resolved response factors for the arsenolipids. Isotopes of germanium ((74)Ge) and indium ((115)In) were suited as internal standards for arsenic, and were used for verification of the arsenic signal response factors during the gradient elution. Dimethylarsinate was the most suitable calibration standard for the quantification of arsenolipids, with recoveries between 91% and 104% compared to total arsenic measurements in the same extracts. A range of marine oils was investigated, including oils of several fish species, cod liver and seal, as well as three commercial fish oils. The AsHCs - C₁₇H₃₈AsO, C₁₉H₄₂AsO and C₂₃H₃₈AsO - were identified as the major arsenolipids in the extracts of all oils by HPLC coupled with quadrupole time-of-flight mass spectrometry (qTOF-MS). Minor amounts of two arsenic-containing fatty acids (AsFAs) (C₂₃H₃₈AsO₃ and C₂₄H₃₈AsO₃) were also detected in the oils. The sum of the AsHCs and the AsFAs determined in the present study accounted for 17-42% of the total arsenic in the oils. Copyright © 2014 Elsevier B.V. All rights reserved.

Quantitative analysis of retinoids in biological fluids by high-performance liquid chromatography using column switching. I. Determination of isotretinoin and tretinoin and their 4-oxo metabolites in plasma.

PubMed

Wyss, R; Bucheli, F

1988-02-26

A fully automated gradient high-performance liquid chromatographic method for the determination of isotretinoin, tretinoin and their 4-oxo metabolites in plasma was developed, using the column-switching technique. After dilution with an internal standard solution containing 20% acetonitrile, 0.5 ml of the sample was injected onto a precolumn (17 X 4.6 mm I.D.), filled with C18 Corasil 37-53 micron. Proteins and polar plasma components were washed out using 1% ammonium acetate-acetonitrile (9:1, v/v) as mobile phase 1. After valve switching, the retained components were transferred to the analytical column in the backflush mode, separated by gradient elution and detected at 360 nm by UV detection. Using two coupled reversed-phase columns (125 mm long), the separation of cis and trans isomers was possible, and all four compounds could be quantified down to 2 ng/ml of plasma. The inter-assay precision in the concentration range 20-100 ng/ml was between 1.0 and 4.7% for all compounds.

A validated stability-indicating UPLC method for desloratadine and its impurities in pharmaceutical dosage forms.

PubMed

Rao, Dantu Durga; Satyanarayana, N V; Malleswara Reddy, A; Sait, Shakil S; Chakole, Dinesh; Mukkanti, K

2010-02-05

A novel stability-indicating gradient reverse phase ultra-performance liquid chromatographic (RP-UPLC) method was developed for the determination of purity of desloratadine in presence of its impurities and forced degradation products. The method was developed using Waters Aquity BEH C18 column with mobile phase containing a gradient mixture of solvents A and B. The eluted compounds were monitored at 280nm. The run time was 8min within which desloratadine and its five impurities were well separated. Desloratadine was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Desloratadine was found to degrade significantly in oxidative and thermal stress conditions and stable in acid, base, hydrolytic and photolytic degradation conditions. The degradation products were well resolved from main peak and its impurities, thus proved the stability-indicating power of the method. The developed method was validated as per ICH guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. This method was also suitable for the assay determination of desloratadine in pharmaceutical dosage forms.

Single-stage plasma-based correlated energy spread compensation for ultrahigh 6D brightness electron beams

DOE PAGES

Manahan, Grace G.; Habib, A. F.; Scherkl, P.; ...

2017-06-05

Plasma photocathode wakefield acceleration combines energy gains of tens of GeV m –1 with generation of ultralow emittance electron bunches, and opens a path towards 5D-brightness orders of magnitude larger than state-of-the-art. This holds great promise for compact accelerator building blocks and advanced light sources. However, an intrinsic by-product of the enormous electric field gradients inherent to plasma accelerators is substantial correlated energy spread—an obstacle for key applications such as free-electron-lasers. Here we show that by releasing an additional tailored escort electron beam at a later phase of the acceleration, when the witness bunch is relativistically stable, the plasma wavemore » can be locally overloaded without compromising the witness bunch normalized emittance. Here, this reverses the effective accelerating gradient, and counter-rotates the accumulated negative longitudinal phase space chirp of the witness bunch. Thereby, the energy spread is reduced by an order of magnitude, thus enabling the production of ultrahigh 6D-brightness beams.« less

Light-driven liquid microlenses

NASA Astrophysics Data System (ADS)

Angelini, A.; Pirani, F.; Frascella, F.; Ricciardi, S.; Descrovi, E.

2017-02-01

We propose a liquid polymeric compound based on photo-responsive azo-polymers to be used as light-activated optical element with tunable and reversible functionalities. The interaction of a laser beam locally modifies the liquid density thus producing a refractive index gradient. The laser induced refractive index profiles are observed along the optical axis of the microscope to evaluate the total phase shift induced and along the orthogonal direction to provide the axial distribution of the refractive index variation. The focusing and imaging properties of the liquid lenses as functions of the light intensity are illustrated.

HPLC-DAD-MS identification of bioactive secondary metabolites from Ferula communis roots.

PubMed

Arnoldi, Lolita; Ballero, Mauro; Fuzzati, Nicola; Maxia, Andrea; Mercalli, Enrico; Pagni, Luca

2004-06-01

A simple HPLC method was developed to distinguish between 'poisonous' and 'non-poisonous' chemotypes of Ferula communis. The method was performed on a C8 reverse phase analytical column using a binary eluent (aqueous TFA 0.01%-TFA 0.01% in acetonitrile) under gradient condition. The two chemotypes showed different fingerprints. The identification of five coumarins and eleven daucane derivatives by HPLC-diode array detection (HPLC-DAD) and HPLC-MS is described. A coumarin, not yet described, was detected. Copyright 2004 Elsevier B.V.

High-performance liquid chromatography separation and intact mass analysis of detergent-solubilized integral membrane proteins

PubMed Central

Berridge, Georgina; Chalk, Rod; D’Avanzo, Nazzareno; Dong, Liang; Doyle, Declan; Kim, Jung-In; Xia, Xiaobing; Burgess-Brown, Nicola; deRiso, Antonio; Carpenter, Elisabeth Paula; Gileadi, Opher

2011-01-01

We have developed a method for intact mass analysis of detergent-solubilized and purified integral membrane proteins using liquid chromatography–mass spectrometry (LC–MS) with methanol as the organic mobile phase. Membrane proteins and detergents are separated chromatographically during the isocratic stage of the gradient profile from a 150-mm C3 reversed-phase column. The mass accuracy is comparable to standard methods employed for soluble proteins; the sensitivity is 10-fold lower, requiring 0.2–5 μg of protein. The method is also compatible with our standard LC–MS method used for intact mass analysis of soluble proteins and may therefore be applied on a multiuser instrument or in a high-throughput environment. PMID:21093405

Quality by design: a systematic and rapid liquid chromatography and mass spectrometry method for eprosartan mesylate and its related impurities using a superficially porous particle column.

PubMed

Kalariya, Pradipbhai D; Kumar Talluri, Murali V N; Gaitonde, Vinay D; Devrukhakar, Prashant S; Srinivas, Ragampeta

2014-08-01

The present work describes the systematic development of a robust, precise, and rapid reversed-phase liquid chromatography method for the simultaneous determination of eprosartan mesylate and its six impurities using quality-by-design principles. The method was developed in two phases, screening and optimization. During the screening phase, the most suitable stationary phase, organic modifier, and pH were identified. The optimization was performed for secondary influential parameters--column temperature, gradient time, and flow rate using eight experiments--to examine multifactorial effects of parameters on the critical resolution and generated design space representing the robust region. A verification experiment was performed within the working design space and the model was found to be accurate. This study also describes other operating features of the column packed with superficially porous particles that allow very fast separations at pressures available in most liquid chromatography instruments. Successful chromatographic separation was achieved in less than 7 min using a fused-core C18 (100 mm × 2.1 mm, 2.6 μm) column with linear gradient elution of 10 mM ammonium formate (pH 3.0) and acetonitrile as the mobile phase. The method was validated for specificity, linearity, accuracy, precision, and robustness in compliance with the International Conference on Harmonization Q2 (R1) guidelines. The impurities were identified by liquid chromatography with mass spectrometry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible electron heating vs. wave-particle interactions in quasi-perpendicular shocks

NASA Technical Reports Server (NTRS)

Veltri, P.; Mangeney, A.; Scudder, J. D.

1992-01-01

The energy necessary to explain the electron heating in quasi-perpendicular collisionless shocks can be derived either from the electron acceleration in the d.c. cross shock electric potential, or by the interactions between the electrons and the waves existing in the shock. A Monte Carlo simulation has been performed to study the electron distribution function evolution through the shock structure, with and without particle diffusion on waves. This simulation has allowed us to clarify the relative importance of the two possible energy sources; in particular it has been shown that the electron parallel temperature is determined by the d.c. electromagnetic field and not by any wave-particle-induced heating. Wave particle interactions are effective in smoothing out the large gradients in phase space produced by the 'reversible' motion of the electrons, thus producing a 'cooling' of the electrons.

Rapid purification of staphylococcal enterotoxin B by high-pressure liquid chromatography.

PubMed Central

Strickler, M P; Neill, R J; Stone, M J; Hunt, R E; Brinkley, W; Gemski, P

1989-01-01

The Staphylococcus aureus enterotoxins represent a group of proteins that cause emesis and diarrhea in humans and other primates. We have developed a rapid two-step high-pressure liquid chromatography (HPLC) procedure for purification of staphylococcal enterotoxin B (SEB). Sterile filtrates (2.5 liters) of strain 10-275 were adsorbed directly onto a reversed-phase column (50 mm by 30 cm Delta Pak; 300 A [30 nm], 15 microns, C18). SEB was obtained by using a unique sequential gradient system. First, an aqueous ammonium acetate to acetonitrile gradient followed by an aqueous trifluoroacetic acid (TFA) wash was used to remove contaminants. A subsequent TFA to acetonitrile-TFA gradient eluted the bound SEB. Further purification was obtained by rechromatography on a cation-exchange column. From 35 to 45% of the SEB in starting filtrates was recovered. Analysis by immunoblotting of samples separated on sodium dodecyl sulfate-polyacrylamide gels indicated that HPLC-purified SEB exhibited immunological and biochemical properties similar to those of the SEB standard. Induction of an emetic response in rhesus monkeys showed that the HPLC-purified toxin also retained biological activity. Images PMID:2745678

Optimization and validation of the reversed-phase high-performance liquid chromatography with fluorescence detection method for the separation of tocopherol and tocotrienol isomers in cereals, employing a novel sorbent material.

PubMed

Irakli, Maria N; Samanidou, Victoria F; Papadoyannis, Ioannis N

2012-03-07

The separation and determination of tocopherols (Ts) and tocotrienols (T3s) by reversed-phase high-performance liquid chromatography with fluorescence detection has been developed and validated after optimization of various chromatographic conditions and other experimental parameters. Analytes were separated on a PerfectSil Target ODS-3 (250 × 4.6 mm, 3 μm) column filled with a novel sorbent material of ultrapure silica gel. The separation of Ts and T3s was optimized in terms of mobile-phase composition and column temperature on the basis of the best compromise among efficiency, resolution, and analysis time. Using a gradient elution of mobile phase composed of isopropanol/water and 7 °C column temperature, a satisfactory resolution was achieved within 62 min. For the quantitative determination, α-T acetate (50 μg/mL) was used as the internal standard. Detection limits ranged from 0.27 μg/mL (γ-T) to 0.76 μg/mL (γ-T3). The validation of the method was examined performing intraday (n = 5) and interday (n = 3) assays and was found to be satisfactory, with high accuracy and precision results. Solid-phase extraction provided high relative extraction recoveries from cereal samples: 87.0% for γ-T3 and 115.5% for δ-T. The method was successfully applied to cereals, such as durum wheat, bread wheat, rice, barley, oat, rye, and corn.

Development and Validation of a Stability-indicating Reversed-phase UPLC-UV Method for the Assay of Imidacloprid and Estimation of its Related Compounds.

PubMed

Tian, Jingzhi; Rustum, Abu

2018-02-01

Imidacloprid is used as an active pharmaceutical ingredient (API) in veterinary drugs to control fleas and ticks for dogs and cats. Here we are reporting for the first time a validated stability-indicating reversed-phase UPLC-UV method for the assay of imidacloprid and estimation of its related compounds. The stability-indicating capability of this method has been demonstrated by a forced degradation study. All related compounds including processing impurities, imidacloprid API and degradates from stressed samples were well separated from each other. Structures of major degradates from forced degradation study were elucidated through UPLC-MS/MS and key degradation pathways were proposed from the proposed chemical structures of major degradates. The UPLC-UV method is carried out using an HSS T3 column (C18, 2.1 × 30 mm, 1.8 μm particle size) maintained at 30°C with mobile phase A (0.05% v/v of phosphoric acid in water) and mobile phase B (methanol/acetonitrile 75/25 v/v). Analytes are separated by a gradient elution and detected at 270 nm. The UPLC method is green and fast with only 6.5 min run time and about 3.5 ml mobile phase consumption for each sample analysis. The UPLC-UV method was validated according to ICH guidelines. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

A fourth gradient to overcome slice dependent phase effects of voxel-sized coils in planar arrays.

PubMed

Bosshard, John C; Eigenbrodt, Edwin P; McDougall, Mary P; Wright, Steven M

2010-01-01

The signals from an array of densely spaced long and narrow receive coils for MRI are complicated when the voxel size is of comparable dimension to the coil size. The RF coil causes a phase gradient across each voxel, which is dependent on the distance from the coil, resulting in a slice dependent shift of k-space. A fourth gradient coil has been implemented and used with the system's gradient set to create a gradient field which varies with slice. The gradients are pulsed together to impart a slice dependent phase gradient to compensate for the slice dependent phase due to the RF coils. However the non-linearity in the fourth gradient which creates the desired slice dependency also results in a through-slice phase ramp, which disturbs normal slice refocusing and leads to additional signal cancelation and reduced field of view. This paper discusses the benefits and limitations of using a fourth gradient coil to compensate for the phase due to RF coils.

Ultrasound extracted flavonoids from four varieties of Portuguese red grape skins determined by reverse-phase high-performance liquid chromatography with electrochemical detection.

PubMed

Novak, Ivana; Janeiro, Patricia; Seruga, Marijan; Oliveira-Brett, Ana Maria

2008-12-23

Several flavonoids present in red grape skins from four varieties of Portuguese grapes were determined by reverse-phase high-performance liquid chromatography (RP-HPLC) with electrochemical detection (ECD). Extraction of flavonoids from red grape skins was performed by ultrasonication, and hydrochloric acid in methanol was used as extraction solvent. The developed RP-HPLC method used combined isocratic and gradient elution with amperometric detection with a glassy carbon-working electrode. Good peak resolution was obtained following direct injection of a sample of red grape extract in a pH 2.20 mobile phase. Eleven different flavonoids: cyanidin-3-O-glucoside (kuromanin), delphinidin-3-O-glucoside (myrtillin), petunidin-3-O-glucoside, peonidin-3-O-glucoside, malvidin-3-O-glucoside (oenin), (+)-catechin, rutin, fisetin, myricetin, morin and quercetin, can be separated in a single run by direct injection of sample solution. The limit of detection obtained for these compounds by ECD was 20-90 pg/L, 1000 times lower when compared with photodiode array (PDA) limit of detection of 12-55 ng/L. RP-HPLC-ECD was characterized by an excellent sensitivity and selectivity, and appropriate for the simultaneous determination of these electroactive phenolic compounds present in red grape skins.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, J. P.; Wang, Y. D.; Hao, Y. L.

Two main explanations exist for the deformation mechanisms in Ti-Nb-based gum metals, i.e. the formation of reversible nanodisturbance and reversible stress-induced martensitic transformation. In this work, we used the in situ synchrotron-based high-energy X-ray diffuse-scattering technique to reveal the existence of a specific deformation mechanism, i.e. deformation-induced spatially confined martensitic transformations, in Ti-24Nb-4Zr-8Sn-0.10O single crystals with cubic 13 parent phase, which explains well some anomalous mechanical properties of the alloy such as low elastic modulus and nonlinear superelasticity. Two kinds of nanosized martensites with different crystal structures were found during uniaxial tensile loading along the [11 0](beta) axis at roommore » temperature and 190 K, respectively. The detailed changes in the martensitic phase transformation characteristics and the transformation kinetics were experimentally observed at different temperatures. The domain switch from non-modulated martensite to a modulated one occurred at 190 K, with its physical origin attributed to the heterogeneity of local phonon softening depending on temperature and inhomogeneous composition in the parent phase. An in-depth understanding of the formation of stress-induced spatially confined nanosized martensites with a large gradient in chemical composition may benefit designs of high-strength and high-ductility alloys. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.« less

Near-field thermal rectification devices using phase change periodic nanostructure.

PubMed

Ghanekar, Alok; Tian, Yanpei; Ricci, Matthew; Zhang, Sinong; Gregory, Otto; Zheng, Yi

2018-01-22

We theoretically analyze two near-field thermal rectification devices: a radiative thermal diode and a thermal transistor that utilize a phase change material to achieve dynamic control over heat flow by exploiting metal-insulator transition of VO 2 near 341 K. The thermal analogue of electronic diode allows high heat flow in one direction while it restricts the heat flow when the polarity of temperature gradient is reversed. We show that with the introduction of 1-D rectangular grating, thermal rectification is dramatically enhanced in the near-field due to reduced tunneling of surface waves across the interfaces for negative polarity. The radiative thermal transistor also works around phase transition temperature of VO 2 and controls heat flow. We demonstrate a transistor-like behavior wherein heat flow across the source and the drain can be greatly varied by making a small change in gate temperature.

Determination of flunixin residues in bovine muscle tissue by liquid chromatography with UV detection.

PubMed

Asea, P A; Patterson, J R; Korsrud, G O; Dowling, P M; Boison, J O

2001-01-01

A new and sensitive liquid chromatography-ultra violet method with a detection limit of 6 ng/g (ppb) and a limit of quantification of 15 ng/g was developed for the determination of flunixin residues in bovine muscle tissue. Flunixin in homogenized animal tissue was extracted with acetonitrile after enzyme digestion. The tissue digest (extract) was then cleaned up on a solid-phase extraction cartridge and eluted with acidified hexane. After the eluate was evaporated to dryness under nitrogen at 55 degrees C, the residue was reconstituted in 1 mL mobile phase solution and analyzed by reversed-phase gradient chromatography with UV detection at 285 nm. The method was then applied in a survey study of slaughter animals to determine whether flunixin is being used in an off-label manner for veal and beef production in Canada.

Changes in the social class gradient of cirrhosis mortality in England and Wales across the 20th century.

PubMed

Crombie, Iain K; Precious, Elaine

2011-01-01

To explore the nature of the social class gradient of cirrhosis mortality in England and Wales across the 20th century. Data on male cirrhosis mortality by social class were obtained from the Registrar General's Decennial Supplements for the years 1921-1991. Data for 1941 were not collected because of the second World War. In 1921, cirrhosis mortality was substantially higher among the professional and managerial classes (I and II) than among the other social classes (III-V). This marked social class difference persisted until 1961 when the differences between the social classes were inconsistent. By 1991, the gradient had reversed and the lower social classes (IV and V) had the higher mortality. The excess mortality was greatest for social class V. The change in the mortality gradient is stark: in 1921social classes I and II had a cirrhosis mortality at least twice that of social classes IV and V, but by 1991 this ratio had reversed. The reversal in the social class gradient of cirrhosis mortality indicates a major change in risk factor distribution across social classes. Differential changes in alcohol consumption are a possible explanation for this change, although the 1991 social class gradient in cirrhosis is inconsistent with alcohol consumption data from national surveys. Further research is required to clarify the explanation for the observed gradient, so that appropriate preventive measures can be put into place.

Quantification of susceptibility change at high-concentrated SPIO-labeled target by characteristic phase gradient recognition.

PubMed

Zhu, Haitao; Nie, Binbin; Liu, Hua; Guo, Hua; Demachi, Kazuyuki; Sekino, Masaki; Shan, Baoci

2016-05-01

Phase map cross-correlation detection and quantification may produce highlighted signal at superparamagnetic iron oxide nanoparticles, and distinguish them from other hypointensities. The method may quantify susceptibility change by performing least squares analysis between a theoretically generated magnetic field template and an experimentally scanned phase image. Because characteristic phase recognition requires the removal of phase wrap and phase background, additional steps of phase unwrapping and filtering may increase the chance of computing error and enlarge the inconsistence among algorithms. To solve problem, phase gradient cross-correlation and quantification method is developed by recognizing characteristic phase gradient pattern instead of phase image because phase gradient operation inherently includes unwrapping and filtering functions. However, few studies have mentioned the detectable limit of currently used phase gradient calculation algorithms. The limit may lead to an underestimation of large magnetic susceptibility change caused by high-concentrated iron accumulation. In this study, mathematical derivation points out the value of maximum detectable phase gradient calculated by differential chain algorithm in both spatial and Fourier domain. To break through the limit, a modified quantification method is proposed by using unwrapped forward differentiation for phase gradient generation. The method enlarges the detectable range of phase gradient measurement and avoids the underestimation of magnetic susceptibility. Simulation and phantom experiments were used to quantitatively compare different methods. In vivo application performs MRI scanning on nude mice implanted by iron-labeled human cancer cells. Results validate the limit of detectable phase gradient and the consequent susceptibility underestimation. Results also demonstrate the advantage of unwrapped forward differentiation compared with differential chain algorithms for susceptibility quantification at high-concentrated iron accumulation. Copyright © 2015 Elsevier Inc. All rights reserved.

[Simultaneous analysis of aromatic aldehydes and coumarins with high pressure liquid chromatography. Application to wines and brandies stored in oak barrels].

PubMed

Salagoity-Auguste, M H; Tricard, C; Sudraud, P

1987-04-17

Aromatic aldehydes (vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde) and coumarins (esculetin, umbelliferone, scopoletin and methylumbelliferone) are natural wood compounds. Storage of wines and brandies in oak barrels increases notably aldehydes and coumarins (particularly scopoletin) concentrations. These compounds were separated by high-performance liquid chromatography, on hydrocarbon bonded reversed-phase packings, with a water-acetonitrile elution gradient. They were first extracted from wines and brandies by diethyl ether and then injected on chromatographic column. A double detection was used to determine simultaneously aromatic aldehydes and coumarins by UV absorption and fluorescence respectively.

Magnetic anisotropy at material interfaces

NASA Astrophysics Data System (ADS)

Greene, Peter Kevin

In this dissertation, a comprehensive set of depth dependent magnetic measurements, as well as structural characterizations, were carried out on the Co/Pd multilayer system. The first-order reversal curve (FORC) technique is applied extensively to identify reversal mechanisms and different reversal phases within the material. In particular, the extension of the FORC technique to x-ray magnetic circular dichroism (XMCD) as a surface sensitive technique that identifies reversible magnetization change was performed for the first time. Polarized neutron reflectivity (PNR) was also used to directly measure the magnetization as a function of depth. The effects of deposition pressure grading within the Co/Pd multilayers were investigated. Structures were graded with three distinct pressure regions. FORC analysis shows that not only does increasing the deposition pressure increase the coercivity and effective anisotropy within that region, but also the order in which the pressure is changed also affects the entire structure. Layers grown at high sputtering pressures tend to reverse via domain wall pinning and rotation while those grown at lower pressures reverse via rapid domain wall propagation laterally across the film. Having high pressure layers underneath low pressure layers causes disorder to vertically propagate and lessen the induced anisotropy gradient. This analysis is confirmed by depth dependent magnetization profiles obtain from PNR. Continuously pressure-graded Co/Pd multilayers were then sputtered at two incident angles onto porous aluminum oxide templates with different pore aspect ratios. The effects of pressure grading versus uniform low pressure deposition is studied, as well as the effect of the angle of the incident deposition flux. The coercivity of the pressure graded perpendicular flux sample is compared to the low pressure sample. Additionally the effect of deposition angle and pore sidewall deposition is investigated. It is shown that sidewall deposition strongly affects the reversal behavior. As another way to induce a vertical anisotropy gradient, Co/Pd multilayers were bombarded with Ar+ ions at different energies and fluences. The effects of the depth dependent structural damage as a function of irradiation conditions were investigated. It is shown that the structural damage weakens the perpendicular anisotropy of the surface layers, causing a tilting of the surface magnetic moment into the plane of the film. The surface behavior is explicitly measured and shown to have a significant tilting angle in the top 5 nm depending on irradiation energy and fluence. Continuing the study of vertical anisotropy gradients in Co/Pd multilayers, multilayers with varied Co thickness were studied. Four films with varying Co thickness profiles were created and then patterned into nanodot arrays with diameters between 700 nm and 70 nm. The different films were graded continuously, or in stacks with varying Co thicknesses. An anisotropy gradient is shown to be established in the graded samples, and the switching field is lowered as a result. Furthermore, in the continuously graded samples the magnetization reversal behavior is fundamentally different from all other samples. The thermal energy barriers are measured in the uniform and continuously graded samples, yielding similar results. Finally, the establishment of exchange anisotropy at the ferromagnet / antiferromagnet (FM/AFM) interface in the epitaxial Fe/CoO system is investigated as a function of AFM thickness. The establishment of frozen AFM moments is analyzed using the FORC technique. The FORC technique combined with vector coil measurements also shows the transition from rotatable AFM to pinned AFM moments and suggests a mechanism of winding domain walls within the bulk AFM. (Abstract shortened by UMI.).

Speciation of inorganic selenium and selenoamino acids by an HPLC-UV-HG-AFS system.

PubMed

Ipolyi, I; Corns, W; Stockwell, P; Fodor, P

2001-01-01

For the on-line speciation of selenocystine (SeCys), selenomethionine (SeMet), selenoethionine (SeEt), selenite (Se(IV)) and selenate (Se(VI)), a high-performance liquid chromatography-UV irradiation-hydride generation-atomic fluorescence spectro- metric method is described. Separation was carried out on a conventional reversed-phase C18 column modified with didodecyl- dimethylammonium bromide with gradient elution applying two concentrations of ammonium acetate as the mobile phase. UV irradiation and hydride generation parameters were optimized. The obtained detection limits for SeCys, SeMet, SeEt, Se(IV) and Se(VI) were 0.31, 0.43, 0.7, 0.44 and 0.32 ng ml(-1), respectively, using a 100-microl loop. The method was tested with spiked mineral water and two volunteers' urine samples.

Speciation of inorganic selenium and selenoamino acids by an HPLC-UV-HG-AFS system

PubMed Central

Ipolyi, I.; Corns, W.; Stockwell, P.; Fodor, P.

2001-01-01

For the on-line speciation of selenocystine (SeCys), selenomethionine (SeMet), selenoethionine (SeEt), selenite (Se(IV)) and selenate (Se(VI)), a high-performance liquid chromatography-UV irradiation-hydride generation-atomic fluorescence spectro- metric method is described. Separation was carried out on a conventional reversed-phase C18 column modified with didodecyl- dimethylammonium bromide with gradient elution applying two concentrations of ammonium acetate as the mobile phase. UV irradiation and hydride generation parameters were optimized. The obtained detection limits for SeCys, SeMet, SeEt, Se(IV) and Se(VI) were 0.31, 0.43, 0.7, 0.44 and 0.32 ng ml−1, respectively, using a 100-wl loop. The method was tested with spiked mineral water and two volunteers' urine samples. PMID:18924707

Reversed magnetic shear suppression of electron-scale turbulence on NSTX

NASA Astrophysics Data System (ADS)

Yuh, Howard Y.; Levinton, F. M.; Bell, R. E.; Hosea, J. C.; Kaye, S. M.; Leblanc, B. P.; Mazzucato, E.; Smith, D. R.; Domier, C. W.; Luhmann, N. C.; Park, H. K.

2009-11-01

Electron thermal internal transport barriers (e-ITBs) are observed in reversed (negative) magnetic shear NSTX discharges^1. These e-ITBs can be created with either neutral beam heating or High Harmonic Fast Wave (HHFW) RF heating. The e-ITB location occurs at the location of minimum magnetic shear determined by Motional Stark Effect (MSE) constrained equilibria. Statistical studies show a threshold condition in magnetic shear for e-ITB formation. High-k fluctuation measurements at electron turbulence wavenumbers^3 have been made under several different transport regimes, including a bursty regime that limits temperature gradients at intermediate magnetic shear. The growth rate of fluctuations has been calculated immediately following a change in the local magnetic shear, resulting in electron temperature gradient relaxation. Linear gyrokinetic simulation results for NSTX show that while measured electron temperature gradients exceed critical linear thresholds for ETG instability, growth rates can remain low under reversed shear conditions up to high electron temperatures gradients. ^1H. Yuh, et. al., PoP 16, 056120 ^2D.R. Smith, E. Mazzucato et al., RSI 75, 3840 ^3E. Mazzucato, D.R. Smith et al., PRL 101, 075001

Shear-strain gradient induced polarization reversal in ferroelectric BaTiO3 thin films: A first-principles total-energy study

NASA Astrophysics Data System (ADS)

Li, Guannan; Huang, Xiaokun; Hu, Jingsan; Zhang, Weiyi

2017-04-01

Based on the first-principles total-energy calculation, we have studied the shear-strain gradient effect on the polarization reversal of ferroelectric BaTiO3 thin films. By calculating the energies of double-domain supercells for different electric polarization, shear-strain gradients, and domain-wall displacement, we extracted, in addition to the domain-wall energy, the polarization energy, elastic energy, and flexoelectric coefficient of a single domain. The constructed Landau-Devonshire phenomenological theory yields a critical shear-strain gradient of 9.091 ×107/m (or a curvature radius (R ) of 110 Å) for reversing the 180∘ domain at room temperature, which is on the same order of the experimentally estimated value of 3.333 ×107/m (R =300 Å ). In contrast to the commonly used linear response theory, the flexoelectric coefficient derived from fitting the total energy to a Landau-Devonshire energy functional does not depend on the specific pseudopotential. Thus, our method offers an alternative numerical approach to study the flexoelectric effect.

Phase gradient imaging for positive contrast generation to superparamagnetic iron oxide nanoparticle-labeled targets in magnetic resonance imaging.

PubMed

Zhu, Haitao; Demachi, Kazuyuki; Sekino, Masaki

2011-09-01

Positive contrast imaging methods produce enhanced signal at large magnetic field gradient in magnetic resonance imaging. Several postprocessing algorithms, such as susceptibility gradient mapping and phase gradient mapping methods, have been applied for positive contrast generation to detect the cells targeted by superparamagnetic iron oxide nanoparticles. In the phase gradient mapping methods, smoothness condition has to be satisfied to keep the phase gradient unwrapped. Moreover, there has been no discussion about the truncation artifact associated with the algorithm of differentiation that is performed in k-space by the multiplication with frequency value. In this work, phase gradient methods are discussed by considering the wrapping problem when the smoothness condition is not satisfied. A region-growing unwrapping algorithm is used in the phase gradient image to solve the problem. In order to reduce the truncation artifact, a cosine function is multiplied in the k-space to eliminate the abrupt change at the boundaries. Simulation, phantom and in vivo experimental results demonstrate that the modified phase gradient mapping methods may produce improved positive contrast effects by reducing truncation or wrapping artifacts. Copyright © 2011 Elsevier Inc. All rights reserved.

Optimized phase gradient measurements and phase-amplitude interplay in optical coherence elastography

NASA Astrophysics Data System (ADS)

Zaitsev, Vladimir Y.; Matveyev, Alexander L.; Matveev, Lev A.; Gelikonov, Grigory V.; Sovetsky, Aleksandr A.; Vitkin, Alex

2016-11-01

In compressional optical coherence elastography, phase-variation gradients are used for estimating quasistatic strains created in tissue. Using reference and deformed optical coherence tomography (OCT) scans, one typically compares phases from pixels with the same coordinates in both scans. Usually, this limits the allowable strains to fairly small values < to 10-3, with the caveat that such weak phase gradients may become corrupted by stronger measurement noises. Here, we extend the OCT phase-resolved elastographic methodology by (1) showing that an order of magnitude greater strains can significantly increase the accuracy of derived phase-gradient differences, while also avoiding error-phone phase-unwrapping procedures and minimizing the influence of decorrelation noise caused by suprapixel displacements, (2) discussing the appearance of artifactual stiff inclusions in resultant OCT elastograms in the vicinity of bright scatterers due to the amplitude-phase interplay in phase-variation measurements, and (3) deriving/evaluating methods of phase-gradient estimation that can outperform conventionally used least-square gradient fitting. We present analytical arguments, numerical simulations, and experimental examples to demonstrate the advantages of the proposed optimized phase-variation methodology.

A sensitive and accurate method for the determination of perfluoroalkyl and polyfluoroalkyl substances in human serum using a high performance liquid chromatography-online solid phase extraction-tandem mass spectrometry.

PubMed

Yu, Chang Ho; Patel, Bhupendra; Palencia, Marilou; Fan, Zhihua Tina

2017-01-13

A selective, sensitive, and accurate analytical method for the measurement of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in human serum, utilizing LC-MS/MS (liquid chromatography-tandem mass spectrometry), was developed and validated according to the Centers for Disease Control and Prevention (CDC) guidelines for biological sample analysis. Tests were conducted to determine the optimal analytical column, mobile phase composition and pH, gradient program, and cleaning procedure. The final analytical column selected for analysis was an extra densely bonded silica-packed reverse-phase column (Agilent XDB-C 8 , 3.0×100mm, 3.5μm). Mobile phase A was an aqueous buffer solution containing 10mM ammonium acetate (pH=4.3). Mobile phase B was a mixture of methanol and acetonitrile (1:1, v/v). The gradient program was programmed by initiating a fast elution (%B, from 40 to 65%) between 1.0 and 1.5min, followed by a slow elution (%B: 65-80%) in the period of 1.5-7.5min. The cleanup procedures were augmented by cleaning with (1) various solvents (isopropyl alcohol, methanol, acetonitrile, and reverse osmosis-purified water); (2) extensive washing steps for the autosampler and solid phase extraction (SPE) cartridge; and (3) a post-analysis cleaning step for the whole system. Under the above conditions, the resolution and sensitivity were significantly improved. Twelve target PFASs were baseline-separated (2.5-7.0min) within a 10-min of acquisition time. The limits of detection (LODs) were 0.01ng/mL or lower for all of the target compounds, making this method 5 times more sensitive than previously published methods. The newly developed method was validated in the linear range of 0.01-50ng/mL, and the accuracy (recovery between 80 and 120%) and precision (RSD<20%) were acceptable at three spiked levels (0.25, 2.5, and 25ng/mL). The method development and validation results demonstrated that this method was precise, accurate, and robust, with high-throughput (∼10min per sample); thus suitable for large-scale epidemiological studies. Published by Elsevier B.V.

New approaches with two cyano columns to the separation of acetaminophen, phenylephrine, chlorpheniramine and related compounds.

PubMed

Olmo, B; García, A; Marín, A; Barbas, C

2005-03-25

The development of new pharmaceutical forms with classical active compounds generates new analytical problems. That is the case of sugar-free sachets of cough-cold products containing acetaminophen, phenylephrine hydrochloride and chlorpheniramine maleate. Two cyanopropyl stationary phases have been employed to tackle the problem. The Discovery cyanopropyl (SUPELCO) column permitted the separation of the three actives, maleate and excipients (mainly saccharine and orange flavour) with a constant proportion of aqueous/ organic solvent (95:5, v/v) and a pH gradient from 7.5 to 2. The run lasted 14 min. This technique avoids many problems related to baseline shifts with classical organic solvent gradients and opens great possibilities to modify selectivity not generally used in reversed phase HPLC. On the other hand, the Agilent Zorbax SB-CN column with a different retention profile permitted us to separate not only the three actives and the excipients but also the three known related compounds: 4-aminophenol, 4-chloracetanilide and 4-nitrophenol in an isocratic method with a run time under 30 min. This method was validated following ICH guidelines and validation parameters showed that it could be employed as stability-indicating method for this pharmaceutical form.

Doppler echo evaluation of pulmonary venous-left atrial pressure gradients: human and numerical model studies

NASA Technical Reports Server (NTRS)

Firstenberg, M. S.; Greenberg, N. L.; Smedira, N. G.; Prior, D. L.; Scalia, G. M.; Thomas, J. D.; Garcia, M. J.

2000-01-01

The simplified Bernoulli equation relates fluid convective energy derived from flow velocities to a pressure gradient and is commonly used in clinical echocardiography to determine pressure differences across stenotic orifices. Its application to pulmonary venous flow has not been described in humans. Twelve patients undergoing cardiac surgery had simultaneous high-fidelity pulmonary venous and left atrial pressure measurements and pulmonary venous pulsed Doppler echocardiography performed. Convective gradients for the systolic (S), diastolic (D), and atrial reversal (AR) phases of pulmonary venous flow were determined using the simplified Bernoulli equation and correlated with measured actual pressure differences. A linear relationship was observed between the convective (y) and actual (x) pressure differences for the S (y = 0.23x + 0.0074, r = 0.82) and D (y = 0.22x + 0.092, r = 0.81) waves, but not for the AR wave (y = 0. 030x + 0.13, r = 0.10). Numerical modeling resulted in similar slopes for the S (y = 0.200x - 0.127, r = 0.97), D (y = 0.247x - 0. 354, r = 0.99), and AR (y = 0.087x - 0.083, r = 0.96) waves. Consistent with numerical modeling, the convective term strongly correlates with but significantly underestimates actual gradient because of large inertial forces.

High temperature-ultra performance liquid chromatography-mass spectrometry for the metabonomic analysis of Zucker rat urine.

PubMed

Gika, Helen G; Theodoridis, Georgios; Extance, Jon; Edge, Anthony M; Wilson, Ian D

2008-08-15

The applicability and potential of using elevated temperatures and sub 2-microm porous particles in chromatography for metabonomics/metabolomics was investigated using, for the first time, solvent temperatures higher than the boiling point of water (up to 180 degrees C) and thermal gradients to reduce the use of organic solvents. Ultra performance liquid chromatography, combined with mass spectrometry, was investigated for the global metabolite profiling of the plasma and urine of normal and Zucker (fa/fa) obese rats (a well established disease animal model). "Isobaric" high temperature chromatography, where the temperature and flow rate follow a gradient program, was developed and evaluated against a conventional organic solvent gradient. LC-MS data were first examined by established chromatographic criteria in order to evaluate the chromatographic performance and next were treated by special peak picking algorithms to allow the application of multivariate statistics. These studies showed that, for urine (but not plasma), chromatography at elevated temperatures provided better results than conventional reversed-phase LC with higher peak capacity and better peak asymmetry. From a systems biology point of view, better group clustering and separation was obtained with a larger number of variables of high importance when using high temperature-ultra performance liquid chromatography (HT-UPLC) compared to conventional solvent gradients.

Systematic Optimization of Long Gradient Chromatography Mass Spectrometry for Deep Analysis of Brain Proteome

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hong; Yang, Yanling; Li, Yuxin

2015-02-06

Development of high resolution liquid chromatography (LC) is essential for improving the sensitivity and throughput of mass spectrometry (MS)-based proteomics. Here we present systematic optimization of a long gradient LC-MS/MS platform to enhance protein identification from a complex mixture. The platform employed an in-house fabricated, reverse phase column (100 μm x 150 cm) coupled with Q Exactive MS. The column was capable of achieving a peak capacity of approximately 700 in a 720 min gradient of 10-45% acetonitrile. The optimal loading level was about 6 micrograms of peptides, although the column allowed loading as many as 20 micrograms. Gas phasemore » fractionation of peptide ions further increased the number of peptide identification by ~10%. Moreover, the combination of basic pH LC pre-fractionation with the long gradient LC-MS/MS platform enabled the identification of 96,127 peptides and 10,544 proteins at 1% protein false discovery rate in a postmortem brain sample of Alzheimer’s disease. As deep RNA sequencing of the same specimen suggested that ~16,000 genes were expressed, current analysis covered more than 60% of the expressed proteome. Further improvement strategies of the LC/LC-MS/MS platform were also discussed.« less

Doppler echo evaluation of pulmonary venous-left atrial pressure gradients: human and numerical model studies.

PubMed

Firstenberg, M S; Greenberg, N L; Smedira, N G; Prior, D L; Scalia, G M; Thomas, J D; Garcia, M J

2000-08-01

The simplified Bernoulli equation relates fluid convective energy derived from flow velocities to a pressure gradient and is commonly used in clinical echocardiography to determine pressure differences across stenotic orifices. Its application to pulmonary venous flow has not been described in humans. Twelve patients undergoing cardiac surgery had simultaneous high-fidelity pulmonary venous and left atrial pressure measurements and pulmonary venous pulsed Doppler echocardiography performed. Convective gradients for the systolic (S), diastolic (D), and atrial reversal (AR) phases of pulmonary venous flow were determined using the simplified Bernoulli equation and correlated with measured actual pressure differences. A linear relationship was observed between the convective (y) and actual (x) pressure differences for the S (y = 0.23x + 0.0074, r = 0.82) and D (y = 0.22x + 0.092, r = 0.81) waves, but not for the AR wave (y = 0. 030x + 0.13, r = 0.10). Numerical modeling resulted in similar slopes for the S (y = 0.200x - 0.127, r = 0.97), D (y = 0.247x - 0. 354, r = 0.99), and AR (y = 0.087x - 0.083, r = 0.96) waves. Consistent with numerical modeling, the convective term strongly correlates with but significantly underestimates actual gradient because of large inertial forces.

A Modified MuDPIT Separation Identified 4,488 Proteins in a System Wide Analysis of Quiescence in Yeast

PubMed Central

Webb, Kristofor J.; Xu, Tao; Park, Sung Kyu; Yates, John R.

2013-01-01

A modified multidimensional protein identification technology (MudPIT) separation was coupled to an LTQ Orbitrap Velos mass spectrometer and used to rapidly identify the near complete yeast proteome from a whole cell tryptic digest. This modified on-line two dimensional liquid chromatography separation consists of 39 strong cation exchange steps followed by a short 18.5 min reversed-phase (RP) gradient. A total of 4,269 protein identifications were made from 4,189 distinguishable protein families from yeast during log phase growth. The “Micro” MudPIT separation performed as well as a standard MudPIT separation in 40% less gradient time. The majority of the yeast proteome can now be routinely covered in less than a days’ time with high reproducibility and sensitivity. The newly devised separation method was used to detect changes in protein expression during cellular quiescence in yeast. An enrichment in the GO annotations ‘oxidation reduction’, ‘catabolic processing’ and ‘cellular response to oxidative stress’ was seen in the quiescent cellular fraction, consistent with their long lived stress resistant phenotypes. Heterogeneity was observed in the stationary phase fraction with a less dense cell population showing reductions in KEGG pathway categories of ‘Ribosome’ and ‘Proteasome’, further defining the complex nature of yeast populations present during stationary phase growth. In total 4,488 distinguishable protein families were identified in all cellular conditions tested. PMID:23540446

Development and validation of a rapid ultra-high performance liquid chromatography method for the assay of benzalkonium chloride using a quality-by-design approach.

PubMed

Mallik, Rangan; Raman, Srividya; Liang, Xiaoli; Grobin, Adam W; Choudhury, Dilip

2015-09-25

A rapid robust reversed-phase UHPLC method has been developed for the analysis of total benzalkonium chloride in preserved drug formulation. A systematic Quality-by-Design (QbD) method development approach using commercial, off the shelf software (Fusion AE(®)) has been used to optimize the column, mobile phases, gradient time, and other HPLC conditions. Total benzalkonium chloride analysis involves simple sample preparation. The method uses gradient elution from an ACE Excel 2 C18-AR column (50mm×2.1mm, 2.0μm particle size), ammonium phosphate buffer (pH 3.3; 10mM) as aqueous mobile phase and methanol/acetonitrile (85/15, v/v) as the organic mobile phase with UV detection at 214nm. Using these conditions, major homologs of the benzalkonium chloride (C12 and C14) have been separated in less than 2.0min. The validation results confirmed that the method is precise, accurate and linear at concentrations ranging from 0.025mg/mL to 0.075mg/mL for total benzalkonium chloride. The recoveries ranged from 99% to 103% at concentrations from 0.025mg/mL to 0.075mg/mL for total benzalkonium chloride. The validation results also confirmed the robustness of the method as predicted by Fusion AE(®). Copyright © 2015 Elsevier B.V. All rights reserved.

Cardiovascular Pressures with Venous Gas Embolism and Decompression

NASA Technical Reports Server (NTRS)

Butler, B. D.; Robinson, R.; Sutton, T.; Kemper, G. B.

1995-01-01

Venous gas embolism (VGE) is reported with decompression to a decreased ambient pressure. With severe decompression, or in cases where an intracardiac septal defect (patent foramen ovale) exists, the venous bubbles can become arterialized and cause neurological decompression illness. Incidence rates of patent foramen ovale in the general population range from 25-34% and yet aviators, astronauts, and deepsea divers who have decompression-induced venous bubbles do not demonstrate neurological symptoms at these high rates. This apparent disparity may be attributable to the normal pressure gradient across the atria of the heart that must be reversed for there to be flow potency. We evaluated the effects of: venous gas embolism (0.025, 0.05 and 0.15 ml/ kg min for 180 min.) hyperbaric decompression; and hypobaric decompression on the pressure gradient across the left and right atria in anesthetized dogs with intact atrial septa. Left ventricular end-diastolic pressure was used as a measure of left atrial pressure. In a total of 92 experimental evaluations in 22 dogs, there were no reported reversals in the mean pressure gradient across the atria; a total of 3 transient reversals occurred during the peak pressure gradient changes. The reasons that decompression-induced venous bubbles do not consistently cause serious symptoms of decompression illness may be that the amount of venous gas does not always cause sufficient pressure reversal across a patent foramen ovale to cause arterialization of the venous bubbles.

Rapid isolation procedure for Δ9-tetrahydrocannabinolic acid A (THCA) from Cannabis sativa using two flash chromatography systems.

PubMed

Wohlfarth, Ariane; Mahler, Hellmut; Auwärter, Volker

2011-10-15

Two isolation procedures for Δ9-tetrahydrocannabinolic acid A (THCA), the biogenetic precursor in the biosynthesis of the psychoactive Δ9-tetrahydrocannabinol (THC) in the cannabis plant, are presented. Two flash chromatography systems that can be used independently from each other were developed to separate THCA from other compounds of a crude cannabis extract. In both systems UV absorption at 209 and 270 nm was monitored. Purity was finally determined by HPLC-DAD, NMR and GC-MS analysis with a focus on the impurity THC. System 1 consisted of a normal phase silica column (120 g) as well as cyclohexane and acetone--both spiked with the modifier pyridine--as mobile phases. Gradient elution was performed over 15 min. After the chromatographic run the fractions containing THCA fractions were pooled, extracted with hydrochloric acid to eliminate pyridine and evaporated to dryness. Loading 1800 mg cannabis extract yielded 623 mg THCA with a purity of 99.8% and a THC concentration of 0.09%. System 2 was based on a reversed-phase C18 column (150 g) combined with 0.55% formic acid and methanol as mobile phases. A very flat gradient was set over 20 minutes. After pooling the THCA-containing fractions methanol was removed in a rotary evaporator. THCA was re-extracted from the remaining aqueous phase with methyl tert-butyl ether. The organic phase was finally evaporated under high vacuum conditions. Loading 300 mg cannabis extract yielded 51 mg THCA with a purity of 98.8% and a THC concentration of 0.67%. Copyright © 2011 Elsevier B.V. All rights reserved.

Theoretical and lidar studies of the density response of the mesospheric sodium layer to gravity wave perturbations

NASA Technical Reports Server (NTRS)

Shelton, J. D.; Gardner, C. S.

1981-01-01

The density response of atmospheric layers to gravity waves is developed in two forms, an exact solution and a perturbation series solution. The degree of nonlinearity in the layer density response is described by the series solution whereas the exact solution gives insight into the nature of the responses. Density perturbation in an atmospheric layer are shown to be substantially greater than the atmospheric density perturbation associated with the propagation of a gravity wave. Because of the density gradients present in atmospheric layers, interesting effects were observed such as a phase reversal in the linear layer response which occurs near the layer peak. Once the layer response is understood, the sodium layer can be used as a tracer of atmospheric wave motions. A two dimensional digital signal processing technique was developed. Both spatial and temporal filtering are utilized to enhance the resolution by decreasing shot noise by more han 10 dB. Many of the features associated with a layer density response to gravity waves were observed in high resolution density profiles of the mesospheric sodium layer. These include nonlinearities as well as the phase reversal in the linear layer response.

Reversed-phase high-performance liquid chromatographic method for the determination of peptidoglycan monomers and structurally related peptides and adamantyltripeptides.

PubMed

Krstanović, Marina; Frkanec, Ruza; Vranesić, Branka; Ljevaković, Durdica; Sporec, Vesna; Tomasić, Jelka

2002-06-25

The reversed-phase HPLC method using UV detection was developed for the determination of (a) immunostimulating peptidoglycan monomers represented by the basic structure GlcNAc-MurNAc-L-Ala-D-isoGln-meso-DAP(omegaNH(2))-D-Ala-D-Ala (PGM) and two more lipophilic derivatives, Boc-Tyr-PGM and (Ada-1-yl)-CH(2)-CO-PGM, (b) two diastereomeric immunostimulating adamantyltripeptides L- and D-(adamant-2-yl)-Gly-L-Ala-D-isoGln and (c) peptides obtained by the enzyme hydrolyses of peptidoglycans and related peptides. The enzymes used, N-acetylmuramyl-L-alanine amidase and an L,D-aminopeptidase are present in mammalian sera and are involved in the metabolism of peptidoglycans and related peptides. Appropriate solvent systems were chosen with regard to structure and lipophilicity of each compound. As well, different gradient systems within the same solvent system had to be applied in order to achieve satisfactory separation and retention time. HPLC separation was developed with the aim to use this method for the study of the stability of the tested compounds, the purity during preparation and isolation and for following the enzyme hydrolyses.

[Simultaneous determination of five cold medicine ingredients in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets by pH/organic solvent double-gradient high performance liquid chromatography].

PubMed

Xuan, Xueyi; Huang, Lina; Pan, Xiaoling; Li, Ning

2013-02-01

A pH/organic solvent double-gradient mode in reversed-phase high performance liquid chromatography (HPLC) has been established as a new approach to the simultaneous determination of acetaminophen, caffeine, salicylamide, pseudoephedrine hydrochloride and triprolidine hydrochloride in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets. Through the optimization of the organic solvent gradient mode and pH/organic solvent double-gradient mode, the optimum double-gradient HPLC system of the five cold medicine ingredients has been built. The determination was carried out on a Diamonsiol C18 column (250 mm x 4.6 mm, 5 microm). The mobile phase consisted of methanol, 0.05 mol/L ammonium acetate solution and 0.08 mol/L acetic acid solution. The column temperature was set at 30 degrees C. The flow rate was 1.0 mL/min. The sample was measured at multiple wavelengths: 0-6 min, 280 nm; 6-7 min, 257 nm; 7-14 min, 280 nm; 14 min, 233 nm. The separation of the five cold medicine ingredients in the tablets was achieved in 25.5 min. The linear ranges of acetaminophen, pseudoephedrine hydrochloride, caffeine, salicylamide and triprolidine hydrochloride were 0.055 -0.998 g/L, 0.053-0.946 g/L, 0.007-0.129 g/L, 0.035-0.622 g/L and 0.002-0.039 g/L, respectively, with their correlation coefficients greater than 0.999 0. The detection limits (S/N = 3) were 0.09, 6, 0.02, 0.128 and 0.02 mg/L, respectively. Their mean recoveries were 97.9%-102.8%. The advantage of the method is the simultaneous determination of acidic, neutral and basic compounds. It also can improve the column efficiency of the analyte, compress the half-peak width and reduce the trailing. The optimized and validated method can be used for the simultaneous determination of the five cold medicine ingredients in the tablets.

Cloud-point extraction and reversed-phase high-performance liquid chromatography for the determination of synthetic phenolic antioxidants in edible oils.

PubMed

Chen, Miao; Xia, Qinghai; Liu, Mousheng; Yang, Yaling

2011-01-01

A cloud-point extraction (CPE) method using Triton X-114 (TX-114) nonionic surfactant was developed for the extraction and preconcentration of propyl gallate (PG), tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) from edible oils. The optimum conditions of CPE were 2.5% (v/v) TX-114, 0.5% (w/v) NaCl and 40 min equilibration time at 50 °C. The surfactant-rich phase was then analyzed by reversed-phase high-performance liquid chromatography with ultraviolet detection at 280 nm, using a gradient mobile phase consisting of methanol and 1.5% (v/v) acetic acid. Under the studied conditions, 4 synthetic phenolic antioxidants (SPAs) were successfully separated within 24 min. The limits of detection (LOD) were 1.9 ng mL(-1) for PG, 11 ng mL(-1) for TBHQ, 2.3 ng mL(-1) for BHA, and 5.9 ng mL(-1) for BHT. Recoveries of the SPAs spiked into edible oil were in the range 81% to 88%. The CPE method was shown to be potentially useful for the preconcentration of the target analytes, with a preconcentration factor of 14. Moreover, the method is simple, has high sensitivity, consumes much less solvent than traditional methods, and is environment-friendly. Practical Application: The method established in this article uses less organic solvent to extract SPAs from edible oils; it is simple, highly sensitive and results in no pollution to the environment.

Subseasonal Reversal of East Asian Surface Temperature Variability in Winter 2014/15

NASA Astrophysics Data System (ADS)

Xu, Xinping; Li, Fei; He, Shengping; Wang, Huijun

2018-06-01

Although there has been a considerable amount of research conducted on the East Asian winter-mean climate, subseasonal surface air temperature (SAT) variability reversals in the early and late winter remain poorly understood. In this study, we focused on the recent winter of 2014/15, in which warmer anomalies dominated in January and February but colder conditions prevailed in December. Moreover, Arctic sea-ice cover (ASIC) in September-October 2014 was lower than normal, and warmer sea surface temperature (SST) anomalies occurred in the Niño4 region in winter, together with a positive Pacific Decadal Oscillation (PDO|+) phase. Using observational data and CMIP5 historical simulations, we investigated the PDO|+ phase modulation upon the winter warm Niño4 phase (autumn ASIC reduction) influence on the subseasonal SAT variability of East Asian winter. The results show that, under a PDO|+ phase modulation, warm Niño4 SST anomalies are associated with a subseasonal delay of tropical surface heating and subsequent Hadley cell and Ferrel cell intensification in January-February, linking the tropical and midlatitude regions. Consistently, the East Asian jet stream (EAJS) is significantly decelerated in January-February and hence promotes the warm anomalies over East Asia. Under the PDO|+ phase, the decrease in ASIC is related to cold SST anomalies in the western North Pacific, which increase the meridional temperature gradient and generate an accelerated and westward-shifted EAJS in December. The westward extension of the EAJS is responsible for the eastward-propagating Rossby waves triggered by declining ASIC and thereby favors the connection between ASIC and cold conditions over East Asia.

Direct coupling of microbore HPLC columns to MS systems

NASA Technical Reports Server (NTRS)

Mcnair, H. M.

1985-01-01

A detailed investigation using electron microscopy was conducted which examined the conditions of materials used in the construction of stable, high performance microbore liquid chromatography (LC) columns. Small details proved to be important. The effects of temperature on the elution of several homologous series used as probe compounds was examined in reverse phase systems. They showed that accessible temperature changes provide roughly half the increase in solvent strength that would be obtained going from a 100% aqueous to a 100% organic mobile phase, which is sufficient to warrant their use in many analyses requiring the use of gradients. Air circulation temperature control systems provide the easiest means of obtaining rapid, wide range changes in column temperature. However, slow heat transfer from the gas leads to thermal nonuniformity in the column and a decrease in resolution as the temperature program progresses.

Acoustic noise reduction in T 1- and proton-density-weighted turbo spin-echo imaging.

PubMed

Ott, Martin; Blaimer, Martin; Breuer, Felix; Grodzki, David; Heismann, Björn; Jakob, Peter

2016-02-01

To reduce acoustic noise levels in T 1-weighted and proton-density-weighted turbo spin-echo (TSE) sequences, which typically reach acoustic noise levels up to 100 dB(A) in clinical practice. Five acoustic noise reduction strategies were combined: (1) gradient ramps and shapes were changed from trapezoidal to triangular, (2) variable-encoding-time imaging was implemented to relax the phase-encoding gradient timing, (3) RF pulses were adapted to avoid the need for reversing the polarity of the slice-rewinding gradient, (4) readout bandwidth was increased to provide more time for gradient activity on other axes, (5) the number of slices per TR was reduced to limit the total gradient activity per unit time. We evaluated the influence of each measure on the acoustic noise level, and conducted in vivo measurements on a healthy volunteer. Sound recordings were taken for comparison. An overall acoustic noise reduction of up to 16.8 dB(A) was obtained by the proposed strategies (1-4) and the acquisition of half the number of slices per TR only. Image quality in terms of SNR and CNR was found to be preserved. The proposed measures in this study allowed a threefold reduction in the acoustic perception of T 1-weighted and proton-density-weighted TSE sequences compared to a standard TSE-acquisition. This could be achieved without visible degradation of image quality, showing the potential to improve patient comfort and scan acceptability.

Phase gradient algorithm based on co-axis two-step phase-shifting interferometry and its application

NASA Astrophysics Data System (ADS)

Wang, Yawei; Zhu, Qiong; Xu, Yuanyuan; Xin, Zhiduo; Liu, Jingye

2017-12-01

A phase gradient method based on co-axis two-step phase-shifting interferometry, is used to reveal the detailed information of a specimen. In this method, the phase gradient distribution can only be obtained by calculating both the first-order derivative and the radial Hilbert transformation of the intensity difference between two phase-shifted interferograms. The feasibility and accuracy of this method were fully verified by the simulation results for a polystyrene sphere and a red blood cell. The empirical results demonstrated that phase gradient is sensitive to changes in the refractive index and morphology. Because phase retrieval and tedious phase unwrapping are not required, the calculation speed is faster. In addition, co-axis interferometry has high spatial resolution.

High-performance liquid chromatographic method for guanylhydrazone compounds.

PubMed

Cerami, C; Zhang, X; Ulrich, P; Bianchi, M; Tracey, K J; Berger, B J

1996-01-12

A high-performance liquid chromatographic method has been developed for a series of aromatic guanylhydrazones that have demonstrated therapeutic potential as anti-inflammatory agents. The compounds were separated using octadecyl or diisopropyloctyl reversed-phase columns, with an acetonitrile gradient in water containing heptane sulfonate, tetramethylammonium chloride, and phosphoric acid. The method was used to reliably quantify levels of analyte as low as 785 ng/ml, and the detector response was linear to at least 50 micrograms/ml using a 100 microliters injection volume. The assay system was used to determine the basic pharmacokinetics of a lead compound, CNI-1493, from serum concentrations following a single intravenous injection in rats.

Submillikelvin Dipolar Molecules in a Radio-Frequency Magneto-Optical Trap.

PubMed

Norrgard, E B; McCarron, D J; Steinecker, M H; Tarbutt, M R; DeMille, D

2016-02-12

We demonstrate a scheme for magneto-optically trapping strontium monofluoride (SrF) molecules at temperatures one order of magnitude lower and phase space densities 3 orders of magnitude higher than obtained previously with laser-cooled molecules. In our trap, optical dark states are destabilized by rapidly and synchronously reversing the trapping laser polarizations and the applied magnetic field gradient. The number of molecules and trap lifetime are also significantly improved from previous work by loading the trap with high laser power and then reducing the power for long-term trapping. With this procedure, temperatures as low as 400  μK are achieved.

Quantitative determination of reserpine, ajmaline, and ajmalicine in Rauvolfia serpentina by reversed-phase high-performance liquid chromatography.

PubMed

Srivastava, A; Tripathi, A K; Pandey, R; Verma, R K; Gupta, M M

2006-10-01

A sensitive and reproducible reversed-phase high-performance liquid chromatography (HPLC) method using photodiode array detection is established for the simultaneous quantitation of important root alkaloids of Rauvolfia serpentina, namely, reserpine, ajmaline, and ajmalicine. A Chromolith Performance RP-18e column (100 x 4.6-mm i.d.) and a binary gradient mobile phase composed of 0.01 M (pH 3.5) phosphate buffer (NaH(2)PO(4)) containing 0.5% glacial acetic acid and acetonitrile are used. Analysis is run at a flow rate of 1.0 mL/min with the detector operated at a wavelength of 254 nm. The calibration curves are linear over a concentration range of 1-20 microg/mL (r = 1.000) for all the alkaloids. The various other aspects of analysis (i.e., peak purity, similarity, recovery, and repeatability) are also validated. For the three components, the recoveries are found to be 98.27%, 97.03%, and 98.38%, respectively. The limits of detection are 6, 4, and 8 microg/mL for ajmaline, ajmalicine, and reserpine, respectively, and the limits of quantitation are 19, 12, and 23 microg/mL for ajmaline, ajmalicine, and reserpine, respectively. The developed method is simple, reproducible, and easy to operate. It is useful for the evaluation of R. serpentina.

High performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry for V and Ni quantification as tetrapyrroles

NASA Astrophysics Data System (ADS)

Duyck, Christiane Béatrice; Saint'Pierre, Tatiana Dillenburg; Miekeley, Norbert; da Fonseca, Teresa Cristina Oliveira; Szatmari, Peter

2011-05-01

A method was developed for the determination of V and Ni as tetrapyrroles by High Performance Liquid Chromatography hyphenated to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) using reversed phase and elution gradient. Chlorinated solvents and tetrahydrofuran were investigated as regard to separation time and ICP-MS detection efficiencies. The final elution gradient program started from pure methanol to a mixture of 20:80 (v/v) chloroform:methanol. External quantification of V and Ni with inorganic standards by flow injection ICP-MS, used online with HPLC, resulted in 95% of recoveries. The Limits of Detection for V during methanol elution and for Ni during the 20% chloroform gradient elution were evaluated by their minimum detectable concentrations, which were, respectively, 5 μg L - 1 and 8 μg L - 1 . The methodology was applied to polar and resin fractions separated from a Brazilian crude oil and a sediment extract from an oil-polluted area in the Guanabara Bay, Rio de Janeiro, Brazil. Vanadium as tetrapyrroles represented the totality of V content in the polar fraction, whereas Ni was in different polar forms in the resin and sediment extract.

Evidence for retrovirus infections in green turtles Chelonia mydas from the Hawaiian islands

USGS Publications Warehouse

Casey, R.N.; Quackenbush, S.L.; Work, Thierry M.; Balazs, G.H.; Bowser, P.R.; Casey, J.W.

1997-01-01

Apparently normal Hawaiian green turtles Chelonia mydas and those displaying fibropapillomas were analyzed for infection by retroviruses. Strikingly, all samples were positive for polymerase enhanced reverse transcriptase (PERT) with levels high enough to quantitate by the conventional reverse transcriptase (RT) assay. However, samples of skin, even from asymptomatic turtles, were RT positive, although the levels of enzyme activity in healthy turtles hatched and raised in captivity were much lower than those observed in asymptomatic free-ranging turtles. Turtles with fibropapillomas displayed a broad range of reverse transcriptase activity. Skin and eye fibropapillomas and a heart tumor were further analyzed and shown to have reverse transcriptase activity that banded in a sucrose gradient at 1.17 g ml-1. The reverse transcriptase activity purified from the heart tumor displayed a temperature optimum of 37??C and showed a preference for Mn2+ over Mg2+. Sucrose gradient fractions of this sample displaying elevated reverse transcriptase activity contained primarily retrovitalsized particles with prominent envelope spikes, when negatively stained and examined by electron microscopy. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analysis of gradient-purified virions revealed a conserved profile among 4 independent tumors and showed 7 prominent proteins having molecular weights of 116, 83, 51, 43, 40, 20 and 14 kDa. The data suggest that retroviral infections are widespread in Hawaiian green turtles and a comprehensive investigation is warranted to address the possibility that these agents cause green turtle fibropapillomatosis (GTFP).

B1 transmit phase gradient coil for single-axis TRASE RF encoding.

PubMed

Deng, Qunli; King, Scott B; Volotovskyy, Vyacheslav; Tomanek, Boguslaw; Sharp, Jonathan C

2013-07-01

TRASE (Transmit Array Spatial Encoding) MRI uses RF transmit phase gradients instead of B0 field gradients for k-space traversal and high-resolution MR image formation. Transmit coil performance is a key determinant of TRASE image quality. The purpose of this work is to design an optimized RF transmit phase gradient array for spatial encoding in a transverse direction (x- or y- axis) for a 0.2T vertical B0 field MRI system, using a single transmitter channel. This requires the generation of two transmit B1 RF fields with uniform amplitude and positive and negative linear phase gradients respectively over the imaging volume. A two-element array consisting of a double Maxwell-type coil and a Helmholtz-type coil was designed using 3D field simulations. The phase gradient polarity is set by the relative phase of the RF signals driving the simultaneously energized elements. Field mapping and 1D TRASE imaging experiments confirmed that the constructed coil produced the fields and operated as designed. A substantially larger imaging volume relative to that obtainable from a non-optimized Maxwell-Helmholtz design was achieved. The Maxwell (sine)-Helmholtz (cosine) approach has proven successful for a horizontal phase gradient coil. A similar approach may be useful for other phase-gradient coil designs. Copyright © 2013 Elsevier Inc. All rights reserved.

Reversible mechanosensitive ion pumping as a part of mechanoelectrical transduction.

PubMed Central

Markin, V. S.; Tsong, T. Y.

1991-01-01

To explain the ability of some mechanosensitive cells to reverse the process of mechanotransduction and to generate mechanical oscillations and emit sound, a piezo-conformational coupling model (PCC model) is proposed. The model includes a transport protein which changes either its volume (PV-coupling) or its area in the membrane (gamma A-coupling) when undergoing conformational transitions. Such a protein can interact with an oscillating pressure to pump ions and create a transmembrane gradient if the affinities of the protein for ions are different at the two sides of membrane. The frequency and concentration windows for mechanical energy transduction were determined. Under optimal conditions, the efficiency of energy transduction can approach the theoretical maximum of 100%. If the concentration gradient exceeds the static head value (quasi-equilibrium which can be built up and maintained by this transport system), the energy transduction reverses and the transporter becomes a generator of mechanical oscillations at the expense of a concentration gradient. Estimation of thermodynamic parameters of the pump shows that the PV-coupling model would require large pressure oscillations to work while the gamma A-coupling model could work in physiological conditions. The gamma A-coupling mechanism may be used by cells for two purposes. In the reverse mode, it can be a force generator for various applications. In the direct mode, it may serve bioenergetic purposes by harvesting the energy of mechanical oscillations and storing it in the form of a concentration gradient. This pump has an unusual thermodynamic feature: it can distinguish the two components of the electrochemical potential gradient,i.e., the concentration gradient and the electrical potential, the latter serving as a permissive switch to open, or close, the pump when the potential reaches the threshold value.Predictions of the PCC model and its probable involvement in biological mechanotransduction are dicussed. PMID:1873468

Reverse phase HPLC method for detection and quantification of lupin seed γ-conglutin.

PubMed

Mane, Sharmilee; Bringans, Scott; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet

2017-09-15

A simple, selective and accurate reverse phase HPLC method was developed for detection and quantitation of γ-conglutin from lupin seed extract. A linear gradient of water and acetonitrile containing trifluoroacetic acid (TFA) on a reverse phase column (Agilent Zorbax 300SB C-18), with a flow rate of 0.8ml/min was able to produce a sharp and symmetric peak of γ-conglutin with a retention time at 29.16min. The identity of γ-conglutin in the peak was confirmed by mass spectrometry (MS/MS identification) and sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) analysis. The data obtained from MS/MS analysis was matched against the specified database to obtain the exact match for the protein of interest. The proposed method was validated in terms of specificity, linearity, sensitivity, precision, recovery and accuracy. The analytical parameters revealed that the validated method was capable of selectively performing a good chromatographic separation of γ-conglutin from the lupin seed extract with no interference of the matrix. The detection and quantitation limit of γ-conglutin were found to be 2.68μg/ml and 8.12μg/ml respectively. The accuracy (precision and recovery) analysis of the method was conducted under repeatable conditions on different days. Intra-day and inter-day precision values less than 0.5% and recovery greater than 97% indicated high precision and accuracy of the method for analysis of γ-conglutin. The method validation findings were reproducible and can be successfully applied for routine analysis of γ-conglutin from lupin seed extract. Copyright © 2017 Elsevier B.V. All rights reserved.

Trail-following behavior ofReticulitermes hesperus Banks (Isoptera: Rhinotermitidae).

PubMed

Grace, J K; Wood, D L; Frankie, G W

1988-02-01

The behavior ofReticulitermes hesperus Banks pseudergates (workers) was assessed on artificial trails containing different concentrations of sternal gland extract. On nongiadient trails, more pseudergates were recruited to trails of greater pheromone concentration, they traveled a greater distance without pausing, and their rate of locomotion increased over that observed on trails of lesser concentration (positive orthokinesis). Of the individuals pausing before completing trails of high concentration, fewer left the trails or reversed direction (negative klinokinesis) than on trails of lower concentration. Termites walking down concentration gradients failed to complete these trails to the low-concentration termini. At a point representing an average decrease of slightly more than 10-fold in the original concentration of pheromone, individuals reversed their direction of travel and returned to the high-concentration terminus. Termites walking up pheromone gradients proceeded to the high-concentration termini without reversing direction.R. hesperus pseudergates are thus able to orient along a gradient of trail pheromone by longitudinal klinotaxis.

Microturbulence studies of pulsed poloidal current drive discharges in the reversed field pinch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carmody, D., E-mail: dcarmody@wisc.edu; Pueschel, M. J.; Anderson, J. K.

2015-01-15

Experimental discharges with pulsed poloidal current drive (PPCD) in the Madison Symmetric Torus reversed field pinch are investigated using a semi-analytic equilibrium model in the gyrokinetic turbulence code GENE. PPCD cases, with plasma currents of 500 kA and 200 kA, exhibit a density-gradient-driven trapped electron mode (TEM) and an ion temperature gradient mode, respectively. Relative to expectations of tokamak core plasmas, the critical gradients for the onset of these instabilities are found to be greater by roughly a factor of the aspect ratio. A significant upshift in the nonlinear TEM transport threshold, previously found for tokamaks, is confirmed in nonlinear reversed fieldmore » pinch simulations and is roughly three times the threshold for linear instability. The simulated heat fluxes can be brought in agreement with measured diffusivities by introducing a small, resonant magnetic perturbation, thus modeling the residual fluctuations from tearing modes. These fluctuations significantly enhance transport.« less

Linear solvation energy relationships in normal phase chromatography based on gradient separations.

PubMed

Wu, Di; Lucy, Charles A

2017-09-22

Coupling the modified Soczewiñski model and one gradient run, a gradient method was developed to build a linear solvation energy relationship (LSER) for normal phase chromatography. The gradient method was tested on dinitroanilinopropyl (DNAP) and silica columns with hexane/dichloromethane (DCM) mobile phases. LSER models built based on the gradient separation agree with those derived from a series of isocratic separations. Both models have similar LSER coefficients and comparable goodness of fit, but the LSER model based on gradient separation required fewer trial and error experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

Measurement by reversed-phase high-performance liquid chromatography of malondialdehyde in normal human urine following derivatisation with 2,4-dinitrophenylhydrazine.

PubMed

Korchazhkina, Olga; Exley, Christopher; Andrew Spencer, Stephen

2003-09-05

A selective and sensitive method based on derivatisation with 2,4-dinitrophenylhydrazine (DNPH) and consecutive HPLC gradient separation is described for the determination of malondialdehyde (MDA) in urine. Preparation of urine samples involved a one-step derivatisation/extraction procedure. Separation was achieved using a Waters SymmetryC(18) column (3.9 x 150 mm) and linear gradient of acetonitrile in water (from 30% to 70% in 30 min). The overall detection limit of the method was 56 nM of MDA in urine. The recovery of MDA was 94.3+/-8.6%. MDA in urine of healthy volunteers, measured using the method of standard additions, was 0.019+/-0.012 microM/mmol creatinine. MDA in the same samples measured using the 2-thiobarbituric acid (TBA) assay was 0.181+/-0.063 microM/mmol creatinine. We demonstrate that the commonly used TBA assay in conjunction with HPLC may overestimate the MDA concentration in human urine by almost 10-fold.

First results of a study on turbulent boundary layers in oscillating flow with a mean adverse pressure gradient

NASA Technical Reports Server (NTRS)

Houdeville, R.; Cousteix, J.

1979-01-01

The development of a turbulent unsteady boundary layer with a mean pressure gradient strong enough to induce separation, in order to complete the extend results obtained for the flat plate configuration is presented. The longitudinal component of the velocity is measured using constant temperature hot wire anemometer. The region where negative velocities exist is investigated with a laser Doppler velocimeter system with BRAGG cells. The boundary layer responds by forced pulsation to the perturbation of potential flow. The unsteady effects observed are very important. The average location of the zero skin friction point moves periodically at the perturbation frequency. Average velocity profiles from different instants in the cycle are compared. The existence of a logarithmic region enables a simple calculation of the maximum phase shift of the velocity in the boundary layer. An attempt of calculation by an integral method of boundary layer development is presented, up to the point where reverse flow starts appearing.

Bioinspired Fabrication of one dimensional graphene fiber with collection of droplets application.

PubMed

Song, Yun-Yun; Liu, Yan; Jiang, Hao-Bo; Li, Shu-Yi; Kaya, Cigdem; Stegmaier, Thomas; Han, Zhi-Wu; Ren, Lu-Quan

2017-09-21

We designed a kind of smart bioinspired fiber with multi-gradient and multi-scale spindle knots by combining polydimethylsiloxane (PDMS) and graphene oxide (GO). Multilayered graphene structures can produce obvious wettability change after laser etching due to increased roughness. We demonstrate that the cooperation between curvature and the controllable wettability play an important role in water gathering, which regulate effectively the motion of tiny water droplets. In addition, due to the effective cooperation of multi-gradient and multi-scale hydrophilic spindle knots, the length of the three-phase contact line (TCL) can be longer, which makes a great contribution to the improvement of collecting efficiency and water-hanging ability. This study offers a novel insight into the design of smart materials that may control the transport of tiny drops reversibly in directions, which could potentially be extended to the realms of in microfluidics, fog harvesting filtration and condensers designs, and further increase water collection efficiency and hanging ability.

Development of a method for the analysis of nucleotides from the mantle tissue of the mussel Mytilus galloprovincialis.

PubMed

Blanco López, S L; Moal, J; San Juan Serrano, F

2000-09-01

Reversed-phase HPLC was applied to obtain a sensitive and efficient means for quantitating nucleotides in the mussel Mytilus galloprovincialis. We obtained a good separation of adenylic, guanylic, uridylic and cytidylic nucleotides. Adenine nucleotides play a critical role in the regulation and integration of cellular metabolism; particularly in the mantle tissue in the mussel, they are involved in the regulation of the enzyme glycogen phosphorylase, a key enzyme in the transfer of bioenergetic reserves (glycogen) to gametogenic development; it is of great importance to have a measure of the concentrations in vivo during the reproductive cycle of the organism. Different elution conditions were tested: isocratic versus step gradient elution, different mobile phase pH and the type and proportion of ion-pairing agent added to the mobile phase. The best method was selected and the separation and accurate determination of adenine, citidine, guanine and uridine nucleotides was accomplished within a 20-min run, with UV-Vis detection (254 nm).

[Study on the analytical methods of catechins in tea and green tea polyphenol samples by high performance liquid chromatography].

PubMed

Dai, J; Wang, H X; Chen, S W; Tang, J

2001-09-01

Hypersil BDS C18 and Zorbax SB C18, suitable to separate simultaneously seven kinds of catechins and caffeine, were screened out from seven brands of reversed-phase columns. Mobile phase was a solution of methanol-water-acetic acid (or trifluoro acetic acid). Seven kinds of catechins in tea samples from six places in China and three green tea polyphenol(GTP) samples from different producers were separated and determined in 30 min by isocratic and gradient elutions. The effects of mobile phase components and temperature of column on retention parameters of catechins and caffeine are reviewed. Chromatographic conditions and pretreatment methods of samples were optimized. Gallocatechin gallate(GCG) and (-)-catechin gallate(CG) were identified by electrospray ionization mass spectrometry(ESI-MS) and prepared by high performance liquid chromatography for quantitative analysis. The other catechins, (-)-epigallocatechin (EGC), (+)-catechin (D-C), (-)-epicatechin(EC), (-)-epigallocatechin gallate(EGCG), (-)-epicatechin gallate(ECG) were identified with standards.

Water-compatible molecularly imprinted polymers for efficient direct injection on-line solid-phase extraction of ropivacaine and bupivacaine from human plasma.

PubMed

Cobb, Zoe; Sellergren, Börje; Andersson, Lars I

2007-12-01

Two novel molecularly imprinted polymers (MIPs) selected from a combinatorial library of bupivacaine imprinted polymers were used for selective on-line solid-phase extraction of bupivacaine and ropivacaine from human plasma. The MIPs were prepared using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linking monomer and in addition hydroxyethylmethacrylate to render the polymer surface hydrophilic. The novel MIPs showed high selectivity for the analytes and required fewer and lower concentrations of additives to suppress non-specific adsorption compared with a conventional MIP. This enabled the development of an on-line system for direct extraction of buffered plasma. Selective extraction was achieved without the use of time-consuming solvent switch steps, and transfer of the analytes from the MIP column to the analytical column was carried out under aqueous conditions fully compatible with reversed-phase LC gradient separation of analyte and internal standard. The MIPs showed excellent aqueous compatibility and yielded extractions with acceptable recovery and high selectivity.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Determination of imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole in fruits and vegetables by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

PubMed

Pous, X; Ruíz, M J; Picó, Y; Font, G

2001-09-01

Imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole have been simultaneously determined in strawberries, oranges, potatoes, pears, and melons by matrix solid-phase dispersion (MSPD) followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) in positive-ion mode. The samples were homogenized with C8 bonded silica as MSPD sorbent, placed in a glass column, and eluted with dichloromethane. Chromatographic separation of the compounds was achieved on a reversed-phase LC column using a methanol-ammonium formate (50 mmol L(-1)) gradient as a mobile phase. Samples were screened by monitoring the protonated molecular ion at m/z 256 for imidacloprid, 280 for metalaxyl, 289 for myclobutanil, and 202 for thiabendazole, and the main fragment at m/z 138 for propham. Positive samples were confirmed by multiple-ion monitoring. The repeatability (<20%) and recovery (>57%) of the method were good, and limits of detection (<0.05 mg kg(-1)) were adequate.

Supplemental optical specifications for imaging systems: parameters of phase gradient

NASA Astrophysics Data System (ADS)

Xuan, Bin; Li, Jun-Feng; Wang, Peng; Chen, Xiao-Ping; Song, Shu-Mei; Xie, Jing-Jiang

2009-12-01

Specifications of phase error, peak to valley (PV), and root mean square (rms) are not able to represent the properties of a wavefront reasonably because of their irresponsibility for spatial frequencies. Power spectral density is a parameter that is especially effective to indicate the frequency regime. However, it seems not convenient for opticians to implement. Parameters of phase gradient, PV gradient, and rms gradient are most correlated with a point-spread function of an imaging system, and they can provide clear instruction of manufacture. The algorithms of gradient parameters have been modified in order to represent the image quality better. In order to demonstrate the analyses, an experimental spherical mirror has been worked out. It is clear that imaging performances can be maintained while manufacture difficulties are decreased when a reasonable trade-off between specifications of phase error and phase gradient is made.

Quality by design approach for the separation of naproxcinod and its related substances by fused core particle technology column.

PubMed

Inugala, Ugandar Reddy; Pothuraju, Nageswara Rao; Vangala, Ranga Reddy

2013-01-01

This paper describes the development of a rapid, novel, stability-indicating gradient reversed-phase high-performance liquid chromatographic method and associated system suitability parameters for the analysis of naproxcinod in the presence of its related substances and degradents using a quality-by-design approach. All of the factors that affect the separation of naproxcinod and its impurities and their mutual interactions were investigated and robustness of the method was ensured. The method was developed using an Ascentis Express C8 150 × 4.6 mm, 2.7 µm column with a mobile phase containing a gradient mixture of two solvents. The eluted compounds were monitored at 230 nm, the run time was 20 min within which naproxcinod and its eight impurities were satisfactorily separated. Naproxcinod was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Naproxcinod was found to degrade significantly in acidic and basic conditions and to be stable in thermal, photolytic, oxidative and aqueous degradation conditions. The degradation products were satisfactorily resolved from the primary peak and its impurities, proving the stability-indicating power of the method. The developed method was validated as per International Conference on Harmonization guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness.

Stability-indicating UPLC method for determination of Valsartan and their degradation products in active pharmaceutical ingredient and pharmaceutical dosage forms.

PubMed

Krishnaiah, Ch; Reddy, A Raghupathi; Kumar, Ramesh; Mukkanti, K

2010-11-02

A simple, precise, accurate stability-indicating gradient reverse phase ultra-performance liquid chromatographic (RP-UPLC) method was developed for the quantitative determination of purity of Valsartan drug substance and drug products in bulk samples and pharmaceutical dosage forms in the presence of its impurities and degradation products. The method was developed using Waters Aquity BEH C18 (100 mm x 2.1 mm, 1.7 microm) column with mobile phase containing a gradient mixture of solvents A and B. The eluted compounds were monitored at 225 nm, the run time was within 9.5 min, which Valsartan and its seven impurities were well separated. Valsartan was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Valsartan was found to degrade significantly in acid and oxidative stress conditions and stable in base, hydrolytic and photolytic degradation conditions. The degradation products were well resolved from main peak and its impurities, proving the stability-indicating power of the method. The developed method was validated as per international conference on harmonization (ICH) guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. This method was also suitable for the assay determination of Valsartan in pharmaceutical dosage forms.

Pulmonary function in microgravity

NASA Technical Reports Server (NTRS)

Guy, H. J.; Prisk, G. K.; West, J. B.

1992-01-01

We report the successful collection of a large quantity of human resting pulmonary function data on the SLS-1 mission. Preliminary analysis suggests that cardiac stroke volumes are high on orbit, and that an adaptive reduction takes at least several days, and in fact may still be in progress after 9 days on orbit. It also suggests that pulmonary capillary blood volumes are high, and remain high on orbit, but that the pulmonary interstitium is not significantly impacted. The data further suggest that the known large gravitational gradients of lung function have only a modest influence on single breath tests such as the SBN washout. They account for only approximately 25% of the phase III slope of nitrogen, on vital capacity SBN washouts. These gradients are only a moderate source of the cardiogenic oscillations seen in argon (bolus gas) and nitrogen (resident gas), on such tests. They may have a greater role in generating the normal CO2 oscillations, as here the phase relationship to argon and nitrogen reverses in microgravity, at least at mid exhalation in those subjects studied to date. Microgravity may become a useful tool in establishing the nature of the non-gravitational mechanisms that can now be seen to play such a large part in the generation of intra-breath gradients and oscillations of expired gas concentration. Analysis of microgravity multibreath nitrogen washouts, single breath washouts from more physiological pre-inspiratory volumes, both using our existing SLS-1 data, and data from the upcoming D-2 and SLS-2 missions, should be very fruitful in this regard.(ABSTRACT TRUNCATED AT 250 WORDS).

Single-laboratory validation of a high-performance liquid chromatographic-diode array detector-fluorescence detector/mass spectrometric method for simultaneous determination of water-soluble vitamins in multivitamin dietary tablets.

PubMed

Chen, Pei; Atkinson, Renata; Wolf, Wayne R

2009-01-01

The purpose of this study was to develop a single-laboratory validated (SLV) method using high-performance liquid chromatography with different detectors [diode array detector (DAD); fluorescence detector (FLD); and mass spectrometry (MS)] for determination of 7 B-complex vitamins (B1-thiamin, B2-riboflavin, B3-nicotinamide, B6-pyridoxine, B9-folic acid, pantothenic acid, and biotin) and vitamin C in multivitamin/multimineral dietary supplements. The method involves the use of a reversed-phase octadecylsilyl column (4 microm, 250 x 2.0 mm id) and a gradient mobile phase profile. Gradient elution was performed at a flow rate of 0.25 mL/min. After a 5 min isocratic elution at 100% A (0.1% formic acid in water), a linear gradient to 50% A and 50% B (0.1% formic acid in acetonitrile) at 15 min was employed. Detection was performed with a DAD as well as either an FLD or a triple-quadrupole MS detector in the multiple reaction monitoring mode. SLV was performed using Standard Reference Material (SRM) 3280 Multivitamin/Multimineral Tablets, being developed by the National Institute of Standards and Technology, with support by the Office of Dietary Supplements of the National Institutes of Health. Phosphate buffer (10 mM, pH 2.0) extracts of the NIST SRM 3280 were analyzed by the liquid chromatographic (LC)-DAD-FLDIMS method. Following extraction, the method does not require any sample cleanup/preconcentration steps except centrifugation and filtration.

Single-Laboratory Validation of a High-Performance Liquid Chromatographic-Diode Array Detector-Fluorescence Detector/Mass Spectrometric Method for Simultaneous Determination of Water-Soluble Vitamins in Multivitamin Dietary Tablets

PubMed Central

Chen, Pei; Atkinson, Renata; Wolf, Wayne R.

2014-01-01

The purpose of this study was to develop a single-laboratory validated (SLV) method using high-performance liquid chromatography with different detectors [diode array detector (DAD); fluorescence detector (FLD); and mass spectrometry (MS)] for determination of 7 B-complex vitamins (B1-thiamin, B2-riboflavin, B3-nicotinamide, B6-pyridoxine, B9-folic acid, pantothenic acid, and biotin) and vitamin C in multivitamin/multimineral dietary supplements. The method involves the use of a reversed-phase octadecylsilyl column (4 µm, 250 × 2.0 mm id) and a gradient mobile phase profile. Gradient elution was performed at a flow rate of 0.25 mL/min. After a 5 min isocratic elution at 100% A (0.1% formic acid in water), a linear gradient to 50% A and 50% B (0.1% formic acid in acetonitrile) at 15 min was employed. Detection was performed with a DAD as well as either an FLD or a triple-quadrupole MS detector in the multiple reaction monitoring mode. SLV was performed using Standard Reference Material (SRM) 3280 Multivitamin/Multimineral Tablets, being developed by the National Institute of Standards and Technology, with support by the Office of Dietary Supplements of the National Institutes of Health. Phosphate buffer (10 mM, pH 2.0) extracts of the NIST SRM 3280 were analyzed by the liquid chromatographic (LC)-DAD-FLD/MS method. Following extraction, the method does not require any sample cleanup/preconcentration steps except centrifugation and filtration. PMID:19485230

Rapid-gradient HPLC method for measuring drug interactions with immobilized artificial membrane: comparison with other lipophilicity measures.

PubMed

Valko, K; Du, C M; Bevan, C D; Reynolds, D P; Abraham, M H

2000-08-01

A fast-gradient high-performance liquid chromatographic (HPLC) method has been suggested to characterize the interactions of drugs with an immobilized artificial membrane (IAM). With a set of standards, the gradient retention times can be converted to Chromatographic Hydrophobicity Index values referring to IAM chromatography (CHI(IAM)) that approximates an acetonitrile concentration with which the equal distribution of compound can be achieved between the mobile phase and IAM. The CHI(IAM) values are more suitable for interlaboratory comparison and for high throughput screening of new molecular entities than the log k(IAM) values (isocratic retention factor on IAM). The fast-gradient method has been validated against the isocratic log k(IAM) values using the linear free energy relationship solvation equations based on the data from 48 compounds. The compound set was selected to provide a wide range and the least cross-correlation between the molecular descriptors in the solvation equation: (2) where SP is a solute property (e.g., logarithm of partition coefficients, reversed-phase (RP)-HPLC retention parameters, such as log k, log k(w), etc.) and the explanatory variables are solute descriptors as follows: R(2) is an excess molar refraction that can be obtained from the measured refractive index of a compound, pi(2)(H) is the solute dipolarity/polarizability, summation operatoralpha(2)(H) and summation operatorbeta(2)(0) are the solute overall or effective hydrogen-bond acidity and basicity, respectively, and V(x) is the McGowan characteristic volume (in cm(3)/100 mol) that can be calculated for any solute simply from molecular structure using a table of atomic constants. It was found that the relative constants of the solvation equation were very similar for the CHI(IAM) and for the log k(IAM). The IAM lipophilicity scale was quite similar to the octanol/water lipophilicity scale for neutral compounds. The effect of charge on the interaction with IAM was studied by varying the mobile phase pH. Copyright 2000 Wiley-Liss, Inc.

A Novel HPLC Method for the Concurrent Analysis and Quantitation of Seven Water-Soluble Vitamins in Biological Fluids (Plasma and Urine): A Validation Study and Application

PubMed Central

Grotzkyj Giorgi, Margherita; Howland, Kevin; Martin, Colin; Bonner, Adrian B.

2012-01-01

An HPLC method was developed and validated for the concurrent detection and quantitation of seven water-soluble vitamins (C, B1, B2, B5, B6, B9, B12) in biological matrices (plasma and urine). Separation was achieved at 30°C on a reversed-phase C18-A column using combined isocratic and linear gradient elution with a mobile phase consisting of 0.01% TFA aqueous and 100% methanol. Total run time was 35 minutes. Detection was performed with diode array set at 280 nm. Each vitamin was quantitatively determined at its maximum wavelength. Spectral comparison was used for peak identification in real samples (24 plasma and urine samples from abstinent alcohol-dependent males). Interday and intraday precision were <4% and <7%, respectively, for all vitamins. Recovery percentages ranged from 93% to 100%. PMID:22536136

A novel HPLC method for the concurrent analysis and quantitation of seven water-soluble vitamins in biological fluids (plasma and urine): a validation study and application.

PubMed

Giorgi, Margherita Grotzkyj; Howland, Kevin; Martin, Colin; Bonner, Adrian B

2012-01-01

An HPLC method was developed and validated for the concurrent detection and quantitation of seven water-soluble vitamins (C, B(1), B(2), B(5), B(6), B(9), B(12)) in biological matrices (plasma and urine). Separation was achieved at 30°C on a reversed-phase C18-A column using combined isocratic and linear gradient elution with a mobile phase consisting of 0.01% TFA aqueous and 100% methanol. Total run time was 35 minutes. Detection was performed with diode array set at 280 nm. Each vitamin was quantitatively determined at its maximum wavelength. Spectral comparison was used for peak identification in real samples (24 plasma and urine samples from abstinent alcohol-dependent males). Interday and intraday precision were <4% and <7%, respectively, for all vitamins. Recovery percentages ranged from 93% to 100%.

Distortion correction of echo-planar diffusion-weighted images of uterine cervix.

PubMed

deSouza, Nandita M; Orton, Matthew; Downey, Kate; Morgan, Veronica A; Collins, David J; Giles, Sharon L; Payne, Geoffrey S

2016-05-01

To investigate the clinical utility of the reverse gradient algorithm in correcting distortions in diffusion-weighted images of the cervix and for increasing diagnostic performance. Forty-one patients ages 25-72 years (mean 40 ± 11 years) with suspected or early stage cervical cancer were imaged at 3T using an endovaginal coil. T2 -weighted (W) and diffusion-weighted images with right and left phase-encode gradient directions were obtained coronal to the cervix (b = 0, 100, 300, 500, 800 s mm(-2) ). Differences in angle of the endocervical canal to the x-axis between T2 W and right-gradient, left-gradient, and corrected images were measured. Uncorrected and corrected images were assessed for diagnostic performance when viewed together with T2 W images by two independent observers against subsequent histology. The angles of the endocervical canal relative to the x-axis were significantly different between the T2 W images and the right-gradient images (P = 0.007), approached significance for left-gradient images (P = 0.055), and were not significantly different after correction (P = 0.95). Corrected images enabled a definitive diagnosis in 34% (n = 14) of patients classified as equivocal on uncorrected images. Tumor volume in this subset was 0.18 ± 0.44 cm(3) (mean ± SD; sensitivity of detection 100% [8/8], specificity 50% [3/6] for an experienced observer). Correction did not improve diagnostic performance for the less-experienced observer. Distortion-corrected diffusion-weighted images improved correspondence with T2 W images and diagnostic performance in a third of cases. © 2015 The Authors Journal of Magnetic Resonance Imaging published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

Electron heating in quasi-perpendicular shocks - A Monte Carlo simulation

NASA Technical Reports Server (NTRS)

Veltri, Pierluigi; Mangeney, Andre; Scudder, Jack D.

1990-01-01

To study the problem of electron heating in quasi-perpendicular shocks, under the combined effects of 'reversible' motion, in the shock electric potential and magnetic field, and wave-particle interactions a diffusion equation was derived, in the drift (adiabatic) approximation and it was solved by using a Monte Carlo method. The results show that most of the observations can be explained within this framework. The simulation has also definitively shown that the electron parallel temperature is determined by the dc electromagnetic field and not by any wave particle induced heating. Wave-particle interactions are effective in smoothing out the large gradients in phase space produced by the 'reversible' motion of the electrons, thus producing a 'cooling' of the electrons. Some constraints on the wave-particle interaction process may be obtained from a detailed comparison between the simulation and observations. In particular, it appears that the adiabatic approximation must be violated in order to explain the observed evolution of the perpendicular temperature.

[Influences of ion-suppressors on retention behaviors of nine food additives in reversed-phase high performance liquid chromatographic separation].

PubMed

Zhao, Yonggang; Chen, Xiaohong; Li, Xiaoping; Yao, Shanshan; Jin, Micong

2011-10-01

The influences of ion-suppressors on retention behaviors of nine food additives, i.e., acesulfame, saccharin, caffeine, aspartame, benzoic acid, sorbic acid, stevioside, dehydroacetic acid and neotame in reversed-phase high performance liquid chromatographic (RP-HPLC) separation were investigated. The organic modification effects of acids, i. e. , trifluoroacetic acid (TFA) and buffer salts, i. e. , TFA-ammonium acetate (AmAc) were studied emphatically. The relationships between retention factors of solutes and volume percentages of ion-suppressors in the mobile phase systems of acetonitrile-TFA aqueous solution and acetonitrile-TFA-AmAc aqueous solution were quantitatively established, separately. The separation of nine food additives was completed by a gradient elution with acetonitrile-TFA (0.01%, v/v)-AmAc (2. 5 mmol/L) aqueous solution as the mobile phases. An RP-HPLC method was established for the simultaneous determination of nine food additives in red wine. In the range of 10. 0 - 100. 0 mg/L, nine food additives showed good linearity with the correlation coefficients ( r2 ) larger than 0. 999 1. The limits of detection (LODs) were in the range of 0. 33 - 2. 36 mg/L and the limits of quantification (LOQs) were in the range of 1. 11 - 7. 80 mg/L. The spiked recoveries were between 87. 61% and 108. 4% with the relative standard deviations (RSDs) of 2. 2% -9. 4%. These results are of referential significance for the rapid establishment and accu- rate optimization of RP-HPLC separation for the simultaneous determination of food additives in other foods.

Analysis of nine food additives in red wine by ion-suppression reversed-phase high-performance liquid chromatography using trifluoroacetic acid and ammonium acetate as ion-suppressors.

PubMed

Zhao, Yong-Gang; Chen, Xiao-Hong; Yao, Shan-Shan; Pan, Sheng-Dong; Li, Xiao-Ping; Jin, Mi-Cong

2012-01-01

A reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed for the simultaneous determination of nine food additives, i.e., acesulfame, saccharin, caffeine, aspartame, benzoic acid, sorbic acid, stevioside, dehydroacetic acid and neotame in red wine. The effects of ion-suppressors, i.e., trifluoroacetic acid (TFA) and ammonium acetate (AmAc) on retention behavior of nine food additives in RP-HPLC separation were discussed in detail. The relationships between retention factors of solutes and volume percent of ion-suppressors in the mobile-phase systems of acetonitrile-TFA aqueous solution and acetonitrile-TFA-AmAc aqueous solution were quantitatively established, respectively. The results showed that the ion suppressors had not only an ion suppression effect, but also an organic modification effect on the acidic analytes. The baseline separation of nine food additives was completed by a gradient elution with acetonitrile-TFA(0.01%, v/v)-AmAc(2.5 mmol L(-1)) aqueous solution as the mobile phase. The recoveries were between 80.2 - 99.5% for all analytes with RSDs in the range of 1.5 - 8.9%. The linearities were in the range of 0.2 - 100.0 mg L(-1) with determination coefficients (r(2)) higher than 0.9991 for all analytes. The limits of quantification (LOQs) were between 0.53 - 0.99 mg L(-1). The applicability of the proposed method to detect and quantify food additives has been demonstrated in the analysis of 30 real samples.

Annular beam with segmented phase gradients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Shubo; Wu, Liang; Tao, Shaohua, E-mail: eshtao@csu.edu.cn

2016-08-15

An annular beam with a single uniform-intensity ring and multiple segments of phase gradients is proposed in this paper. Different from the conventional superposed vortices, such as the modulated optical vortices and the collinear superposition of multiple orbital angular momentum modes, the designed annular beam has a doughnut intensity distribution whose radius is independent of the phase distribution of the beam in the imaging plane. The phase distribution along the circumference of the doughnut beam can be segmented with different phase gradients. Similar to a vortex beam, the annular beam can also exert torques and rotate a trapped particle owingmore » to the orbital angular momentum of the beam. As the beam possesses different phase gradients, the rotation velocity of the trapped particle can be varied along the circumference. The simulation and experimental results show that an annular beam with three segments of different phase gradients can rotate particles with controlled velocities. The beam has potential applications in optical trapping and optical information processing.« less

Gradient design for liquid chromatography using multi-scale optimization.

PubMed

López-Ureña, S; Torres-Lapasió, J R; Donat, R; García-Alvarez-Coque, M C

2018-01-26

In reversed phase-liquid chromatography, the usual solution to the "general elution problem" is the application of gradient elution with programmed changes of organic solvent (or other properties). A correct quantification of chromatographic peaks in liquid chromatography requires well resolved signals in a proper analysis time. When the complexity of the sample is high, the gradient program should be accommodated to the local resolution needs of each analyte. This makes the optimization of such situations rather troublesome, since enhancing the resolution for a given analyte may imply a collateral worsening of the resolution of other analytes. The aim of this work is to design multi-linear gradients that maximize the resolution, while fulfilling some restrictions: all peaks should be eluted before a given maximal time, the gradient should be flat or increasing, and sudden changes close to eluting peaks are penalized. Consequently, an equilibrated baseline resolution for all compounds is sought. This goal is achieved by splitting the optimization problem in a multi-scale framework. In each scale κ, an optimization problem is solved with N κ  ≈ 2 κ variables that are used to build the gradients. The N κ variables define cubic splines written in terms of a B-spline basis. This allows expressing gradients as polygonals of M points approximating the splines. The cubic splines are built using subdivision schemes, a technique of fast generation of smooth curves, compatible with the multi-scale framework. Owing to the nature of the problem and the presence of multiple local maxima, the algorithm used in the optimization problem of each scale κ should be "global", such as the pattern-search algorithm. The multi-scale optimization approach is successfully applied to find the best multi-linear gradient for resolving a mixture of amino acid derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of Temperature Gradient in Advanced Automated Directional Solidification Furnace (AADSF) by Numerical Simulation

NASA Technical Reports Server (NTRS)

Bune, Andris V.; Gillies, Donald C.; Lehoczky, Sandor L.

1996-01-01

A numerical model of heat transfer using combined conduction, radiation and convection in AADSF was used to evaluate temperature gradients in the vicinity of the crystal/melt interface for variety of hot and cold zone set point temperatures specifically for the growth of mercury cadmium telluride (MCT). Reverse usage of hot and cold zones was simulated to aid the choice of proper orientation of crystal/melt interface regarding residual acceleration vector without actual change of furnace location on board the orbiter. It appears that an additional booster heater will be extremely helpful to ensure desired temperature gradient when hot and cold zones are reversed. Further efforts are required to investigate advantages/disadvantages of symmetrical furnace design (i.e. with similar length of hot and cold zones).

Stabilization of lower hybrid drift modes by finite parallel wavenumber and electron temperature gradients in field-reversed configurations

NASA Astrophysics Data System (ADS)

Farengo, R.; Guzdar, P. N.; Lee, Y. C.

1989-08-01

The effect of finite parallel wavenumber and electron temperature gradients on the lower hybrid drift instability is studied in the parameter regime corresponding to the TRX-2 device [Fusion Technol. 9, 48 (1986)]. Perturbations in the electrostatic potential and all three components of the vector potential are considered and finite beta electron orbit modifications are included. The electron temperature gradient decreases the growth rate of the instability but, for kz=0, unstable modes exist for ηe(=T'en0/Ten0)>6. Since finite kz effects completely stabilize the mode at small values of kz/ky(≂5×10-3), magnetic shear could be responsible for stabilizing the lower hybrid drift instability in field-reversed configurations.

LAZY Genes Mediate the Effects of Gravity on Auxin Gradients and Plant Architecture1[OPEN

PubMed Central

2017-01-01

A rice (Oryza sativa) mutant led to the discovery of a plant-specific LAZY1 protein that controls the orientation of shoots. Arabidopsis (Arabidopsis thaliana) possesses six LAZY genes having spatially distinct expression patterns. Branch angle phenotypes previously associated with single LAZY genes were here studied in roots and shoots of single and higher-order atlazy mutants. The results identify the major contributors to root and shoot branch angles and gravitropic behavior of seedling hypocotyls and primary roots. AtLAZY1 is the principal determinant of inflorescence branch angle. The weeping inflorescence phenotype of atlazy1,2,4 mutants may be due at least in part to a reversal in the gravitropism mechanism. AtLAZY2 and AtLAZY4 determined lateral root branch angle. Lateral roots of the atlazy2,4 double mutant emerged slightly upward, approximately 10° greater than perpendicular to the primary root axis, and they were agravitropic. Etiolated hypocotyls of the quadruple atlazy1,2,3,4 mutant were essentially agravitropic, but their phototropic response was robust. In light-grown seedlings, the root of the atlazy2,3,4 mutant was also agravitropic but when adapted to dim red light it displayed a reversed gravitropic response. A reversed auxin gradient across the root visualized by a fluorescent signaling reporter explained the reversed, upward bending response. We propose that AtLAZY proteins control plant architecture by coupling gravity sensing to the formation of auxin gradients that override a LAZY-independent mechanism that creates an opposing gravity-induced auxin gradient. PMID:28821594

Simple method for RF pulse measurement using gradient reversal.

PubMed

Landes, Vanessa L; Nayak, Krishna S

2018-05-01

To develop and evaluate a simple method for measuring the envelope of small-tip radiofrequency (RF) excitation waveforms in MRI, without extra hardware or synchronization. Gradient reversal approach to evaluate RF (GRATER) involves RF excitation with a constant gradient and reversal of that gradient during signal reception to acquire the time-reversed version of an RF envelope. An outer-volume suppression prepulse is used optionally to preselect a uniform volume. GRATER was evaluated in phantom and in vivo experiments. It was compared with the programmed waveform and the traditional pick-up coil method. In uniform phantom experiments, pick-up coil, GRATER, and outer-volume suppression + GRATER matched the programmed waveforms to less than 2.1%, less than 6.1%, and less than 2.4% normalized root mean square error, respectively, for real RF pulses with flip angle less than or equal to 30°, time-bandwidth product 2 to 8, and two to five excitation bands. For flip angles greater than 30°, GRATER measurement error increased as predicted by Bloch simulation. Fat-water phantom and in vivo experiments with outer-volume suppression + GRATER demonstrated less than 6.4% normalized root mean square error. The GRATER sequence measures small-tip RF envelopes without extra hardware or synchronization in just over two times the RF duration. The sequence may be useful in prescan calibration and for measurement and precompensation of RF amplifier nonlinearity. Magn Reson Med 79:2642-2651, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

A reversed-phase high-performance liquid chromatography method for bovine serum albumin assay in pharmaceutical dosage forms and protein/antigen delivery systems.

PubMed

Hamidi, Mehrdad; Zarei, Najmeh

2009-05-01

Bovine serum albumin (BSA) is among the most widely used proteins in protein formulations as well as in the development of novel delivery systems as a typical model for therapeutic/diagnostic proteins and the new versions of vaccines. The development of reliable and easily available assay methods for quantitation of this protein would therefore play a crucial role in these types of studies. A simple gradient reversed-phase high-performance liquid chromatography with ultra-violet detection (HPLC-UV) method has been developed for quantitation of BSA in dosage forms and protein delivery systems. The method produced linear responses throughout the wide BSA concentration range of 1 to 100 micro g/mL. The average within-run and between-run variations of the method within the linear concentration range of BSA were 2.46% and 2.20%, respectively, with accuracies of 104.49% and 104.58% for within-run and between-run samples, respectively. The limits of detection (LOD) and quantitation (LOQ) of the method were 0.5 and 1 microg/mL, respectively. The method showed acceptable system suitability indices, which enabled us to use it successfully during our particulate vaccine delivery research project. Copyright 2009 John Wiley & Sons, Ltd.

Determination of theanine, GABA, and other amino acids in green, oolong, black, and Pu-erh teas with dabsylation and high-performance liquid chromatography.

PubMed

Syu, Kai-Yang; Lin, Chih-Li; Huang, Hsiu-Chen; Lin, Jen-Kun

2008-09-10

Dabsyl chloride (dimethylaminoazobenzene sulfonyl chloride), a useful chromophoric labeling reagent for amino acids and amines, was developed in this laboratory in 1975. Although several methods have been developed to determine various types of amino acids, a quick and easy method of determining theanine, GABA, and other amino acids has not been developed in one HPLC system. In this paper are analyzed the free amino acid contents of theanine and GABA in different teas (green tea, black tea, oolong tea, Pu-erh tea, and GABA tea) with a dabsylation and reverse phase high-performance liquid chromatography (HPLC) system coupled with a detector at 425 nm absorbance. Two reverse phase columns, Hypersil GOLD and Zorbax ODS, were used and gave different resolutions of dabsyl amino acids in the gradient elution program. The data suggest that the tea source or the steps of tea-making may contribute to the theanine contents variations. High theanine contents of high-mountain tea were observed in both green tea and oolong tea. Furthermore, the raw (natural fermented) Pu-erh tea contained more theanine than ripe (wet fermented) Pu-erh tea, and the GABA contents in normal teas were generally lower than that in GABA tea.

Resolution and identification of the protein components of the photosystem II antenna system of higher plants by reversed-phase liquid chromatography with electrospray-mass spectrometric detection.

PubMed

Corradini, D; Huber, C G; Timperio, A M; Zolla, L

2000-07-21

Reversed-phase liquid chromatography (RPLC) was interfaced to mass spectrometry (MS) with an electrospray ion (ESI) source for the separation and accurate molecular mass determination of the individual intrinsic membrane proteins that comprise the photosystem II (PS II) major light-harvesting complex (LHC II) and minor (CP24, CP26 and CP29) antenna system, whose molecular masses range between 22,000 and 29,000. PS II is a supramolecular complex intrinsic of the thylacoid membrane, which plays the important role in photosynthesis of capturing solar energy, and transferring it to photochemical reaction centers where energy conversion occurs. The protein components of the PS II major and minor antenna systems were extracted from spinach thylacoid membranes and separated using a butyl-silica column eluted by an acetonitrile gradient in 0.05% (v/v) aqueous trifluoroacetic acid. On-line electrospray MS allowed accurate molecular mass determination and identification of the protein components of PS II major and minor antenna system. The proposed RPLC-ESI-MS method holds several advantages over sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the conventional technique for studying membrane proteins, including a better protein separation, mass accuracy, speed and efficiency.

Concentration-related metabolic rate and behavioral thermoregulatory adaptations to serial administrations of nitrous oxide in rats

PubMed Central

2018-01-01

Background Initial administration of ≥60% nitrous oxide (N2O) to rats evokes hypothermia, but after repeated administrations the gas instead evokes hyperthermia. This sign reversal is driven mainly by increased heat production. To determine whether rats will behaviorally oppose or assist the development of hyperthermia, we previously performed thermal gradient testing. Inhalation of N2O at ≥60% causes rats to select cooler ambient temperatures both during initial administrations and during subsequent administrations in which the hyperthermic state exists. Thus, an available behavioral response opposes (but does not completely prevent) the acquired hyperthermia that develops over repeated high-concentration N2O administrations. However, recreational and clinical uses of N2O span a wide range of concentrations. Therefore, we sought to determine the thermoregulatory adaptations to chronic N2O administration over a wide range of concentrations. Methods This study had two phases. In the first phase we adapted rats to twelve 3-h N2O administrations at either 0%, 15%, 30%, 45%, 60% or 75% N2O (n = 12 per group); outcomes were core temperature (via telemetry) and heat production (via respirometry). In the second phase, we used a thermal gradient (range 8°C—38°C) to assess each adapted group’s thermal preference, core temperature and locomotion on a single occasion during N2O inhalation at the assigned concentration. Results In phase 1, repeated N2O administrations led to dose related hyperthermic and hypermetabolic states during inhalation of ≥45% N2O compared to controls (≥ 30% N2O compared to baseline). In phase 2, rats in these groups selected cooler ambient temperatures during N2O inhalation but still developed some hyperthermia. However, a concentration-related increase of locomotion was evident in the gradient, and theoretical calculations and regression analyses both suggest that locomotion contributed to the residual hyperthermia. Conclusions Acquired N2O hyperthermia in rats is remarkably robust, and occurs even despite the availability of ambient temperatures that might fully counter the hyperthermia. Increased locomotion in the gradient may contribute to hyperthermia. Our data are consistent with an allostatic dis-coordination of autonomic and behavioral thermoregulatory mechanisms during drug administration. Our results have implications for research on N2O abuse as well as research on the role of allostasis in drug addiction. PMID:29672605

Development of a thermodynamic model for a cold cycle 3He-4He dilution refrigerator

NASA Astrophysics Data System (ADS)

Mueller, B. W.; Miller, F. K.

2016-10-01

A thermodynamic model of a 3He-4He cold cycle dilution refrigerator with no actively-driven mechanical components is developed and investigated. The refrigerator employs a reversible superfluid magnetic pump, passive check valves, a phase separation chamber, and a series of recuperative heat exchangers to continuously circulate 3He-4He and maintain a 3He concentration gradient across the mixing chamber. The model predicts cooling power and mixing chamber temperature for a range of design and operating parameters, allowing an evaluation of feasibility for potential 3He-4He cold cycle dilution refrigerator prototype designs. Model simulations for a prototype refrigerator design are presented.

Determination of urinary 2- and 3-dechloroethylated metabolites of ifosfamide by high-performance liquid chromatography.

PubMed

Goren, M P

1991-10-04

In vivo oxidation of chloroethyl side-chains on ifosfamide produces the toxin chloroacetaldehyde. Production of this labile metabolite can be indirectly quantitated by monitoring the excretion of the residual 2- and 3-dechloroethylated ifosfamide. Urinary ifosfamide and the two dechloroethylated metabolites were extracted into chloroform from alkalinized salt-saturated urine, followed by high-performance liquid chromatographic separation using an acetonitrile gradient on a reversed-phase column and ultraviolet detection at 190 nm. In five patients given 1.6 g/m2 ifosfamide, 11-30% of the dose was excreted over 24 h as unchanged drug, 11-21% as 3-dechloroethylated and 3-10% as 2-dechloroethylated ifosfamide.

Chern-Simons theory and Wilson loops in the Brillouin zone

NASA Astrophysics Data System (ADS)

Lian, Biao; Vafa, Cumrun; Vafa, Farzan; Zhang, Shou-Cheng

2017-03-01

Berry connection is conventionally defined as a static gauge field in the Brillouin zone. Here we show that for three-dimensional (3D) time-reversal invariant superconductors, a generalized Berry gauge field behaves as a fluctuating field of a Chern-Simons gauge theory. The gapless nodal lines in the momentum space play the role of Wilson loop observables, while their linking and knot invariants modify the gravitational theta angle. This angle induces a topological gravitomagnetoelectric effect where a temperature gradient induces a rotational energy flow. We also show how topological strings may be realized in the six-dimensional phase space, where the physical space defects play the role of topological D-branes.

Dynamical Chern-Simons Theory in the Brillouin Zone

NASA Astrophysics Data System (ADS)

Lian, Biao; Vafa, Cumrun; Vafa, Farzan; Zhang, Shou-Cheng

Berry connection is conventionally defined as a static gauge field in the Brillouin zone. Here we show that for three-dimensional (3d) time-reversal invariant superconductors, a generalized Berry gauge field behaves as a dynamical fluctuating field of a Chern-Simons gauge theory. The gapless nodal lines in the momentum space play the role of Wilson loop observables, while their linking and knot invariants modify the gravitational theta angle. This angle induces a topological gravitomagnetoelectric effect where a temperature gradient induces a rotational energy flow. We also show how topological strings may be realized in the 6 dimensional phase space, where the physical space defects play the role of topological D-branes.

Electrical characteristics in reverse electrodialysis using nanoporous membranes

NASA Astrophysics Data System (ADS)

Chanda, Sourayon; Tsai, Peichun Amy

2017-11-01

We experimentally and numerically investigate the effects of concentration difference and flow velocity on sustainable electricity generation and associated fluid dynamics using a single reverse electrodialysis (RED) cell. By exploiting the charge-selective nature of nanoporous interfaces, electrical energy is generated by reverse electrodialysis harnessing chemical Gibbs energy via a salinity gradient. Experimentally, a RED cell was designed with two reservoirs, which are separated by a nanoporous, cation-selective membrane. We injected deionized water through one reservoir, whereas a solution of high salt concentration through the other. The gradient of salt concentration primarily drives the flow in the charged nano-pores, due to the interplay between charge selectivity, diffusion processes, and electro-migration. The current-voltage characteristics of the single RED cell shows a linear current-voltage relationship, similar to an electrochemical cell. The membrane resistance is increased with increasing salt concentration difference and external flow rate. The present experimental work was further analyzed numerically to better understand the detailed electrical and flow fields under different concentration gradients and external flows. NSERC Discovery, Accelerator, and CRC Programs.

Development and validation of a HPLC method for the assay of dapivirine in cell-based and tissue permeability experiments.

PubMed

das Neves, José; Sarmento, Bruno; Amiji, Mansoor; Bahia, Maria Fernanda

2012-12-12

Dapivirine, a non-nucleoside reverse transcriptase inhibitor, is being currently used for the development of potential anti-HIV microbicide formulations and delivery systems. A new high-performance liquid chromatography (HPLC) method with UV detection was developed for the assay of this drug in different biological matrices, namely cell lysates, receptor media from permeability experiments and homogenates of mucosal tissues. The method used a reversed-phase C18 column with a mobile phase composed of trifluoroacetic acid solution (0.1%, v/v) and acetonitrile in a gradient mode. Injection volume was 50μL and the flow rate 1mL/min. The total run time was 12min and UV detection was performed at 290nm for dapivirine and the internal standard (IS) diphenylamine. A Box-Behnken experimental design was used to study different experimental variables of the method, namely the ratio of the mobile phase components and the gradient time, and their influence in responses such as the retention factor, tailing factor, and theoretical plates for dapivirine and the IS, as well as the peak resolution between both compounds. The optimized method was further validated and its usefulness assessed for in vitro and ex vivo experiments using dapivirine or dapivirine-loaded nanoparticles. The method showed to be selective, linear, accurate and precise in the range of 0.02-1.5μg/mL. Other chromatographic parameters, namely carry-over, lower limit of quantification (0.02μg/mL), limit of detection (0.006μg/mL), recovery (equal or higher than 90.7%), and sample stability at different storage conditions, were also determined and found adequate for the intended purposes. The method was successfully used for cell uptake assays and permeability studies across cell monolayers and pig genital mucosal tissues. Overall, the proposed method provides a simple, versatile and reliable way for studying the behavior of dapivirine in different biological matrices and assessing its potential as an anti-HIV microbicide drug. Copyright © 2012 Elsevier B.V. All rights reserved.

Reverse Shape Memory Effect Related to α → γ Transformation in a Fe-Mn-Al-Ni Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Peng, Huabei; Huang, Pan; Zhou, Tiannan; Wang, Shanling; Wen, Yuhua

2017-05-01

In this study, we investigated the shape memory behavior and phase transformations of solution-treated Fe43.61Mn34.74Al13.38Ni8.27 alloy between room temperature and 1173 K (900 °C). This alloy exhibits the reverse shape memory effect resulting from the phase transformation of α (bcc) → γ (fcc) between 673 K and 1073 K (400 °C and 800 °C) in addition to the shape memory effect resulting from the martensitic reverse transformation of γ' (fcc) → α (bcc) below 673 K (400 °C). There is a high density of hairpin-shaped dislocations in the α phase undergoing the martensitic reverse transformation of γ' → α. The lath γ phase, which preferentially nucleates and grows in the reversed α phase, has the same crystal orientation with the reverse-transformed γ' martensite. However, the vermiculate γ phase, which is precipitated in the α phase between lath γ phase, has different crystal orientations. The lath γ phase is beneficial to attaining better reverse shape memory effect than the vermiculate γ phase.

Acceleration of Convergence to Equilibrium in Markov Chains by Breaking Detailed Balance

NASA Astrophysics Data System (ADS)

Kaiser, Marcus; Jack, Robert L.; Zimmer, Johannes

2017-07-01

We analyse and interpret the effects of breaking detailed balance on the convergence to equilibrium of conservative interacting particle systems and their hydrodynamic scaling limits. For finite systems of interacting particles, we review existing results showing that irreversible processes converge faster to their steady state than reversible ones. We show how this behaviour appears in the hydrodynamic limit of such processes, as described by macroscopic fluctuation theory, and we provide a quantitative expression for the acceleration of convergence in this setting. We give a geometrical interpretation of this acceleration, in terms of currents that are antisymmetric under time-reversal and orthogonal to the free energy gradient, which act to drive the system away from states where (reversible) gradient-descent dynamics result in slow convergence to equilibrium.

Simultaneous determination of bifonazole and tinctures of calendula flower in pharmaceutical creams by reversed-phase liquid chromatography.

PubMed

Ferreyra, Carola F; Ortiz, Cristina S

2005-01-01

The aim of this research was to develop and validate a sensitive, rapid, easy, and precise reversed-phase liquid chromatography (LC) method for stability studies of bifonazole (I) formulated with tinctures of calendula flower (II). The method was especially developed for the analysis and quantitative determination of I and II in pure and combined forms in cream pharmaceutical formulations without using gradient elution and at room temperature. The influence on the stability of compound I of temperature, artificial radiation, and drug II used for the new pharmaceutical design was evaluated. The LC separation was carried out using a Supelcosil LC-18 column (25 cm x 4.6 mm id, 5 microm particle size); the mobile phase was composed of methanol-0.1 M ammonium acetate buffer (85 + 15, v/v) pumped isocratically at a flow rate of 1 mL/min; and ultraviolet detection was at 254 nm. The analysis time was less than 10 min. Calibration graphs were found to be linear in the 0.125-0.375 mg/mL (rI = 0.9991) and 0.639-1.916 mg/mL (rII = 0.9995) ranges for I and II, respectively. The linearity, precision, recovery, and limits of detection and quantification were satisfactory for I and II. The results obtained suggested that the developed LC method is selective and specific for the analysis of I and II in pharmaceutical products, and that it can be applied to stability studies.

Resolution and isolation of enantiomers of (±)-isoxsuprine using thin silica gel layers impregnated with L-glutamic acid, comparison of separation of its diastereomers prepared with chiral derivatizing reagents having L-amino acids as chiral auxiliaries.

PubMed

Bhushan, Ravi; Nagar, Hariom

2015-03-01

Thin silica gel layers impregnated with optically pure l-glutamic acid were used for direct resolution of enantiomers of (±)-isoxsuprine in their native form. Three chiral derivatizing reagents, based on DFDNB moiety, were synthesized having l-alanine, l-valine and S-benzyl-l-cysteine as chiral auxiliaries. These were used to prepare diastereomers under microwave irradiation and conventional heating. The diastereomers were separated by reversed-phase high-performance liquid chromatography on a C18 column with detection at 340 nm using gradient elution with mobile phase containing aqueous trifluoroacetic acid and acetonitrile in different compositions and by thin-layer chromatography (TLC) on reversed phase (RP) C18 plates. Diastereomers prepared with enantiomerically pure (+)-isoxsuprine were used as standards for the determination of the elution order of diastereomers of (±)-isoxsuprine. The elution order in the experimental study of RP-TLC and RP-HPLC supported the developed optimized structures of diastereomers based on density functional theory. The limit of detection was 0.1-0.09 µg/mL in TLC while it was in the range of 22-23 pg/mL in HPLC and 11-13 ng/mL in RP-TLC for each enantiomer. The conditions of derivatization and chromatographic separation were optimized. The method was validated for accuracy, precision, limit of detection and limit of quantification. Copyright © 2014 John Wiley & Sons, Ltd.

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Novel determinants of the neuronal Cl− concentration

PubMed Central

Delpire, Eric; Staley, Kevin J

2014-01-01

It is now a well-accepted view that cation-driven Cl− transporters in neurons are involved in determining the intracellular Cl− concentration. In the present review, we propose that additional factors, which are often overlooked, contribute substantially to the Cl− gradient across neuronal membranes. After briefly discussing the data supporting and opposing the role of cation–chloride cotransporters in regulating Cl−, we examine the participation of the following factors in the formation of the transmembrane Cl− gradient: (i) fixed ‘Donnan’ charges inside and outside the cell; (ii) the properties of water (free vs. bound); and (iii) water transport through the cotransporters. We demonstrate a steep relationship between intracellular Cl− and the concentration of fixed negative charges on macromolecules. We show that in the absence of water transport through the K+–Cl− cotransporter, a large osmotic gradient builds at concentrations below or above a set value of ‘Donnan’ charges, and show that at any value of these fixed charges, the reversal potential for Cl− equates that of K+. When the movement of water across the membrane is a source of free energy, it is sufficient to modify the movement of Cl− through the cotransporter. In this scenario, the reversal potential for Cl− does not closely follow that of K+. Furthermore, our simulations demonstrate that small differences in the availability of freely diffusible water between inside and outside the cell greatly affect the Cl− reversal potential, particularly when osmolar transmembrane gradients are minimized, for example by idiogenic osmoles. We also establish that the presence of extracellular charges has little effect on the chloride reversal potential, but greatly affects the effective inhibitory conductance for Cl−. In conclusion, our theoretical analysis of the presence of fixed anionic charges and water bound on macromolecules inside and outside the cell greatly impacts both Cl− gradient and Cl− conductance across neuronal membranes. PMID:25107928

Influence of surface wettability on transport mechanisms governing water droplet evaporation.

PubMed

Pan, Zhenhai; Weibel, Justin A; Garimella, Suresh V

2014-08-19

Prediction and manipulation of the evaporation of small droplets is a fundamental problem with importance in a variety of microfluidic, microfabrication, and biomedical applications. A vapor-diffusion-based model has been widely employed to predict the interfacial evaporation rate; however, its scope of applicability is limited due to incorporation of a number of simplifying assumptions of the physical behavior. Two key transport mechanisms besides vapor diffusion-evaporative cooling and natural convection in the surrounding gas-are investigated here as a function of the substrate wettability using an augmented droplet evaporation model. Three regimes are distinguished by the instantaneous contact angle (CA). In Regime I (CA ≲ 60°), the flat droplet shape results in a small thermal resistance between the liquid-vapor interface and substrate, which mitigates the effect of evaporative cooling; upward gas-phase natural convection enhances evaporation. In Regime II (60 ≲ CA ≲ 90°), evaporative cooling at the interface suppresses evaporation with increasing contact angle and counterbalances the gas-phase convection enhancement. Because effects of the evaporative cooling and gas-phase convection mechanisms largely neutralize each other, the vapor-diffusion-based model can predict the overall evaporation rates in this regime. In Regime III (CA ≳ 90°), evaporative cooling suppresses the evaporation rate significantly and reverses entirely the direction of natural convection induced by vapor concentration gradients in the gas phase. Delineation of these counteracting mechanisms reconciles previous debate (founded on single-surface experiments or models that consider only a subset of the governing transport mechanisms) regarding the applicability of the classic vapor-diffusion model. The vapor diffusion-based model cannot predict the local evaporation flux along the interface for high contact angle (CA ≥ 90°) when evaporative cooling is strong and the temperature gradient along the interface determines the peak local evaporation flux.

Development and validation of an HPLC method for the determination of dibenzoylmethane in rat plasma and its application to the pharmacokinetic study.

PubMed

Shen, Guoxiang; Hong, Jin-Liern; Kong, Ah-Ng Tony

2007-06-01

A highly sensitive and simple high-performance liquid chromatographic (HPLC) assay has been developed and validated for the quantification of dibenzoylmethane (DBM) in rat plasma. DBM and internal standard (I.S.) 1-(5-chloro-2-hydroxy-4-methylphenyl)-3-phenyl-1,3-propanedione (CHMPP) were extracted from rat plasma by ethyl acetate/methanol (95:5, v/v) and analyzed using reverse-phase gradient elution with a Phenomenex Gemini C18 5-mum column. A gradient of mobile phase (mobile phase A: water/methanol (80:20, v/v) with 0.1% TFA and mobile phase B: acetonitrile with 0.1% TFA) at a flow rate of 0.2 mL/min, and ultraviolet (UV) detection at 335 nm were utilized. The lower limit of quantification (LLOQ) using 50 microL rat plasma was 0.05 microg/mL. The calibration curve was linear over a concentration range of 0.05-20 microg/mL. The mean recoveries were 80.6+/-5.7, 83.4+/-1.6 and 77.1+/-3.4% with quality control (QC) level of 0.05, 1 and 20 microg/mL, respectively. Intra- and inter-day assay accuracy and precision fulfilled US FDA guidance for industry bioanalytical method validation. Stability studies showed that DBM was stable in rat plasma after 4h incubation at room temperature, one month storage at -80 degrees C and three freeze/thaw cycles, as well as in reconstitute buffer for 48 h at 4 degrees C. The utility of the assay was confirmed by the successful analysis of plasma samples from DBM pharmacokinetics studies in the rats after oral and intravenous administrations.

C18 solid-phase isolation and high-performance liquid chromatography/ultraviolet diode array determination of fully methoxylated flavones in citrus juices.

PubMed

Sendra, J M; Navarro, J L; Izquierdo, L

1988-09-01

A new analytical methodology for the determination of fully methoxylated flavones (FMFs) in citrus juices is described. Isolation of the FMFs is carried out by percolation of 30 mL of clarified citrus juice (to which tetramethyl-o-kaempferol is previously added as internal standard) through a C18 Sep-Pak cartridge, washing with 3 mL of water followed by 5 mL of water/acetonitrile (3:1), and selective elution of the retained FMFs with 5 mL of water/acetonitrile (9:11). Determination of the isolated FMFs is carried out by reversed-phase high-performance liquid chromatography (HPLC) and UV diode array detection (DAD). Signals at wavelengths 320, 335, and 345 nm (bandwidth 4 nm) are simultaneously acquired, stored, plotted, and integrated. The column used is a microbore (200 x 2.1-mm) Hypersil ODS 5 microns. Elution is in gradient mode, using a ternary mobile phase (water/acetonitrile/tetrahydrofuran). Column temperature is 40 degrees C. Recovery yields are nearly 100% for all the FMFs detected and identified: isosinensetin, hexamethyl-o-gossypetin, sinensetin, tetramethyl-o-isoscutellarein, hexamethyl-o-quercetagetin, nobiletin, tetramethyl-o-scutellarein, heptamethoxyflavone, and tangeretin. Chromatographic separation of the FMFs is extremely dependent upon the minor changes of the mobile phase composition and percentages, gradient rate, and temperature. The UV spectra (230 to 400 nm) of the FMFs obtained under chromatographic conditions are given. The FMFs relative response factors at 320, 335, and 345 nm and their concentrations in hand-squeezed and commercial concentrated orange and mandarin juices are tabulated. The FMF concentration differences found among samples are discussed.

Determination of the electric field gradient in RbCaF3 near the phase transition

NASA Astrophysics Data System (ADS)

Hepp, M. A.; Man, P. P.; Trokiner, A.; Zanni, H.; Fraissard, J.

1992-12-01

The fluoroperovskite, RbCaF 3 undergoes a phase transition at 195.5K from a cubic to a tetragonal phase. The order parameter for this transition is directly related to the electric field gradient which arises in the tetragonal phase. In this work, we have used three NMR methods to measure the electric field gradient at the 87Rb site in a single crystal of RbCaF 3, very near this transition. These experiments are based on recent theoretical developments which allow the measurement of quadrupole parameters even for nuclei in a weak electric field gradient.

Solar energy powered microbial fuel cell with a reversible bioelectrode.

PubMed

Strik, David P B T B; Hamelers, Hubertus V M; Buisman, Cees J N

2010-01-01

The solar energy powered microbial fuel cell is an emerging technology for electricity generation via electrochemically active microorganisms fueled by solar energy via in situ photosynthesized metabolites from algae, cyanobacteria, or living higher plants. A general problem with microbial fuel cells is the pH membrane gradient which reduces cell voltage and power output. This problem is caused by acid production at the anode, alkaline production at the cathode, and the nonspecific proton exchange through the membrane. Here we report a solution for a new kind of solar energy powered microbial fuel cell via development of a reversible bioelectrode responsible for both biocatalyzed anodic and cathodic electron transfer. Anodic produced protons were used for the cathodic reduction reaction which held the formation of a pH membrane gradient. The microbial fuel cell continuously generated electricity and repeatedly reversed polarity dependent on aeration or solar energy exposure. Identified organisms within biocatalyzing biofilm of the reversible bioelectrode were algae, (cyano)bacteria and protozoa. These results encourage application of solar energy powered microbial fuel cells.

Integrating Reverse-Electrodialysis Stacks with Flow Batteries for Improved Energy Recovery from Salinity Gradients and Energy Storage.

PubMed

Zhu, Xiuping; Kim, Taeyoung; Rahimi, Mohammad; Gorski, Christopher A; Logan, Bruce E

2017-02-22

Salinity gradient energy can be directly converted into electrical power by using reverse electrodialysis (RED) and other technologies, but reported power densities have been too low for practical applications. Herein, the RED stack performance was improved by using 2,6-dihydroxyanthraquinone and ferrocyanide as redox couples. These electrolytes were then used in a flow battery to produce an integrated RED stack and flow battery (RED-FB) system capable of capturing, storing, and discharging salinity gradient energy. Energy captured from the RED stack was discharged in the flow battery at a maximum power density of 3.0 kW m -2 -anode, which was similar to the flow batteries charged by electrical power and could be used for practical applications. Salinity gradient energy captured from the RED stack was recovered from the electrolytes as electricity with 30 % efficiency, and the maximum energy density of the system was 2.4 kWh m -3 -anolyte. The combined RED-FB system overcomes many limitations of previous approaches to capture, store, and use salinity gradient energy from natural or engineered sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Remobilizing the Interfaces of Thermocapillary Driven Bubbles Retarded by the Adsorption of a Surfactant Impurity on the Bubble Surface

NASA Technical Reports Server (NTRS)

Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim S. (Technical Monitor)

2000-01-01

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is applied to the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow which propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillarity to direct the movement of bubbles in space is the fact that surfactant impurities which are unavoidably present in the continuous phase can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature tension gradient, and decreases to near zero the thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have been retarded by the adsorption onto the bubble surface of a surfactant impurity, Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition the rapid kinetic exchange and high bulk concentration maintain a saturated surface with a uniform surface concentrations. This prevents retarding surface tension gradients and keeps the velocity high. In our first report last year, we detailed experimental results which verified the theory of remobilization in ground based experiments in which the steady velocity of rising bubbles was measured in a continuous phase consisting of a glycerol/water mixture containing a polyethylene glycol surfactant C12E6 (CH3(CH2)11(OCH2CH2)6OH). In our report this year, we detail our efforts to describe theoretically the remobilization observed. We construct a model in which a bubble rises steadily by buoyancy in a continuous (Newtonian) viscous fluid containing surfactant with a uniform far field bulk concentration. We account for the effects of inertia as well as viscosity in the flow in the continuous phase caused by the bubble motion (order one Reynolds number), and we assume that the bubble shape remains spherical (viscous and inertial forces are smaller than capillary forces, i e. small Weber and capillary numbers). The surfactant distribution is calculated by solving the mass transfer equations including convection and diffusion in the bulk, and finite kinetic exchange the bulk and the surface. Convective effects dominate diffusive mass transfer in the bulk of the liquid (high Peclet numbers) except in a thin boundary layer near the surface. A finite volume method is used to numerically solve the hydrodynamic and mass transfer equations on a staggered grid which accounts specifically for the thin boundary layer. We present the results of the nondimensional drag as a function of the bulk concentration of surfactant for different rates of kinetic exchange, from which we develop criteria for the concentration necessary to develop a prescribed degree of remobilization. The criteria compare favorably with the experimental results.

Isolation and purification of series bioactive components from Hypericum perforatum L. by counter-current chromatography.

PubMed

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Xu, Chunming; Ito, Yoichiro

2011-03-01

Counter-current chromatography (CCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate-water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, ¹HNMR and ¹³CNMR. Copyright © 2011 Elsevier B.V. All rights reserved.

Isolation and purification of series bioactive components from Hypericum Perforatum L. by high-speed counter-current chromatography

PubMed Central

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Ito, Yiochiro

2011-01-01

High-speed counter-current chromatography (HSCCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate–water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, 1HNMR and 13CNMR. PMID:21306961

High-resolution ultrahigh-pressure long column reversed-phase liquid chromatography for top-down proteomics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yufeng; Tolic, Nikola; Piehowski, Paul D.

We report development of an approach providing high-resolution RPLC of proteins and its utility for mass spectrometry-based top-down proteomics. A chromatographic peak capacity of ~450 was achieved for proteins and large polypeptides having MWs up to 43 kDa in the context of proteomics applications. RPLC column lengths from 20 to 200 cm, particle sizes from 1.5 to 5 m, bonding alkyl chains from C1 to C2, C4, C8, and C18, and particle surface structures that spanned porous, superficially porous (porous shell, core-shell), and nonporous were investigated at pressures up to14K psi. Column length was found as the most important factormore » for >20 kDa proteins in gradient RPLC, and shortening column length degraded RPLC resolution and sensitivity regardless of the size and surface structure of the packing particles used. The alkyl chains bonded to the silica particle surface significantly affected the RPLC recovery and efficiency, and short alkyl C1-C4 phases provided higher sensitivity and resolution than C8 and C18 phases. Long gradient separations (e.g., >10 hours) with long columns (e.g., 100 cm) were particularly effective in conjunction with use of high accuracy mass spectrometers (e.g., the Orbitrap Elite) for top-down proteomics with improved proteoform coverage by allowing multiple HCD, CID, and ETD dissociation modes. It was also found that HCD produced small fragments useful for proteoform identification, while low energy CID and ETD often complemented HCD by providing large fragments.« less

Development and validation of a stability-indicating RP-HPLC method for assay of betamethasone and estimation of its related compounds.

PubMed

Fu, Qiang; Shou, Minshan; Chien, Dwight; Markovich, Robert; Rustum, Abu M

2010-02-05

Betamethasone (9alpha-fluoro-16beta-methylprednisolone) is one of the members of the corticosteriod family of active pharmaceutical ingredient (API), which is widely used as an anti-inflammatory agent and also as a starting material to manufacture various esters of betamethasone. A stability-indicating reverse-phase high performance liquid chromatography (RP-HPLC) method has been developed and validated which can separate and accurately quantitate low levels of 26 betamethasone related compounds. The stability-indicating capability of the method was demonstrated through adequate separation of all potential betamethasone related compounds from betamethasone and also from each other that are present in aged and stress degraded betamethasone stability samples. Chromatographic separation of betamethasone and its related compounds was achieved by using a gradient elution at a flow rate of 1.0mL/min on a ACE 3 C18 column (150mmx4.6mm, 3microm particle size, 100A pore size) at 40 degrees C. Mobile phase A of the gradient was 0.1% methanesulfonic acid in aqueous solution and mobile phase B was a mixture of tert-butanol and 1,4-dioxane (7:93, v/v). UV detection at 254nm was employed to monitor the analytes. For betamethasone 21-aldehyde, the QL and DL were 0.02% and 0.01% respectively. For betamethasone and the rest of the betamethasone related compounds, the QL and DL were 0.05% and 0.02%. The precision of betamethasone assay is 0.6% and the accuracy of betamethasone assay ranged from 98.1% to 99.9%.

HPLC separation of acetaminophen and its impurities using a mixed-mode reversed-phase/cation exchange stationary phase.

PubMed

Călinescu, Octavian; Badea, Irinel A; Vlădescu, Luminiţa; Meltzer, Viorica; Pincu, Elena

2012-04-01

Determination of acetaminophen and its main impurities: 4-nitrophenol, 4'-chloroacetanilide, as well as 4-aminophenol and its degradation products, p-benzoquinone and hydroquinone has been developed and validated by a new high-performance liquid chromatography method. Chromatographic separation has been obtained on a Hypersil Duet C18/SCX column, using gradient elution, with a mixture of phosphate buffer (pH = 4.88) and methanol as a mobile phase. Analysis time did not exceed 14.5 min and good resolutions, peak shapes and asymmetries have resulted. The linearity of the method has been tested in the range of 5.0-60 µg/mL for acetaminophen and 0.5-6 µg/mL for the other compounds. The limits of detection and quantification have been also established to be lower than 0.1 µg/mL and 0.5 µg/mL, respectively. The method has been successfully applied for the analysis of commercial acetaminophen preparations. © The Author [2012]. Published by Oxford University Press. All rights reserved.

Development and validation of a novel stability-indicating HPLC method for the simultaneous assay of betamethasone-17-valerate, fusidic acid, potassium sorbate, methylparaben and propylparaben in a topical cream preparation.

PubMed

Byrne, Jonathan; Velasco-Torrijos, Trinidad; Reinhardt, Robert

2014-08-05

A novel stability-indicating reversed phase high performance liquid chromatographic (RP-HPLC) method for the simultaneous assay of betamethasone-17-valerate, fusidic acid and potassium sorbate as well as methyl- and propylparaben in a topical cream preparation has been developed. A 100mm×3.0mm ID. Ascentis Express C18 column maintained at 30°C and UV detection at 240nm were used. A gradient programme was employed at a flow-rate of 0.75ml/min. Mobile phase A comprised of an 83:17 (v/v) mixture of acetonitrile and methanol and mobile phase B of a 10g/l solution of 85% phosphoric acid in purified water. The method has been validated according to current International Conference on Harmonisation (ICH) guidelines and applied during formulation development and stability studies. The procedure has been shown to be stability-indicating for the topical cream. Copyright © 2014 Elsevier B.V. All rights reserved.

Simultaneous determination of 11 antibiotics and their main metabolites from four different groups by reversed-phase high-performance liquid chromatography-diode array-fluorescence (HPLC-DAD-FLD) in human urine samples.

PubMed

Fernandez-Torres, R; Consentino, M Olías; Lopez, M A Bello; Mochon, M Callejon

2010-05-15

A new, accurate and sensitive reversed-phase high-performance liquid chromatography (RP-HPLC) as analytical method for the quantitative determination of 11 antibiotics (drugs) and the main metabolites of five of them present in human urine has been worked out, optimized and validated. The analytes belong to four different groups of antibiotics (sulfonamides, tetracyclines, penicillins and anphenicols). The analyzed compounds were sulfadiazine (SDI) and its N(4)-acetylsulfadiazine (NDI) metabolite, sulfamethazine (SMZ) and its N(4)-acetylsulfamethazine (NMZ), sulfamerazine (SMR) and its N(4)-acetylsulfamerazine (NMR), sulfamethoxazole (SMX), trimetroprim (TMP), amoxicillin (AMX) and its main metabolite amoxicilloic acid (AMA), ampicillin (AMP) and its main metabolite ampicilloic acid (APA), chloramphenicol (CLF), thiamphenicol (TIF), oxytetracycline (OXT) and chlortetracycline (CLT). For HPLC analysis, diode array (DAD) and fluorescence (FLD) detectors were used. The separation of the analyzed compounds was conducted by means of a Phenomenex Gemini C(18) (150mm x 4.6mm I.D., particle size 5microm) analytical column with LiChroCART LiChrospher C(18) (4mm x 4mm, particle size 5microm) guard column. Analyzed drugs were determined within 34min using formic acid 0.1% in water and acetonitrile in gradient elution mode as mobile phase. A linear response was observed for all compounds in the range of concentration studied. Two procedures were optimized for sample preparation: a direct treatment with methanol and acetonitrile and a solid phase extraction procedure using Bond Elut Plexa columns. The method was applied to the determination of the analytes in human urine from volunteers under treatment with different pharmaceutical formulations. This method can be successfully applied to routine determination of all these drugs in human urine samples.

Separation and determination of polyurethane amine catalysts in polyether polyols by using UHPLC-Q-TOF-MS on a reversed-phase/cation-exchange mixed-mode column.

PubMed

Li, Jiaxiao; Zhu, Marcel

2018-02-01

A simple, selective, and accurate ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry method was established and validated for the efficient separation and quantification of polyurethane amine catalysts in polyether polyols. Amine catalysts were primarily separated in polyether polyol-based sample by solid-phase extraction, and further baseline separated on a reversed-phase/cation-exchange mixed-mode column (SiELC Primesep™ 200) using 0.1% trifluoroacetic acid/acetonitrile as a mobile phase in gradient elution mode at a flow rate of 0.2 mL/min. High-resolution quadrupole time-of-flight mass spectrometry analysis in electrospray ionization positive mode allowed the identification as N,N'-bis[3-(dimethylamino)propyl]urea, N-[2-(2-dimethylaminoethoxy)ethyl]-N-methyl-1,3-propanediamine, and N,N,N',N'-tetramethyldipropylenetriamine. The method was validated and presented good linearity for all the analytes in blank matrices within the concentration range of 0.20-5.0 or 0.1-2.0 μg/mL with the correlation coefficients (R 2 ) ranging from 0.986 to 0.997. Method recovery ranged within 81-105% at all three levels (80, 100, and 120% of the original amount) with relative standard deviations of 1.0-6.2%. The limits of detection were in the range of 0.007-0.051 μg/mL. Good precision was obtained with relative standard deviation below 3.2 and 0.72% for peak area and retention time of three amines, respectively. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of the phenolic composition of fruit juices by single step gradient HPLC analysis of multiple components versus multiple chromatographic runs optimised for individual families.

PubMed

Bremner, P D; Blacklock, C J; Paganga, G; Mullen, W; Rice-Evans, C A; Crozier, A

2000-06-01

After minimal sample preparation, two different HPLC methodologies, one based on a single gradient reversed-phase HPLC step, the other on multiple HPLC runs each optimised for specific components, were used to investigate the composition of flavonoids and phenolic acids in apple and tomato juices. The principal components in apple juice were identified as chlorogenic acid, phloridzin, caffeic acid and p-coumaric acid. Tomato juice was found to contain chlorogenic acid, caffeic acid, p-coumaric acid, naringenin and rutin. The quantitative estimates of the levels of these compounds, obtained with the two HPLC procedures, were very similar, demonstrating that either method can be used to analyse accurately the phenolic components of apple and tomato juices. Chlorogenic acid in tomato juice was the only component not fully resolved in the single run study and the multiple run analysis prior to enzyme treatment. The single run system of analysis is recommended for the initial investigation of plant phenolics and the multiple run approach for analyses where chromatographic resolution requires improvement.

Reynolds and Maxwell stress measurements in the reversed field pinch experiment Extrap-T2R

NASA Astrophysics Data System (ADS)

Vianello, N.; Antoni, V.; Spada, E.; Spolaore, M.; Serianni, G.; Cavazzana, R.; Bergsåker, H.; Cecconello, M.; Drake, J. R.

2005-08-01

The complete Reynolds stress (RS) has been measured in the edge region of the Extrap-T2R reversed field pinch experiment. The RS exhibits a strong gradient in the region where a high E × B shear takes place. Experimental results show this gradient to be almost entirely due to the electrostatic contribution. This has been interpreted as experimental evidence of flow generation via turbulence mechanism. The scales involved in flow generation are deduced from the frequency decomposition of RS tensor. They are found related to magnetohydrodynamic activity but are different with respect to the scales responsible for turbulent transport.

Conjugate gradient and cross-correlation based least-square reverse time migration and its application

NASA Astrophysics Data System (ADS)

Sun, Xiao-Dong; Ge, Zhong-Hui; Li, Zhen-Chun

2017-09-01

Although conventional reverse time migration can be perfectly applied to structural imaging it lacks the capability of enabling detailed delineation of a lithological reservoir due to irregular illumination. To obtain reliable reflectivity of the subsurface it is necessary to solve the imaging problem using inversion. The least-square reverse time migration (LSRTM) (also known as linearized reflectivity inversion) aims to obtain relatively high-resolution amplitude preserving imaging by including the inverse of the Hessian matrix. In practice, the conjugate gradient algorithm is proven to be an efficient iterative method for enabling use of LSRTM. The velocity gradient can be derived from a cross-correlation between observed data and simulated data, making LSRTM independent of wavelet signature and thus more robust in practice. Tests on synthetic and marine data show that LSRTM has good potential for use in reservoir description and four-dimensional (4D) seismic images compared to traditional RTM and Fourier finite difference (FFD) migration. This paper investigates the first order approximation of LSRTM, which is also known as the linear Born approximation. However, for more complex geological structures a higher order approximation should be considered to improve imaging quality.

Velocity encoding with the slice select refocusing gradient for faster imaging and reduced chemical shift-induced phase errors.

PubMed

Middione, Matthew J; Thompson, Richard B; Ennis, Daniel B

2014-06-01

To investigate a novel phase-contrast MRI velocity-encoding technique for faster imaging and reduced chemical shift-induced phase errors. Velocity encoding with the slice select refocusing gradient achieves the target gradient moment by time shifting the refocusing gradient, which enables the use of the minimum in-phase echo time (TE) for faster imaging and reduced chemical shift-induced phase errors. Net forward flow was compared in 10 healthy subjects (N = 10) within the ascending aorta (aAo), main pulmonary artery (PA), and right/left pulmonary arteries (RPA/LPA) using conventional flow compensated and flow encoded (401 Hz/px and TE = 3.08 ms) and slice select refocused gradient velocity encoding (814 Hz/px and TE = 2.46 ms) at 3 T. Improved net forward flow agreement was measured across all vessels for slice select refocused gradient compared to flow compensated and flow encoded: aAo vs. PA (1.7% ± 1.9% vs. 5.8% ± 2.8%, P = 0.002), aAo vs. RPA + LPA (2.1% ± 1.7% vs. 6.0% ± 4.3%, P = 0.03), and PA vs. RPA + LPA (2.9% ± 2.1% vs. 6.1% ± 6.3%, P = 0.04), while increasing temporal resolution (35%) and signal-to-noise ratio (33%). Slice select refocused gradient phase-contrast MRI with a high receiver bandwidth and minimum in-phase TE provides more accurate and less variable flow measurements through the reduction of chemical shift-induced phase errors and a reduced TE/repetition time, which can be used to increase the temporal/spatial resolution and/or reduce breath hold durations. Copyright © 2013 Wiley Periodicals, Inc.

Urea transport through composite polyallylamine membranes

NASA Technical Reports Server (NTRS)

Ballou, E. V.; Kubo, L. Y.; Spitze, L. A.; Wydeven, T.; Clark, J. A.

1977-01-01

Polyallylamine composite reverse osmosis membranes were prepared by plasma polymerization and deposition onto small-pored cellulose acetate/cellulose nitrate films. The polyallylamine coated the porous substrate with a thin uniform polymer film which exhibited water permeability and urea rejection, of interest because of the potential application of reverse osmosis to urine purification in closed environmental systems. The flux of C-14 labeled urea was studied under the influence of osmotic gradients provided by sodium chloride solutions. The urea flux was found to be enhanced by an osmotic pressure gradient in the same direction and diminished, but not prevented, by an opposing osmotic pressure gradient. Consideration is given to the mechanism of the urea transport, as well as to the influence of concentration polarization on the experimental results. The minimization of coupled flow in pores of a critical size range is apparently necessary to improve urea rejection.

Simulation of elution profiles in liquid chromatography - II: Investigation of injection volume overload under gradient elution conditions applied to second dimension separations in two-dimensional liquid chromatography.

PubMed

Stoll, Dwight R; Sajulga, Ray W; Voigt, Bryan N; Larson, Eli J; Jeong, Lena N; Rutan, Sarah C

2017-11-10

An important research direction in the continued development of two-dimensional liquid chromatography (2D-LC) is to improve the detection sensitivity of the method. This is especially important in applications where injection of large volumes of effluent from the first dimension ( 1 D) column into the second dimension ( 2 D) column leads to severe 2 D peak broadening and peak shape distortion. For example, this is common when coupling two reversed-phase columns and the organic solvent content of the 1 D mobile phase overwhelms the 2 D column with each injection of 1 D effluent, leading to low resolution in the second dimension. In a previous study we validated a simulation approach based on the Craig distribution model and adapted from the work of Czok and Guiochon [1] that enabled accurate simulation of simple isocratic and gradient separations with very small injection volumes, and isocratic separations with mismatched injection and mobile phase solvents [2]. In the present study we have extended this simulation approach to simulate separations relevant to 2D-LC. Specifically, we have focused on simulating 2 D separations where gradient elution conditions are used, there is mismatch between the sample solvent and the starting point in the gradient elution program, injection volumes approach or even exceed the dead volume of the 2 D column, and the extent of sample loop filling is varied. To validate this simulation we have compared results from simulations and experiments for 101 different conditions, including variation in injection volume (0.4-80μL), loop filling level (25-100%), and degree of mismatch between sample organic solvent and the starting point in the gradient elution program (-20 to +20% ACN). We find that that the simulation is accurate enough (median errors in retention time and peak width of -1.0 and -4.9%, without corrections for extra-column dispersion) to be useful in guiding optimization of 2D-LC separations. However, this requires that real injection profiles obtained from 2D-LC interface valves are used to simulate the introduction of samples into the 2 D column. These profiles are highly asymmetric - simulation using simple rectangular pulses leads to peak widths that are far too narrow under many conditions. We believe the simulation approach developed here will be useful for addressing practical questions in the development of 2D-LC methods. Copyright © 2017 Elsevier B.V. All rights reserved.

Reverse-phase liquid chromatography with electrospray ionization/mass spectrometry for the quantification of pseudoephedrine in human plasma and application to a bioequivalence study.

PubMed

Kim, Jin-Ki; Jee, Jun-Pil; Park, Jeong-Sook; Kim, Hyung Tae; Kim, Chong-Kook

2011-01-01

A sensitive and selective reverse-phase liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) method was developed and validated to quantify pseudoephedrine (CAS 90-82-4) in human plasma. Phenacetin was used as the internal standard (I.S.). Sample preparation was performed with a deproteinization step using acetonitrile. Pseudoephedrine and I.S. were successfully separated using gradient elution with 0.5% trifluoroacetic acid (TFA) in water and 0.5% TFA in methanol at a flow-rate of 0.2 mL/min. Detection was performed on a single quadrupole mass spectrometer by a selected ion monitoring (SIM) mode via electrospray ionization (ESI) source. The ESI source was set at positive ionization mode. The ion signals of m/z 166.3 and 180.2 were measured for the protonated molecular ions of pseudoephedrine and I.S., respectively. The lower limit of quantification (LLOQ) of pseudoephedrine in human plasma was 10 ng/mL and good linearity was observed in the range of concentrations 10-500 ng/mL (R2 = 1). The intra-day accuracy of the drug containing plasma samples was more than 97.60% with a precision of 3.99-11.82%. The inter-day accuracy was 99.36% or more, with a precision of 7.65-18.42%. By using this analytical method, the bioequivalence study of the pseudoephedrine preparation was performed and evaluated by statistical analysis of the log transformed mean ratios of pharmacokinetic parameters. All the results fulfilled the standard criteria of bioequivalence, being within the 80-125% range which is required by the Korea FDA, US FDA, and EMEA to conclude bioequivalence. Consequently, the developed reverse-phase LC-ESI-MS method was successfully applied to bioequivalence studies of pseudoephedrine in healthy male volunteers.

Aqueous Reversed-Phase HPLC/FT-IR Using Diffuse Reflectance Detections

NASA Astrophysics Data System (ADS)

Kalasinsky, Victor F.; Pai, T. H.; Kenton, R. C.; Kalasinsky, Kathryn S.

1989-12-01

Solvent-elimination HPLC/FT-IR has become a viable combination of two important techniques, and we have been developing a system which is adaptable to both normal and reversed-phase liquid chromatography. The interface involves the deposition of HPLC eluites onto a KCI-laden train with subsequent analysis via diffuse reflectance spectroscopy, and with minor modifications, the system can be used with microbore and analytical columns. With aqueous solvents, the water is converted to methanol and acetone in a post-column reaction with 2,2-dimethoxypropane before the eluites are deposited. A number of different samples have been used to demonstrate the interface and its flexibility. Steroids, analgesics, and other pharmaceutical preparations have been separated with reverse-phase solvents and identified by their infrared spectra. For some of the compounds studied, different infrared spectra of a given compound have been found to exhibit intensity variations, which arise from different crystalline states. The differences can be concentration dependent and may be useful in obtaining semi-quantitative information from the infrared spectra. Applications involving both gradient elution and isocratic separations have been successful. The former provides the same advantages for HPLC/FT-IR as one finds in conventional HPLC. More recent work has been applied to the use of buffers such as those frequently used in bioanalytical separations. In trying to simplify the post-column reaction with water, we have immobilized dehydration reagents onto silica particles and packed these materials into a column which is inserted in-line after the analytical column. Of the reagents utilized to date, 3,3-dimethoxypropyltrimethoxysilane has been found to perform most efficiently. It has advantages over the simpler reagents because it can be regenerated in the reaction column. Results and the efficiency of the dehydration process and its relation to the type of reagent and its coverage will be discussed.

High-Throughput Analysis of Sucrose Fatty Acid Esters by Supercritical Fluid Chromatography/Tandem Mass Spectrometry

PubMed Central

Hori, Katsuhito; Tsumura, Kazunobu; Fukusaki, Eiichiro; Bamba, Takeshi

2014-01-01

Supercritical fluid chromatography (SFC) coupled with triple quadrupole mass spectrometry was applied to the profiling of sucrose fatty acid esters (SEs). The SFC conditions (column and modifier gradient) were optimized for the effective separation of SEs. In the column test, a silica gel reversed-phase column was selected. Then, the method was used for the detailed characterization of commercial SEs and the successful analysis of SEs containing different fatty acids. The present method allowed for fast and high-resolution separation of monoesters to tetra-esters within a shorter time (15 min) as compared to the conventional high-performance liquid chromatography. The applicability of our method for the analysis of SEs was thus demonstrated. PMID:26819875

An improved method for the analysis of sennosides in Cassia angustifolia by high-performance liquid chromatography.

PubMed

Bala, S; Uniyal, G C; Dubey, T; Singh, S P

2001-01-01

A reversed-phase column liquid chromatographic method for the analysis of sennosides A and B present in leaf and pod extracts of Cassia angustifolia has been developed using a Symmetry C18 column and a linear binary gradient profile. The method can be utilised for the quantitative determination of other sennosides as a baseline resolution for most of the constituents was achieved. The method is economical in terms of the time taken and the amount of solvent used (25 mL) for each analysis. The validity of the method with respect to analysis was confirmed by comparing the UV spectra of each peak with those of reference compounds using a photodiode array detector.

High energy X-ray diffraction study of a dental ceramics–titanium functional gradient material prepared by field assisted sintering technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witte, K., E-mail: kerstin.witte@uni-rostock.de; Bodnar, W.; Schell, N.

A functional gradient material with eleven layers composed of a dental ceramics and titanium was successfully consolidated using field assisted sintering technique in a two-step sintering process. High energy X-ray diffraction studies on the gradient were performed at High Energy Material Science beamline at Desy in Hamburg. Phase composition, crystal unit edges and lattice mismatch along the gradient were determined applying Rietveld refinement procedure. Phase analysis revealed that the main crystalline phase present in the gradient is α-Ti. Crystallinity increases stepwisely along the gradient with a decreasing increment between every next layer, following rather the weight fraction of titanium. Themore » crystal unit edge a of titanium remains approximately constant with a value of 2.9686(1) Å, while c is reduced with increasing amount of titanium. In the layer with pure titanium the crystal unit edge c is constant with a value of 4.7174(2) Å. The lattice mismatch leading to an internal stress was calculated over the whole gradient. It was found that the maximal internal stress in titanium embedded in the studied gradient is significantly smaller than its yield strength, which implies that the structure of titanium along the whole gradient is mechanically stable. - Highlights: • High energy XRD studies of dental ceramics–Ti gradient material consolidated by FAST. • Phase composition, crystallinity and lattice parameters are determined. • Crystallinity increases stepwisely along the gradient following weight fraction of Ti. • Lattice mismatch leading to internal stress is calculated over the whole gradient. • Internal stress in α-Ti embedded in the gradient is smaller than its yield strength.« less

High-efficiency tri-band quasi-continuous phase gradient metamaterials based on spoof surface plasmon polaritons

PubMed Central

Li, Yongfeng; Ma, Hua; Wang, Jiafu; Pang, Yongqiang; Zheng, Qiqi; Chen, Hongya; Han, Yajuan; Zhang, Jieqiu; Qu, Shaobo

2017-01-01

A high-efficiency tri-band quasi-continuous phase gradient metamaterial is designed and demonstrated based on spoof surface plasmon polaritons (SSPPs). High-efficiency polarizaiton conversion transmission is firstly achieved via tailoring phase differece between the transmisive SSPP and the space wave in orthogonal directions. As an example, a tri-band circular-to-circular (CTC) polarization conversion metamateiral (PCM) was designed by a nonlinearly dispersive phase difference. Using such PCM unit cell, a tri-band quasi-continuous phase gradient metamaterial (PGM) was then realized by virtue of the Pancharatnam-Berry phase. The distribution of the cross-polarization transmission phase along the x-direction is continuous except for two infinitely small intervals near the phases 0° and 360°, and thus the phase gradient has definition at any point along the x-direction. The simulated normalized polarization conversion transmission spectrums together with the electric field distributions for circularly polarized wave and linearly polarized wave demonstrated the high-efficiency anomalous refraction of the quasi-continuous PGM. The experimental verification for the linearly polarized incidence was also provided. PMID:28079185

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, John L.; Smith, Richard D.

1993-01-01

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, J.L.; Smith, R.D.

1993-11-30

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

Experimental Study of Unsteady Flow Separation in a Laminar Boundary Layer

NASA Astrophysics Data System (ADS)

Bonacci, Andrew; Lang, Amy; Wahidi, Redha; Santos, Leonardo

2017-11-01

Flow separation, caused by an adverse pressure gradient, is a major problem in many applications. Reversing flow near the wall is the first sign of incipient separation and can bristle shark scales which may be linked to a passive, flow actuated separation control mechanism. An investigation of how this backflow forms and how it interacts with shark skin is of interest due to the fact that this could be used as a bioinspired means of initiating flow control. A water tunnel experiment aims to study unsteady separation with a focus on the reversing flow development near the wall within a flat plate laminar boundary layer (Re on order of 105) as an increasing adverse pressure gradient is induced by a rotating cylinder. Unsteady reversing flow development is documented using DPIV. Funding was provided by the National Science Foundation under the Research Experience for Undergraduates (REU) program (EEC 1659710) and the Army Research Office.

Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

PubMed

Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

2017-11-01

A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R 2 >0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

One Dimension Analytical Model of Normal Ballistic Impact on Ceramic/Metal Gradient Armor

NASA Astrophysics Data System (ADS)

Liu, Lisheng; Zhang, Qingjie; Zhai, Pengcheng; Cao, Dongfeng

2008-02-01

An analytical model of normal ballistic impact on the ceramic/metal gradient armor, which is based on modified Alekseevskii-Tate equations, has been developed. The process of gradient armour impacted by the long rod can be divided into four stages in this model. First stage is projectile's mass erosion or flowing phase, mushrooming phase and rigid phase; second one is the formation of comminuted ceramic conoid; third one is the penetration of gradient layer and last one is the penetration of metal back-up plate. The equations of third stage have been advanced by assuming the behavior of gradient layer as rigid-plastic and considering the effect of strain rate on the dynamic yield strength.

One Dimension Analytical Model of Normal Ballistic Impact on Ceramic/Metal Gradient Armor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Lisheng; Zhang Qingjie; Zhai Pengcheng

2008-02-15

An analytical model of normal ballistic impact on the ceramic/metal gradient armor, which is based on modified Alekseevskii-Tate equations, has been developed. The process of gradient armour impacted by the long rod can be divided into four stages in this model. First stage is projectile's mass erosion or flowing phase, mushrooming phase and rigid phase; second one is the formation of comminuted ceramic conoid; third one is the penetration of gradient layer and last one is the penetration of metal back-up plate. The equations of third stage have been advanced by assuming the behavior of gradient layer as rigid-plastic andmore » considering the effect of strain rate on the dynamic yield strength.« less

Highly crosslinked polymeric monoliths for reversed-phase capillary liquid chromatography of small molecules.

PubMed

Liu, Kun; Tolley, H Dennis; Lee, Milton L

2012-03-02

Seven crosslinking monomers, i.e., 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), neopentyl glycol dimethacrylate (NPGDMA), 1,5-pentanediol dimethacrylate (1,5-PDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,10-decanediol dimethacrylate (1,10-DDDMA), and 1,12-dodecanediol dimethacrylate (1,12-DoDDMA), were used to synthesize highly cross-linked monolithic capillary columns for reversed-phase liquid chromatography (RPLC) of small molecules. Dodecanol and methanol were chosen as "good" and "poor" porogenic solvents, respectively, for these monoliths, and were investigated in detail to provide insight into the selection of porogen concentration using 1,12-DoDDMA. Isocratic elution of alkylbenzenes at a flow rate of 300 nL/min was conducted for all of the monoliths. Gradient elution of alkylbenzenes and alkylparabens provided high resolution separations. Optimized monoliths synthesized from all seven crosslinking monomers showed high permeability. Several of the monoliths demonstrated column efficiencies in excess of 50,000 plates/m. Monoliths with longer alkyl-bridging chains showed very little shrinking or swelling in solvents of different polarities. Column preparation was highly reproducible; the relative standard deviation (RSD) values (n=3) for run-to-run and column-to-column were less than 0.25% and 1.20%, respectively, based on retention times of alkylbenzenes. Copyright © 2012 Elsevier B.V. All rights reserved.

Reversible ratchet effects for vortices in conformal pinning arrays

DOE PAGES

Reichhardt, Charles; Ray, Dipanjan; Reichhardt, Cynthia Jane Olson

2015-05-04

A conformal transformation of a uniform triangular pinning array produces a structure called a conformal crystal which preserves the sixfold ordering of the original lattice but contains a gradient in the pinning density. Here we use numerical simulations to show that vortices in type-II superconductors driven with an ac drive over gradient pinning arrays produce the most pronounced ratchet effect over a wide range of parameters for a conformal array, while square gradient or random gradient arrays with equivalent pinning densities give reduced ratchet effects. In the conformal array, the larger spacing of the pinning sites in the direction transversemore » to the ac drive permits easy funneling of interstitial vortices for one driving direction, producing the enhanced ratchet effect. In the square array, the transverse spacing between pinning sites is uniform, giving no asymmetry in the funneling of the vortices as the driving direction switches, while in the random array, there are numerous easy-flow channels present for either direction of drive. We find multiple ratchet reversals in the conformal arrays as a function of vortex density and ac amplitude, and correlate the features with a reversal in the vortex ordering, which is greater for motion in the ratchet direction. In conclusion, the enhanced conformal pinning ratchet effect can also be realized for colloidal particles moving over a conformal array, indicating the general usefulness of conformal structures for controlling the motion of particles.« less

Geomorphic origin of Merritt Island-Cape Canaveral, Florida, USA: A paleodelta of the reversed St. Johns River?

NASA Astrophysics Data System (ADS)

Adams, Peter N.

2018-04-01

The Merritt Island-Cape Canaveral (MICCSC) sedimentary complex consists of a series of adjacent, non-conformable, beach ridge sets that suggest a multi-phase constructional history, but the feature's geomorphic and sedimentary origins are not well-understood. In spite of its notable sedimentary volume (surface area = 1200 km2), the MICCSC lacks a clear sediment source, or supply mechanism, to explain its presence today. Previously published U/Th, radiocarbon and OSL dates indicate that beach ridge deposition was active during MIS 5 (130-80 ka) on Merritt Island, but has occurred over a shorter, younger time interval on Cape Canaveral proper (6 ka to present). In this paper, it is proposed that the MICCSC is an abandoned paleodelta whose fluvial source provided a sediment supply sufficient for coastal progradation. Although the MICCSC, today, does not receive an appreciable sediment supply, the nearly 23,000 km2 drainage basin of the St. Johns River may well have provided such a sediment supply during MIS 5 times. This low-gradient fluvial system currently empties to the Atlantic Ocean some 200 km north of the MICCSC (near Jacksonville, Florida) but may have flowed southward during the time of MICCSC sedimentary construction, then experienced flow reversal since MIS 5 times. Three possible uplift mechanisms are proposed to explain the northward down-tilting that may have reversed the flow direction of the St. Johns, abandoning deltaic construction of the MICCSC: (1) karst-driven, flexural isostatic uplift in response to carbonate rock dissolution in central Florida, (2) glacio-hydro-isostatic tilting/back-tilting cycles during loading and unloading of the Laurentide ice sheet during the Pleistocene, and (3) mantle convection-driven dynamic topography operating within southeastern North America since the Pliocene. This example testifies to the sensitivity of low-gradient, low-relief landscapes to various sources of uplift, be they isostatic or otherwise.

Determination of phenolic xenoestrogens in water by liquid chromatography with coulometric-array detection.

PubMed

Inoue, Koichi; Yoshie, Yuriko; Kondo, Sachiko; Yoshimura, Yoshihiro; Nakazawa, Hiroyuki

2002-02-08

A sensitive method for the simultaneous determination of phenolic xenoestrogens such as bisphenol A, 2,4-dichlorophenol, 4-tert,-butylphenol, 4-n2-pentylphenol, 4-n-hexylphenol, 4-n-heptylphenol, 4-octylphenol, 4-nonylphenol was developed using reversed-phase LC and coulometric-array detection. Stepwise gradient elution with phosphoric acid in water-acetonitrile was used. The calibration curves were linear in the range of 5.0 (or 10.0)-1000 ng ml(-1) with correlation coefficients of 0.9978-0.9999, the limits of detection were 0.01-0.02 ng ml(-1). Sample clean-up was performed by solid-phase extraction (SPE) using 3M Empore extraction disks. Three commercial sorbents, C18, SDB-XD (styrene-divinylbenzene polymer) and SDB-RPS (sulfonated styrene-divinylbenzene polymer) were compared. The highest recoveries were obtained with SDB-RPS. They were above 70% with a relative standard deviation of less than 15%. The proposed method was applied to the determination of phenolic xenoestrogens in various water samples.

Rapid and sensitive method for determination of withaferin-A in human plasma by HPLC.

PubMed

Patial, Pankaj; Gota, Vikram

2011-02-01

To develop and validate a rapid and sensitive high-performance liquid chromatographic method for determination of withaferin-A in human plasma. Withaferin-A, the active molecule of a traditional Indian herb, has demonstrated several biological activities in preclinical models. A validated bioassay is not available for its pharmacokinetic evaluation. The chromatographic system used a reverse-phase C18 column with UV-visible detection at 225 nm. The mobile phase consisted of water and acetonitrile applied in a gradient flow. Withaferin-A was extracted by simple protein-precipitation technique. The calibration curve was linear in the concentration range of 0.05-1.6 µg/ml. The method has the desired sensitivity to detect the plasma concentration range of withaferin-A that is likely to show biological activity based on in vitro data. This is the first HPLC method ever described for the estimation of withaferin-A in human plasma which could be applied for pharmacokinetic studies.

Development and Validation of RP-LC Method for the Determination of Cinnarizine/Piracetam and Cinnarizine/Heptaminol Acefyllinate in Presence of Cinnarizine Reported Degradation Products

PubMed Central

EL-Houssini, Ola M.; Zawilla, Nagwan H.; Mohammad, Mohammad A.

2013-01-01

Specific stability indicating reverse-phase liquid chromatography (RP-LC) assay method (SIAM) was developed for the determination of cinnarizine (Cinn)/piracetam (Pira) and cinnarizine (Cinn)/heptaminol acefyllinate (Hept) in the presence of the reported degradation products of Cinn. A C18 column and gradient mobile phase was applied for good resolution of all peaks. The detection was achieved at 210 nm and 254 nm for Cinn/Pira and Cinn/Hept, respectively. The responses were linear over concentration ranges of 20–200, 20–1000 and 25–1000 μgmL−1 for Cinn, Pira, and Hept respectively. The proposed method was validated for linearity, accuracy, repeatability, intermediate precision, and robustness via statistical analysis of the data. The method was shown to be precise, accurate, reproducible, sensitive, and selective for the analysis of Cinn/Pira and Cinn/Hept in laboratory prepared mixtures and in pharmaceutical formulations. PMID:24137049

Authentication and Quantitation of Fraud in Extra Virgin Olive Oils Based on HPLC-UV Fingerprinting and Multivariate Calibration

PubMed Central

Carranco, Núria; Farrés-Cebrián, Mireia; Saurina, Javier

2018-01-01

High performance liquid chromatography method with ultra-violet detection (HPLC-UV) fingerprinting was applied for the analysis and characterization of olive oils, and was performed using a Zorbax Eclipse XDB-C8 reversed-phase column under gradient elution, employing 0.1% formic acid aqueous solution and methanol as mobile phase. More than 130 edible oils, including monovarietal extra-virgin olive oils (EVOOs) and other vegetable oils, were analyzed. Principal component analysis results showed a noticeable discrimination between olive oils and other vegetable oils using raw HPLC-UV chromatographic profiles as data descriptors. However, selected HPLC-UV chromatographic time-window segments were necessary to achieve discrimination among monovarietal EVOOs. Partial least square (PLS) regression was employed to tackle olive oil authentication of Arbequina EVOO adulterated with Picual EVOO, a refined olive oil, and sunflower oil. Highly satisfactory results were obtained after PLS analysis, with overall errors in the quantitation of adulteration in the Arbequina EVOO (minimum 2.5% adulterant) below 2.9%. PMID:29561820

Simultaneous UHPLC-UV analysis of hydroxychloroquine, minocycline and doxycycline from serum samples for the therapeutic drug monitoring of Q fever and Whipple's disease.

PubMed

Armstrong, Nicholas; Richez, Magali; Raoult, Didier; Chabriere, Eric

2017-08-15

A fast UHPLC-UV method was developed for the simultaneous analysis of Hydroxychloroquine, Minocycline and Doxycycline drugs from 100μL of human serum samples. Serum samples were extracted by liquid-liquid extraction and injected into a phenyl hexyl reverse phase column. Compounds were separated using a mobile phase linear gradient and monitored by UV detection at 343nm. Chloroquine and Oxytetracycline were used as internal standards. Lower and upper limits of quantifications, as well as the other levels of calibration, were validated with acceptable accuracy (<15% deviation) and precision (<15% coefficient of variation) according to the European Medicines Agency guidelines. This new method enables cost and time reduction and was considered suitable for the clinical laboratory. It is the first published assay for the therapeutic drug monitoring of patients diagnosed with Q fever or Whipple's disease. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of tilmicosin residues in chicken, cattle, swine, and sheep tissues by liquid chromatography.

PubMed

Stobba-Wiley, C M; Chang, J P; Elsbury, D T; Moran, J W; Turner, J M; Readnour, R S; Stobba-Wiley, C M; Chang, J P; Elsbury, D T; Moran, J W; Turner, J M; Readnour, R S

2000-01-01

A method was developed and validated for determination and quantitation of tilmicosin residues in swine, cattle, and sheep edible tissues, as well as chicken fat, skin, and muscle over a concentration range of 0.025 microg/g-20 microg/g. For chicken kidney and liver, the method was validated over a range of 0.060 microg/g-20 microg/g. The tissue sample was extracted with methanol and a C18 cartridge was used for solid-phase extraction cleanup. A reversed-phase gradient liquid chromatographic method with detection at 280 nm was used to separate the tilmicosin from matrix components in 30 min run time. The limit of quantitation (LOQ) of the method was 0.025 microg/g for all tested tissues except chicken kidney and liver, for which the LOQ was 0.06 microg/g. Average recoveries for tissue samples ranged from 73 to 98%. Relative standard deviation values ranged from 0.6 to 14.7%.

First gas-phase metallicity gradients of 0.1 ≲ z ≲ 0.8 galaxies with MUSE

NASA Astrophysics Data System (ADS)

Carton, David; Brinchmann, Jarle; Contini, Thierry; Epinat, Benoît; Finley, Hayley; Richard, Johan; Patrício, Vera; Schaye, Joop; Nanayakkara, Themiya; Weilbacher, Peter M.; Wisotzki, Lutz

2018-05-01

Galaxies at low-redshift typically possess negative gas-phase metallicity gradients (centres more metal-rich than their outskirts). Whereas, it is not uncommon to observe positive metallicity gradients in higher-redshift galaxies (z ≳ 0.6). Bridging these epochs, we present gas-phase metallicity gradients of 84 star-forming galaxies between 0.08 < z < 0.84. Using the galaxies with reliably determined metallicity gradients, we measure the median metallicity gradient to be negative (-0.039^{+0.007}_{-0.009} dex/kpc). Underlying this, however, is significant scatter: (8 ± 3)% [7] of galaxies have significantly positive metallicity gradients, (38 ± 5)% [32] have significantly negative gradients, (31 ± 5)% [26] have gradients consistent with being flat. (The remaining (23 ± 5)% [19] have unreliable gradient estimates.) We notice a slight trend for a more negative metallicity gradient with both increasing stellar mass and increasing star formation rate (SFR). However, given the potential redshift and size selection effects, we do not consider these trends to be significant. Indeed, once we normalize the SFR relative to that of the main sequence, we do not observe any trend between the metallicity gradient and the normalized SFR. This is contrary to recent studies of galaxies at similar and higher redshifts. We do, however, identify a novel trend between the metallicity gradient of a galaxy and its size. Small galaxies (rd < 3 kpc) present a large spread in observed metallicity gradients (both negative and positive gradients). In contrast, we find no large galaxies (rd > 3 kpc) with positive metallicity gradients, and overall there is less scatter in the metallicity gradient amongst the large galaxies. These large (well-evolved) galaxies may be analogues of present-day galaxies, which also show a common negative metallicity gradient.

Fast gradient screening of pharmaceuticals with 5 cm long, narrow bore reversed-phase columns packed with sub-3 μm core-shell and sub-2 μm totally porous particles.

PubMed

Fekete, Szabolcs; Fekete, Jeno

2011-04-15

The performance of 5 cm long narrow-bore columns packed with 2.6-2.7 μm core-shell particles and a column packed with 1.7 μm totally porous particles was compared in very fast gradient separations of polar neutral active pharmaceutical compounds. Peak capacities as a function of flow-rate and gradient time were measured. Peak capacities around 160-170 could be achieved within 25 min with these 5 cm long columns. The highest peak capacity was obtained with the Kinetex column however it was found that as the flow-rate increases, the peak capacity of the new Poroshell-120 column is getting closer to that obtained with the Kinetex column. Considering the column permeability, peak capacity per unit time and per unit pressure was also calculated. In this comparison the advantage of sub-3 μm core-shell particles is more significant compared to sub-2 μm totally porous particles. Moreover it was found that the very similar sized (d(p)=2.7 μm) and structured (ρ=0.63) new Poroshell-120 and the earlier introduced Ascentis Express particles showed different efficiency. Results obtained showed that the 5 cm long narrow bore columns packed with sub-3 μm core-shell particles offer the chance of very fast and efficient gradient separations, thus these columns can be applied for fast screening measurements of routine pharmaceutical analysis such as cleaning validation. Copyright © 2011 Elsevier B.V. All rights reserved.

Gradient free energy in the axially anisotropic superfluid phases of /sup 3/He in the BCS approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brand, H.; Doerfle, M.

1981-02-01

We present the gradient free energy in the BCS approximation for the A phase in high magnetic fields and the A/sub 1/ phase. The A phase without external magnetic field, which has been considered previously by Blount and Cross, emerges as a special case of the result for the A phase in high magnetic fields.

Prediction of gradient retention data for hydrophilic interaction liquid chromatographic separation of native and fluorescently labeled oligosaccharides.

PubMed

Vaňková, Nikola; Česla, Petr

2017-02-17

In this work, we have investigated the predictive properties of mixed-mode retention model and oligomeric mixed-mode model, taking into account the contribution of monomeric units to the retention, in hydrophilic interaction liquid chromatography. The gradient retention times of native maltooligosaccharides and their fluorescent derivatives were predicted in the oligomeric series with number of monomeric glucose units in the range from two to seven. The maltooligosaccharides were separated on a packed column with carbamoyl-bonded silica stationary phase and 15 gradient profiles with different initial and final mobile phase composition were used with the gradient times 5; 7.5 and 10min. The predicted gradient retention times were compared for calculations based on isocratic retention data and gradient retention data, which provided better accuracy of the results. By comparing two different mobile phase additives, the more accurate retention times were predicted in mobile phases containing ammonium acetate. The acidic derivatives, prepared by reaction of an oligosaccharide with 2-aminobenzoic acid or 8-aminonaphthalene-1,3,6-trisulfonic acid, provided more accurate predictions of the retention data in comparison to native oligosaccharides or their neutral derivatives. The oligomeric mixed-mode model allowed prediction of gradient retention times using only one gradient profile, which significantly speeded-up the method development. Copyright © 2017 Elsevier B.V. All rights reserved.

Gradient Self-Doped CuBi2O4 with Highly Improved Charge Separation Efficiency.

PubMed

Wang, Fuxian; Septina, Wilman; Chemseddine, Abdelkrim; Abdi, Fatwa F; Friedrich, Dennis; Bogdanoff, Peter; van de Krol, Roel; Tilley, S David; Berglund, Sean P

2017-10-25

A new strategy of using forward gradient self-doping to improve the charge separation efficiency in metal oxide photoelectrodes is proposed. Gradient self-doped CuBi 2 O 4 photocathodes are prepared with forward and reverse gradients in copper vacancies using a two-step, diffusion-assisted spray pyrolysis process. Decreasing the Cu/Bi ratio of the CuBi 2 O 4 photocathodes introduces Cu vacancies that increase the carrier (hole) concentration and lowers the Fermi level, as evidenced by a shift in the flat band toward more positive potentials. Thus, a gradient in Cu vacancies leads to an internal electric field within CuBi 2 O 4 , which can facilitate charge separation. Compared to homogeneous CuBi 2 O 4 photocathodes, CuBi 2 O 4 photocathodes with a forward gradient show highly improved charge separation efficiency and enhanced photoelectrochemical performance for reduction reactions, while CuBi 2 O 4 photocathodes with a reverse gradient show significantly reduced charge separation efficiency and photoelectrochemical performance. The CuBi 2 O 4 photocathodes with a forward gradient produce record AM 1.5 photocurrent densities for CuBi 2 O 4 up to -2.5 mA/cm 2 at 0.6 V vs RHE with H 2 O 2 as an electron scavenger, and they show a charge separation efficiency of 34% for 550 nm light. The gradient self-doping accomplishes this without the introduction of external dopants, and therefore the tetragonal crystal structure and carrier mobility of CuBi 2 O 4 are maintained. Lastly, forward gradient self-doped CuBi 2 O 4 photocathodes are protected with a CdS/TiO 2 heterojunction and coated with Pt as an electrocatalyst. These photocathodes demonstrate photocurrent densities on the order of -1.0 mA/cm 2 at 0.0 V vs RHE and evolve hydrogen with a faradaic efficiency of ∼91%.

Effect of structural in-depth heterogeneities on electrical properties of Pb(Zr0.52Ti0.48) O3 thin films as revealed by nano-beam X-ray diffraction

NASA Astrophysics Data System (ADS)

Vaxelaire, N.; Kovacova, V.; Bernasconi, A.; Le Rhun, G.; Alvarez-Murga, M.; Vaughan, G. B. M.; Defay, E.; Gergaud, P.

2016-09-01

A direct quantification of a structural in-depth composition in the lead zirconate titanate Pb(Zr,Ti)O3 thin films of morphotropic composition has been conducted using the newly available X-ray nano-pencil beam (i.e., beam size of 100 nm × 1 μm) diffraction approach. We tested two samples with different Zr/Ti chemical gradients. Here, we demonstrate the presence of a significant microstructural gradient between the rhombohedral and tetragonal phases through PbZrxTi1-xO3 (PZT) films with a 100 nm in-depth resolution. The phase gradient extends over around 350 nm, and it is repeated through the PZT film three times, which corresponds to the number of thermal annealings. Moreover, this microstructural gradient is in agreement with the Zr/Ti chemical gradient observed by the secondary ion mass spectroscopy (SIMS). Indeed, the quantity of tetragonal phases rises in the Ti-rich zones as revealed by SIMS, and the quantity of rhombohedral phases rises in the Zr-rich zones. We also demonstrated a huge difference in the in-depth phase variation between the two tested samples. The gradient free sample still contains 4.7% of phase variation through the film and the amplified gradient contains 9.6% of phase variation through the film. Knowing that the gradient free sample shows better electric and piezoelectric coefficients, one can draw a correlation between the chemical composition, crystallographic homogeneity, and electro-mechanical properties of the film. The more close the film is to the morphotropic composition and the more it is crystallographically homogeneous, the higher the piezoelectric coefficients of the PZT are. Finally, the adequate knowledge of phase variation and its relation to the fabrication technique are crucial for the enhancement of the PZT electro-mechanical properties. Our methodology and findings open up new perspectives in establishing a relevant quantitative feedback to reach an ultimate electro-mechanical coupling in the sol-gel PZT thin films.

Separation of alkylphenols by normal-phase and reversed-phase high-performance liquid chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schabron, J.F.; Hurtubise, R.J.; Silver, H.F.

1978-11-01

Empirical correlation factors were developed which relate log k' values for alkylphenols, the naphthols, and two phenylphenols to structural features. Both normal-phase and reversed-phase chromatographic systems were studied. The stationary phases employed in the normal-phase work were ..mu..-Bondapak CN, ..mu..-Bondapak NH/sub 2/, and ..mu..-Porasil. The structural features which affect retention in the normal-phase chromatographic systems are the number of ortho substituents, the number of aliphatic carbons, and the number of aromatic rings. The stationary phases employed in the reversed-phase work were ..mu..-Bondapak C/sub 18/ and ..mu..-Bondapak CN. The structural features which affect retention in the reversed-phase chromatographic systems are themore » number of aliphatic carbons and the number of aromatic double bonds. On ..mu..-Bondapak C/sub 18/, the presence or absence of a nonaromatic ring is of added importance.« less

Evaluation of Selected MR Pulse Sequences

NASA Astrophysics Data System (ADS)

Shin, Yong-Jin

1990-01-01

This research addressed four main areas of radiofrequency (rf) pulse programming: (1) correction of instrumentation errors in spin echo sequences by use of phase rolling of the rf pulses; (2) chemical shift imaging of water and lipid; (3) development of special pulse sequences for the measurement of phosphorus metabolites by ^ {31}P spectroscopy and lactate by ^1H spectroscopy; and (4) flow methods to measure and separate diffusion from perfusion. All experiments were performed on a horizontal 2.0T (superconducting magnet) 31-cm small-bore MR system. Computer programming and data analysis were performed on a PDP 11/84 computer system. 1. The effects of rf tips, dc and gain misadjustments in the rf spectrometer were evaluated for a series of MR images. Four different phase cycling schemes (FIXED, ALTERNATE, FORWARD, REVERSED) to suppress unwanted signal components such as mirror and ghost images were evaluated using two signal acquisitions. When the receiver phase factor is cycled counter-clockwise (REVERSED), these artifacts are completely removed. 2. A major problem common to all chemical shift imaging methods is static magnetic field non-uniformity. Four methods (Dixon's, CHESS, SECSI and modified CHESS-SECSI) were quantitatively evaluated for the measurement of water and fat content, which are separated by approximately 3.5 ppm, in in vivo biological tissues. It was demonstrated in phantoms that the modified CHESS+SECSI method gave superior results even without field shimming. 3. The development of new MR rf pulse sequences is essential in order to acquire specialized in vivo information concerning biologic metabolites. The time course of change in concentration of lactate and of phosphorus metabolites in human forearm muscle before and after exercise was determined. Lactate concentration returned to normal in 25 minutes after exercise. The Pi/PCr ratio was 0.25 before exercise, and increased to 0.5 at 4.5 minutes after exercise. 4. The fourth study involved the incorporation of a bipolar gradient pulse technique into a spin echo sequence; by varying the strength of the bipolar gradients, diffusion as well as perfusion can be quantitatively determined. The diffusion coefficient (D) for H_2O and acetone were 2.10 and 5.06 (times10 ^{-3} mm^2 /sec), respectively. The perfusion factor was linearly incremental for stepwise increases in flow velocities.

Nocturnal Reversed Flows Above Parallel Ridges in Perdigão, Portugal

NASA Astrophysics Data System (ADS)

Krishnamurthy, R.; Fernando, H. J.; Leo, L. S.; Vassallo, D.; Hocut, C. M.; Creegan, E.; Rodriguez, C. V.; Palma, J. L.

2017-12-01

Prediction of topographically forced or induced wind events is extremely important for dispersion modeling and wind energy studies in complex terrain. To improve the current understanding of micro-scale processes over complex terrain, a large-scale field experiment was conducted in Perdigão, Portugal from May 1st, 2017 to June 15th, 2017. Measurements over a periodic valley were performed using 52 meteorological met-masts, 30 Doppler Lidars (scanning & vertical profilers), 2 tethered lifting systems and other remote sensing instruments (Sodar-rass, wind profilers & radiometer), and radiosondes were released every 6 hours over the period of study. The observations showed several cases of flow reversals confined to a thin layer of 70 - 100 m above the ridge under stably stratified conditions. These flow reversals were mostly observed during the lee wave formation over the periodic valley. It was observed that the flow reversal occurs predominantly under two atmospheric conditions: a) presence of large recirculation zones on the lee side of the hill causing a pressure gradient between the lee-side floor and the mountain ridge, and b) local change in the horizontal pressure gradient due to differential heating rates of the neighboring valley atmospheres. Microscale flow simulations could capture these observed flow reversals. Based on the network of tower instruments and remote sensing devices, the development, structure and occurrences of the flow reversals are being analyzed and quantified. Since these flow reversals are observed within the rotor swept area of modern wind turbines, they would drastically increase the fatigue loads on wind turbine blades. This presentation will include reversed flow observations from several synchronized scanning Doppler Lidars and meteorological towers and a theoretical framework for reverse flow over parallel valleys.

A reversed-phase compatible thin-layer chromatography autography for the detection of acetylcholinesterase inhibitors.

PubMed

Ramallo, I Ayelen; García, Paula; Furlan, Ricardo L E

2015-11-01

A dual readout autographic assay to detect acetylcholinesterase inhibitors present in complex matrices adsorbed on reversed-phase or normal-phase thin-layer chromatography plates is described. Enzyme gel entrapment with an amphiphilic copolymer was used for assay development. The effects of substrate and enzyme concentrations, pH, incubation time, and incubation temperature on the sensitivity and the detection limit of the assay were evaluated. Experimental design and response surface methodology were used to optimize conditions with a minimum number of experiments. The assay allowed the detection of 0.01% w/w of physostigmine in both a spiked Sonchus oleraceus L. extract chromatographed on normal phase and a spiked Pimenta racemosa (Mill.) J.W. Moore leaf essential oil chromatographed on reversed phase. Finally, the reversed-phase thin-layer chromatography assay was applied to reveal the presence of an inhibitor in the Cymbopogon citratus (DC.) Stapf essential oil. The developed assay is able to detect acetylcholinesterase inhibitors present in complex matrixes that were chromatographed in normal phase or reversed-phase thin-layer chromatography. The detection limit for physostigmine on both normal and reversed phase was of 1×10(-4) μg. The results can be read by a change in color and/or a change in fluorescence. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of the chloride gradient across red cell membranes on sodium and potassium movements

PubMed Central

Cotterrell, D.; Whittam, R.

1971-01-01

1. A study has been made to see whether active and passive movements of sodium and potassium in human red blood cells are influenced by changing the chloride gradient and hence the potential difference across the cell membrane. 2. Chloride distribution was measured between red cells and isotonic solutions with a range of concentrations of chloride and non-penetrating anions (EDTA, citrate, gluconate). The cell chloride concentration was greater than that outside with low external chloride, suggesting that the sign of the membrane potential was reversed. The chloride ratio (internal/external) was approximately equal to the inverse of the hydrogen ion ratio at normal and low external chloride, and inversely proportional to external pH. These results show that chloride is passively distributed, making it valid to calculate the membrane potential from the chloride ratio. 3. Ouabain-sensitive (pump) potassium influx and sodium efflux were decreased by not more than 20 and 40% respectively on reversing the chloride gradient, corresponding to a change in membrane potential from -9 to +30 mV. In contrast, passive (ouabain-insensitive) movements were reversibly altered — potassium influx was decreased about 60% and potassium efflux was increased some tenfold. Sodium influx was unaffected by the nature of the anion and depended only on the external sodium concentration, whereas ouabain-insensitive sodium efflux was increased about threefold. When external sodium was replaced by potassium there was a decrease in ouabain-insensitive sodium efflux with normal chloride, but an increase in low-chloride medium. 4. Net movements of sodium and potassium were roughly in accord with the unidirectional fluxes. 5. The results suggest that reversing the chloride gradient and, therefore, the sign of the membrane potential, had little effect on the sodium pump, but caused a marked increase in passive outward movements of both sodium and potassium ions. PMID:4996368

Increasing Paid Work Time? A New Puzzle for Multinational Time-Diary Research

ERIC Educational Resources Information Center

Gershuny, Jonathan

2011-01-01

This explores the reasons that paid work time may be rising, at least in anglophone countries. Three explanations are discussed. (1) An historical reversal of the work/leisure gradient with respect to social position or social status. This gradient was once positive, but is now negative; evidence of this change from 11 developed countries is drawn…

Gradient stationary phase optimized selectivity liquid chromatography with conventional columns.

PubMed

Chen, Kai; Lynen, Frédéric; Szucs, Roman; Hanna-Brown, Melissa; Sandra, Pat

2013-05-21

Stationary phase optimized selectivity liquid chromatography (SOSLC) is a promising technique to optimize the selectivity of a given separation. By combination of different stationary phases, SOSLC offers excellent possibilities for method development under both isocratic and gradient conditions. The so far available commercial SOSLC protocol utilizes dedicated column cartridges and corresponding cartridge holders to build up the combined column of different stationary phases. The present work is aimed at developing and extending the gradient SOSLC approach towards coupling conventional columns. Generic tubing was used to connect short commercially available LC columns. Fast and base-line separation of a mixture of 12 compounds containing phenones, benzoic acids and hydroxybenzoates under both isocratic and linear gradient conditions was selected to demonstrate the potential of SOSLC. The influence of the connecting tubing on the deviation of predictions is also discussed.

On the relation between phase-field crack approximation and gradient damage modelling

NASA Astrophysics Data System (ADS)

Steinke, Christian; Zreid, Imadeddin; Kaliske, Michael

2017-05-01

The finite element implementation of a gradient enhanced microplane damage model is compared to a phase-field model for brittle fracture. Phase-field models and implicit gradient damage models share many similarities despite being conceived from very different standpoints. In both approaches, an additional differential equation and a length scale are introduced. However, while the phase-field method is formulated starting from the description of a crack in fracture mechanics, the gradient method starts from a continuum mechanics point of view. At first, the scope of application for both models is discussed to point out intersections. Then, the analysis of the employed mathematical methods and their rigorous comparison are presented. Finally, numerical examples are introduced to illustrate the findings of the comparison which are summarized in a conclusion at the end of the paper.

A Validated Stability-Indicating RP-UPLC Method for Simultaneous Determination of Desloratadine and Sodium Benzoate in Oral Liquid Pharmaceutical Formulations.

PubMed

Kumar, Navneet; Sangeetha, Dhanaraj; Reddy, Pingili Sunil; Prakash, Lakkireddy

2012-01-01

A novel, sensitive and selective stability-indicating gradient reverse phase ultra performance liquid chromatographic method was developed and validated for the quantitative determination of desloratadine and sodium benzoate in pharmaceutical oral liquid formulation. The chromatographic separation was achieved on Acquity BEH C8 (100 mm × 2.1 mm) 1.7 μm column by using mobile phase containing a gradient mixture of solvent A (0.05 M KH(2)PO(4) and 0.07 M triethylamine, pH 3.0) and B (50:25:25 v/v/v mixture of acetonitrile, methanol and water) at flow rate of 0.4 mL/min. Column temperature was maintained at 40°C and detection was carried out at a wavelength of 272 nm. The described method shows excellent linearity over a range of 0.254 μg/mL to 76.194 μg/mL for desloratadine and 1.006 μg/mL to 301.67 μg/mL for sodium benzoate. The correlation coefficient for desloratadine and sodium benzoate was more than 0.999. To establish stability-indicating capability of the method, drug product was subjected to the stress conditions of acid, base, oxidative, hydrolytic, thermal and photolytic degradation. The degradation products were well resolved from desloratadine and sodium benzoate. The developed method was validated as per international ICH guidelines with respect to specificity, linearity, LOD, LOQ, accuracy, precision and robustness.

Quality-by-design-based ultra high performance liquid chromatography related substances method development by establishing the proficient design space for sumatriptan and naproxen combination.

PubMed

Patel, Prinesh N; Karakam, Vijaya Saradhi; Samanthula, Gananadhamu; Ragampeta, Srinivas

2015-10-01

Quality-by-design-based methods hold greater level of confidence for variations and greater success in method transfer. A quality-by-design-based ultra high performance liquid chromatography method was developed for the simultaneous assay of sumatriptan and naproxen along with their related substances. The first screening was performed by fractional factorial design comprising 44 experiments for reversed-phase stationary phases, pH, and organic modifiers. The results of screening design experiments suggested phenyl hexyl column and acetonitrile were the best combination. The method was further optimized for flow rate, temperature, and gradient time by experimental design of 20 experiments and the knowledge space was generated for effect of variable on response (number of peaks ≥ 1.50 - resolution). Proficient design space was generated from knowledge space by applying Monte Carlo simulation to successfully integrate quantitative robustness metrics during optimization stage itself. The final method provided the robust performance which was verified and validated. Final conditions comprised Waters® Acquity phenyl hexyl column with gradient elution using ammonium acetate (pH 4.12, 0.02 M) buffer and acetonitrile at 0.355 mL/min flow rate and 30°C. The developed method separates all 13 analytes within a 15 min run time with fewer experiments compared to the traditional quality-by-testing approach. ©2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prototyping of thermoplastic microfluidic chips and their application in high-performance liquid chromatography separations of small molecules.

PubMed

Wouters, Sam; De Vos, Jelle; Dores-Sousa, José Luís; Wouters, Bert; Desmet, Gert; Eeltink, Sebastiaan

2017-11-10

The present paper discusses practical aspects of prototyping of microfluidic chips using cyclic olefin copolymer as substrate and the application in high-performance liquid chromatography. The developed chips feature a 60mm long straight separation channel with circular cross section (500μm i.d.) that was created using a micromilling robot. To irreversibly seal the top and bottom chip substrates, a solvent-vapor-assisted bonding approach was optimized, allowing to approximate the ideal circular channel geometry. Four different approaches to establish the micro-to-macro interface were pursued. The average burst pressure of the microfluidic chips in combination with an encasing holder was established at 38MPa and the maximum burst pressure was 47MPa, which is believed to be the highest ever report for these polymer-based microfluidic chips. Porous polymer monolithic frits were synthesized in-situ via UV-initiated polymerization and their locations were spatially controlled by the application of a photomask. Next, high-pressure slurry packing was performed to introduce 3μm silica reversed-phase particles as the stationary phase in the separation channel. Finally, the application of the chip technology is demonstrated for the separation of alkyl phenones in gradient mode yielding baseline peak widths of 6s by applying a steep gradient of 1.8min at a flow rate of 10μL/min. Copyright © 2017 Elsevier B.V. All rights reserved.

Improving liquid chromatography-mass spectrometry sensitivity using a subambient pressure ionization with nanoelectrospray (SPIN) interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Keqi; Page, Jason S.; Marginean, Ioan

2011-04-22

In this work the Subambient Pressure Ionization with Nanoelectrospray (SPIN) ion source and interface which operates at ~15-30 Torr is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100-400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5-12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospraymore » ionization (ESI) source was obtained for detected peptides.« less

Spectroscopic characterization and quantitative determination of atorvastatin calcium impurities by novel HPLC method

NASA Astrophysics Data System (ADS)

Gupta, Lokesh Kumar

2012-11-01

Seven process related impurities were identified by LC-MS in the atorvastatin calcium drug substance. These impurities were identified by LC-MS. The structure of impurities was confirmed by modern spectroscopic techniques like 1H NMR and IR and physicochemical studies conducted by using synthesized authentic reference compounds. The synthesized reference samples of the impurity compounds were used for the quantitative HPLC determination. These impurities were detected by newly developed gradient, reverse phase high performance liquid chromatographic (HPLC) method. The system suitability of HPLC analysis established the validity of the separation. The analytical method was validated according to International Conference of Harmonization (ICH) with respect to specificity, precision, accuracy, linearity, robustness and stability of analytical solutions to demonstrate the power of newly developed HPLC method.

Transformations of fluxes and forces describing the simultaneous transport of water and heat in unsaturated porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raats, P.A.C.

1975-12-01

Balances of mass for the water in N distinct phases and a balance of heat for the medium as a whole were formulated. Following Philip and de Vries, it was assumed that the flux of water in each phase is proportional to the gradient of the pressure in that phase and that the diffusive component of the flux of heat is proportional to the gradient of the temperature. Clapeyron equations were used to express the gradient of the pressure in any phase in terms of the gradient of the pressure in a reference state and of the temperature. The referencemore » state may be the water in one of the phases or the water in some measuring device such as a tensiometer or a psychrometer. Expressions for the total flux of water and for the diffusive flux of heat plus the convective flux of heat associated with the conversion from any phase to the reference state were shown to satisfy the onsager reciprocal relations. A theorem due to Meixner was used to delineate the class of fluxes and forces that preserves these relations. In particular, it was shown that if the gradients of water content and temperature are used as the driving forces, the onsager relations are no longer satisfied.« less

Effects of internal structure on equilibrium of field-reversed configuration plasma sustained by rotating magnetic field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yambe, Kiyoyuki; Inomoto, Michiaki; Okada, Shigefumi

The effects of an internal structure on the equilibrium of a field-reversed configuration (FRC) plasma sustained by rotating magnetic field is investigated by using detailed electrostatic probe measurements in the FRC Injection Experiment apparatus [S. Okada, et al., Nucl. Fusion. 45, 1094 (2005)]. An internal structure installed axially on the geometrical axis, which simulates Ohmic transformer or external toroidal field coils on the FRC device, brings about substantial changes in plasma density profile. The internal structure generates steep density-gradients not only on the inner side but on the outer side of the torus. The radial electric field is observed tomore » sustain the ion thermal pressure-gradient in the FRC without the internal structure; however, the radial electric field is not sufficient to sustain the increased ion thermal pressure-gradient in the FRC with the internal structure. Spontaneously driven azimuthal ion flow will be accountable for the imbalance of the radial pressure which is modified by the internal structure.« less

Observation of trapped-electron-mode microturbulence in reversed field pinch plasmas

NASA Astrophysics Data System (ADS)

Duff, J. R.; Williams, Z. R.; Brower, D. L.; Chapman, B. E.; Ding, W. X.; Pueschel, M. J.; Sarff, J. S.; Terry, P. W.

2018-01-01

Density fluctuations in the large-density-gradient region of improved confinement Madison Symmetric Torus reversed field pinch (RFP) plasmas exhibit multiple features that are characteristic of the trapped-electron mode (TEM). Core transport in conventional RFP plasmas is governed by magnetic stochasticity stemming from multiple long-wavelength tearing modes. Using inductive current profile control, these tearing modes are reduced, and global confinement is increased to that expected for comparable tokamak plasmas. Under these conditions, new short-wavelength fluctuations distinct from global tearing modes appear in the spectrum at a frequency of f ˜ 50 kHz, which have normalized perpendicular wavenumbers k⊥ρs≲ 0.2 and propagate in the electron diamagnetic drift direction. They exhibit a critical-gradient threshold, and the fluctuation amplitude increases with the local electron density gradient. These characteristics are consistent with predictions from gyrokinetic analysis using the Gene code, including increased TEM turbulence and transport from the interaction of remnant tearing magnetic fluctuations and zonal flow.

The development of an elastic reverse gradient garment to be used as a countermeasure for cardiovascular deconditioning

NASA Technical Reports Server (NTRS)

Annis, J. F.; Webb, P.

1980-01-01

Using a new nomex lycra elastic fabric and individualized garment engineering techniques, reverse gradient garments (RGG's) were designed, constructed, and tested for effectiveness as a countermeasure against cardiovascular deconditioning. By combining torso compensated positive pressure breathing with a distally diminishing gradient of counterpressure supplied by the elastic fabric on the limbs, the RGG acts to pool blood in the extremities of recumbent persons much as though they were standing erect in 1 g. The RGG stresses the vasculature in a fashion similar to that experienced by the normally active man, hence preventing or limiting the development of post weightlessness orthostatic intolerance and related conditions. Four male, college age subjects received daily treatments with the RGG during a 15 day bedrest study. Four additional subjects also underwent the bedrest, but received no treatments; they served as controls. The preliminary indication was that the RGG was somewhat effective in limiting the deconditioning process.

[Application of general retention time formula for gradient liquid chromatography in the studies of ladder-like gradient elution].

PubMed

Sun, Xiaoli; Hao, Weiqiang; Wang, Junde; Di, Bin; Chen, Qiang; Zhuang, Wei; Yu, Qiang; Zhang, Peipei

2013-08-01

By not explicitly specifying the type of solvent strength model, the features of ladder-like gradient elution were studied based on the general retention time formula that was derived in our previous work. For the case where the solute is eluted at like gradient, we derived the expression that connects the mobile phase composition (phiR), at which the solute is eluted from the column, with the gradient slope (B). It was shown that phiR will increase with the increase of B in this case. For the case where the solute is eluted at the last isocratic segment of the ladder-like gradient, it was proven that the retention time (tR) will correlate linearly with the reciprocal of the gradient slope (1/B) when the initial and final mobile phase compositions are set to be constant. In experiments, by taking biphenyl as the sample, the values of retention time in isocratic and gradient elution were measured on a C18 column by using a mixture of methanol and water as the mobile phase. The experimental values were found to be well consistent with the theoretical values that were calculated from the expressions. These expressions will be helpful to understand the features of the ladder-like gradient in practice.

Rational and Efficient Preparative Isolation of Natural Products by MPLC-UV-ELSD based on HPLC to MPLC Gradient Transfer.

PubMed

Challal, Soura; Queiroz, Emerson Ferreira; Debrus, Benjamin; Kloeti, Werner; Guillarme, Davy; Gupta, Mahabir Prashad; Wolfender, Jean-Luc

2015-11-01

In natural product research, the isolation of biomarkers or bioactive compounds from complex natural extracts represents an essential step for de novo identification and bioactivity assessment. When pure natural products have to be obtained in milligram quantities, the chromatographic steps are generally labourious and time-consuming. In this respect, an efficient method has been developed for the reversed-phase gradient transfer from high-performance liquid chromatography to medium-performance liquid chromatography for the isolation of pure natural products at the level of tens of milligrams from complex crude natural extracts. The proposed method provides a rational way to predict retention behaviour and resolution at the analytical scale prior to medium-performance liquid chromatography, and guarantees similar performances at both analytical and preparative scales. The optimisation of the high-performance liquid chromatography separation and system characterisation allows for the prediction of the gradient at the medium-performance liquid chromatography scale by using identical stationary phase chemistries. The samples were introduced in medium-performance liquid chromatography using a pressure-resistant aluminium dry load cell especially designed for this study to allow high sample loading while maintaining a maximum achievable flow rate for the separation. The method has been validated with a mixture of eight natural product standards. Ultraviolet and evaporative light scattering detections were used in parallel for a comprehensive monitoring. In addition, post-chromatographic mass spectrometry detection was provided by high-throughput ultrahigh-performance liquid chromatography time-of-flight mass spectrometry analyses of all fractions. The processing of all liquid chromatography-mass spectrometry data in the form of an medium-performance liquid chromatography x ultra high-performance liquid chromatography time-of-flight mass spectrometry matrix enabled an efficient localisation of the compounds of interest in the generated fractions. The methodology was successfully applied for the separation of three different plant extracts that contain many diverse secondary metabolites. The advantages and limitations of this approach and the theoretical chromatographic background that rules such as liquid chromatography gradient transfer are presented from a practical viewpoint. Georg Thieme Verlag KG Stuttgart · New York.

Topological superconductivity in the extended Kitaev-Heisenberg model

NASA Astrophysics Data System (ADS)

Schmidt, Johann; Scherer, Daniel D.; Black-Schaffer, Annica M.

2018-01-01

We study superconducting pairing in the doped Kitaev-Heisenberg model by taking into account the recently proposed symmetric off-diagonal exchange Γ . By performing a mean-field analysis, we classify all possible superconducting phases in terms of symmetry, explicitly taking into account effects of spin-orbit coupling. Solving the resulting gap equations self-consistently, we map out a phase diagram that involves several topologically nontrivial states. For Γ <0 , we find a competition between a time-reversal symmetry-breaking chiral phase with Chern number ±1 and a time-reversal symmetric nematic phase that breaks the rotational symmetry of the lattice. On the other hand, for Γ ≥0 we find a time-reversal symmetric phase that preserves all the lattice symmetries, thus yielding clearly distinguishable experimental signatures for all superconducting phases. Both of the time-reversal symmetric phases display a transition to a Z2 nontrivial phase at high doping levels. Finally, we also include a symmetry-allowed spin-orbit coupling kinetic energy and show that it destroys a tentative symmetry-protected topological order at lower doping levels. However, it can be used to tune the time-reversal symmetric phases into a Z2 nontrivial phase even at lower doping.

Simultaneous quantification of paracetamol, acetylsalicylic acid and papaverine with a validated HPLC method.

PubMed

Kalmár, Eva; Gyuricza, Anett; Kunos-Tóth, Erika; Szakonyi, Gerda; Dombi, György

2014-01-01

Combined drug products have the advantages of better patient compliance and possible synergic effects. The simultaneous application of several active ingredients at a time is therefore frequently chosen. However, the quantitative analysis of such medicines can be challenging. The aim of this study is to provide a validated method for the investigation of a multidose packed oral powder that contained acetylsalicylic acid, paracetamol and papaverine-HCl. Reversed-phase high-pressure liquid chromatography was used. The Agilent Zorbax SB-C18 column was found to be the most suitable of the three different stationary phases tested for the separation of the components of this sample. The key parameters in the method development (apart from the nature of the column) were the pH of the aqueous phase (set to 3.4) and the ratio of the organic (acetonitrile) and the aqueous (25 mM phosphate buffer) phases, which was varied from 7:93 (v/v) to 25:75 (v/v) in a linear gradient, preceded by an initial hold. The method was validated: linearity, precision (repeatability and intermediate precision), accuracy, specificity and robustness were all tested, and the results met the ICH guidelines. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Characterizing the nature of subpulse drifting in pulsars

NASA Astrophysics Data System (ADS)

Basu, Rahul; Mitra, Dipanjan

2018-04-01

We report a detailed study of subpulse drifting in four long-period pulsars. These pulsars were observed in the Meterwavelength Single-pulse Polarimetric Emission Survey and the presence of phase-modulated subpulse drifting was reported in each case. We carried out longer duration and more sensitive observations lasting 7000-12 000 periods in the frequency range 306-339 MHz. The drifting features were characterized in great detail, including the phase variations across the pulse window. For two pulsars, J0820-1350 and J1720-2933, the phases changed steadily across the pulse window. The pulsar J1034-3224 has five components. The leading component was very weak and was barely detectable in our single-pulse observations. The four trailing components showed subpulse drifting. The phase variations changed in alternate components with a reversal in the sign of the gradient. This phenomenon is known as bi-drifting. The pulsar J1555-3134 showed two distinct peak frequencies of comparable strengths in the fluctuation spectrum. The two peaks did not appear to be harmonically related and were most likely a result of different physical processes. Additionally, the long observations enabled us to explore the temporal variations of the drifting features. The subpulse drifting was largely constant with time but small fluctuations around a mean value were seen.

Simultaneous analysis of different classes of phytohormones in coconut (Cocos nucifera L.) water using high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry after solid-phase extraction.

PubMed

Ma, Zhen; Ge, Liya; Lee, Anna S Y; Yong, Jean Wan Hong; Tan, Swee Ngin; Ong, Eng Shi

2008-03-10

Coconut (Cocos nucifera L.) water, which contains many uncharacterized phytohormones is extensively used as a growth promoting supplement in plant tissue culture. In this paper, a high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination of various classes phytohormones, including indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), abscisic acid (ABA), gibberellic acid (GA), zeatin (Z), N(6)-benzyladenine (BA), alpha-naphthaleneacetic acid (NAA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in young coconut water (CW). The analysis was carried out using a reverse-phase HPLC gradient elution, with an aqueous mobile phase (containing 0.1% formic acid, pH adjusted to 3.2 with triethylamine (TEA)) modified by methanol, and solute detection made at 265 nm wavelength. The method was validated for specificity, quantification, accuracy and precision. After preconcentration of putative endogenous phytohormones in CW using C(18) solid-phase extraction (SPE) cartridges, the HPLC method was able to screen for putative endogenous phytohormones present in CW. Finally, the identities of the putative phytohormones present in CW were further confirmed using independent liquid chromatography-tandem mass spectrometry (LC-MS/MS) equipped with an electrospray ionization (ESI) interface.

Improved quality-by-design compliant methodology for method development in reversed-phase liquid chromatography.

PubMed

Debrus, Benjamin; Guillarme, Davy; Rudaz, Serge

2013-10-01

A complete strategy dedicated to quality-by-design (QbD) compliant method development using design of experiments (DOE), multiple linear regressions responses modelling and Monte Carlo simulations for error propagation was evaluated for liquid chromatography (LC). The proposed approach includes four main steps: (i) the initial screening of column chemistry, mobile phase pH and organic modifier, (ii) the selectivity optimization through changes in gradient time and mobile phase temperature, (iii) the adaptation of column geometry to reach sufficient resolution, and (iv) the robust resolution optimization and identification of the method design space. This procedure was employed to obtain a complex chromatographic separation of 15 antipsychotic basic drugs, widely prescribed. To fully automate and expedite the QbD method development procedure, short columns packed with sub-2 μm particles were employed, together with a UHPLC system possessing columns and solvents selection valves. Through this example, the possibilities of the proposed QbD method development workflow were exposed and the different steps of the automated strategy were critically discussed. A baseline separation of the mixture of antipsychotic drugs was achieved with an analysis time of less than 15 min and the robustness of the method was demonstrated simultaneously with the method development phase. Copyright © 2013 Elsevier B.V. All rights reserved.

Amplification of thermostable lipase genes fragment from thermogenic phase of domestic waste composting process

NASA Astrophysics Data System (ADS)

Nurhasanah, Nurbaiti, Santi; Madayanti, Fida; Akhmaloka

2015-09-01

Lipases are lipolytic enzymes, catalyze the hydrolysis of fatty acid ester bonds of triglycerides to produce free fatty acids and glycerol. The enzyme is widely used in various fields of biotechnological industry. Hence, lipases with unique properties (e.g.thermostable lipase) are still being explored by variation methods. One of the strategy is by using metagenomic approach to amplify the gene directly from environmental sample. This research was focused on amplification of lipase gene fragment directly from the thermogenic phase of domestic waste composting in aerated trenches. We used domestic waste compost from waste treatment at SABUGA, ITB for the sample. Total chromosomal DNA were directly extracted from several stages at thermogenic phase of compost. The DNA was then directly used as a template for amplification of thermostable lipase gene fragments using a set of internal primers namely Flip-1a and Rlip-1a that has been affixed with a GC clamp in reverse primer. The results showed that the primers amplified the gene from four stages of thermogenic phase with the size of lipase gene fragment of approximately 570 base pairs (bp). These results were further used for Denaturing Gradient Gel Electrophoresis (DGGE) analysis to determine diversity of thermostable lipase gene fragments.

On the feasibility to conduct gradient liquid chromatography separations in narrow-bore columns at pressures up to 2000bar.

PubMed

De Pauw, Ruben; Swier, Tim; Degreef, Bart; Desmet, Gert; Broeckhoven, Ken

2016-11-18

The limits in operating pressures are extended for narrow-bore columns in gradient elution up to 2000bar. As the required pumps for these pressures are incompatible with common chromatographic solvents and are not suitable to apply a mobile phase composition gradient, a mobile phase delivery and injection system is described and experimentally validated which allows to use any possible chromatographic solvent in isocratic and gradient elution. The mobile phase delivery and injection system also allows to perform multiple separations without the need to depressurize the column. This system consists out of 5 dual on/off valves and two large volume loops in which the gradient and equilibration volume of initial mobile phase are loaded by a commercial liquid chromatography pump. The loops are then flushed toward the column at extreme pressures. The mobile phase delivery and injection system is first evaluated in isocratic elution and shows a comparable performance to a state-of-the-art commercial flow-through-needle injector but with twice the pressure rating. Distortion of the loaded gradient by dispersion in the gradient storage loop is studied. The effect of the most important parameters (such as flow rate, pressure and gradient steepness) is experimentally investigated. Different gradient steepnesses and volumes can be applied at different flow rates and operating pressures with a good repeatability. Due to the isobaric operation of the pumps, the gradient is monitored in real-time by a mass flow meter installed at the detector outlet. The chromatograms are then converted from time to volume-base. A separation of a 19-compound sample is performed on a 300×2.1mm column at 1000bar and on a 600×2.1mm column at 2000bar. The peak capacity was found to increase from 141 to 199 and thus scales with L as is predicted by theory. This allows to conclude that the inlet pressure for narrow-bore columns in gradient elution can be increased up to 2000bar without fundamental pressure-induced limitations. Copyright © 2016 Elsevier B.V. All rights reserved.

Surprising SES Gradients in Mortality, Health, and Biomarkers in a Latin American Population of Adults

PubMed Central

Dow, William H.

2009-01-01

Background To determine socioeconomic status (SES) gradients in the different dimensions of health among elderly Costa Ricans. Hypothesis: SES disparities in adult health are minimal in Costa Rican society. Methods Data from the Costa Rican Study on Longevity and Healthy Aging study: 8,000 elderly Costa Ricans to determine mortality in the period 2000–2007 and a subsample of 3,000 to determine prevalence of several health conditions and biomarkers from anthropometry and blood and urine specimens. Results The ultimate health indicator, mortality, as well as the metabolic syndrome, reveals that better educated and wealthier individuals are worse off. In contrast, quality of life–related measures such as functional and cognitive disabilities, physical frailty, and depression all clearly worsen with lower SES. Overall self-reported health (SRH) also shows a strong positive SES gradient. Traditional cardiovascular risk factors such as diabetes and cholesterol are not significantly related to SES, but hypertension and obesity are worse among high-SES individuals. Reflecting mixed SES gradients in behaviors, smoking and lack of exercise are more common among low SES, but high calorie diets are more common among high SES. Conclusions Negative modern behaviors among high-SES groups may be reversing cardiovascular risks across SES groups, hence reversing mortality risks. But negative SES gradients in healthy years of life persist. PMID:19196695

Photothermal Nanocomposite Hydrogel Actuator with Electric-Field-Induced Gradient and Oriented Structure.

PubMed

Yang, Yang; Tan, Yun; Wang, Xionglei; An, Wenli; Xu, Shimei; Liao, Wang; Wang, Yuzhong

2018-03-07

Recent research of hydrogel actuators is still not sophisticated enough to meet the requirement of fast, reversible, complex, and robust reconfiguration. Here, we present a new kind of poly( N-isopropylacrylamide)/graphene oxide gradient hydrogel by utilizing direct current electric field to induce gradient and oriented distribution of graphene oxide into poly( N-isopropylacrylamide) hydrogel. Upon near-infrared light irradiation, the hydrogel exhibited excellent comprehensive actuation performance as a result of directional bending deformation, promising great potential in the application of soft actuators and optomechanical system.

Generalized gradient algorithm for trajectory optimization

NASA Technical Reports Server (NTRS)

Zhao, Yiyuan; Bryson, A. E.; Slattery, R.

1990-01-01

The generalized gradient algorithm presented and verified as a basis for the solution of trajectory optimization problems improves the performance index while reducing path equality constraints, and terminal equality constraints. The algorithm is conveniently divided into two phases, of which the first, 'feasibility' phase yields a solution satisfying both path and terminal constraints, while the second, 'optimization' phase uses the results of the first phase as initial guesses.

Analysis of sesquiterpene lactones, lignans, and flavonoids in wormwood (Artemisia absinthium L.) using high-performance liquid chromatography (HPLC)-mass spectrometry, reversed phase HPLC, and HPLC-solid phase extraction-nuclear magnetic resonance.

PubMed

Aberham, Anita; Cicek, Serhat Sezai; Schneider, Peter; Stuppner, Hermann

2010-10-27

Today, the medicinal use of wormwood (Artemisia absinthium) is enjoying a resurgence of popularity. This study presents a specific and validated high-performance liquid chromatography (HPLC)-diode array detection method for the simultaneous determination and quantification of bioactive compounds in wormwood and commercial preparations thereof. Five sesquiterpene lactones, two lignans, and a polymethoxylated flavonoid were baseline separated on RP-18 material, using a solvent gradient consisting of 0.085% (v/v) o-phosphoric acid and acetonitrile. The flow rate was 1.0 mL/min, and chromatograms were recorded at 205 nm. The stability of absinthin was tested exposing samples to light, moisture, and different temperatures. Methanolic and aqueous solutions of absinthin were found to be stable for up to 6 months. This was also the case when the solid compound was kept in the refrigerator at -35 °C. In contrast, the colorless needles, when stored at room temperature, turned yellow. Three degradation compounds (anabsin, anabsinthin, and the new dimer 3'-hydroxyanabsinthin) were identified by HPLC-mass spectrometry and HPLC-solid-phase extraction-nuclear magnetic resonance and quantified by the established HPLC method.

Rapid quantification of resveratrol in mouse plasma by ultra high pressure liquid chromatography (UPLC) coupled to tandem mass spectrometry.

PubMed

Castillo-Pichardo, Linette; Dharmawardhane, Suranganie; Rodríguez-Orengo, José F

2014-12-01

The objective of this study was to develop a rapid and sensitive method for the quantification of resveratrol, a polyphenolic compound with multiple health beneficial effects, in mouse plasma. We used reversed-phase ultra high pressure-liquid chromatography with tandem mass spectrometry detection for the determination of resveratrol levels in mouse plasma. An Agilent Zorbax Eclipse Plus C18 column (2.1 mm x 50 mm, 1.8 μm) was used as the stationary phase. The mobile phase consisted of a gradient formed using 1 mM ammonium fluoride and methanol. Using this improved method, we obtained a retention time of 2.2 min and a total run time of 5 min, for resveratrol. The calibration curve for resveratrol showed a linear range from 0.5 to 100 ng/mL. The average coefficient of variation was 6% for interday variation and 4% for intraday variation. The recovery for resveratrol in mouse plasma was 85 ± 10% (mean ± standard deviation). The method presented herein allows a rapid and very sensitive quantification of resveratrol in mouse plasma at concentrations as low as 500 ppt.

Multi heart-cutting two-dimensional liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry method for the determination of endocrine disrupting compounds in water.

PubMed

Matějíček, David

2012-03-30

The multi-heart-cutting two-dimensional liquid chromatography-tandem mass spectrometry method using atmospheric pressure photoionization has been developed and successfully validated for the determination of nine endocrine disrupting compounds in river water. The method is based on the use of two different reverse-phase columns connected through a six-port two-position switching valve equipped with a 200 μl loop. An orthogonal separation was achieved by proper selection of stationary phases, mobile phases, and the use of a gradient elution in both dimensions. The method shows excellent performance in terms of accuracy (86.2-111.1%), precision (intra-batch: 6.7-11.2%, inter-batch: 7.2-13.5%), and sensitivity (1.2-7.1 ng l(-1)). Twenty real samples collected from the Loučka and the Svratka rivers were analyzed, the studied compounds were found in all Svratka samples (9.7-11.2 ng l(-1) for β-estradiol, 7.6-9.3 ng l(-1) for estrone, and 24.6-38.7 ng l(-1) for bisphenol A). Copyright © 2012 Elsevier B.V. All rights reserved.

A Study of the Development of Steady and Periodic Unsteady Turbulent Wakes Through Curved Channels at Positive, Zero, and Negative Streamwise Pressure Gradients, Part 1

NASA Technical Reports Server (NTRS)

Schobeiri, M. T.; John, J.

1996-01-01

The turbomachinery wake flow development is largely influenced by streamline curvature and streamwise pressure gradient. The objective of this investigation is to study the development of the wake under the influence of streamline curvature and streamwise pressure gradient. The experimental investigation is carried out in two phases. The first phase involves the study of the wake behind a stationary circular cylinder (steady wake) in curved channels at positive, zero, and negative streamwise pressure gradients. The mean velocity and Reynolds stress components are measured using a X-hot-film probe. The measured quantities obtained in probe coordinates are transformed to a curvilinear coordinate system along the wake centerline and are presented in similarity coordinates. The results of the steady wakes suggest strong asymmetry in velocity and Reynolds stress components. However, the velocity defect profiles in similarity coordinates are almost symmetrical and follow the same distribution as the zero pressure gradient straight wake. The results of Reynolds stress distributions show higher values on the inner side of the wake than the outer side. Other quantities, including the decay of maximum velocity defect, growth of wake width, and wake integral parameters, are also presented for the three different pressure gradient cases of steady wake. The decay rate of velocity defect is fastest for the negative streamwise pressure gradient case and slowest for the positive pressure gradient case. Conversely, the growth of the wake width is fastest for the positive streamwise pressure gradient case and slowest for the negative streamwise pressure gradient. The second phase studies the development of periodic unsteady wakes generated by the circular cylinders of the rotating wake generator in a curved channel at zero streamwise pressure gradient. Instantaneous velocity components of the periodic unsteady wakes, measured with a stationary X-hot-film probe, are analyzed by the phase averaging techniques. The temporal distribution of velocity and Reynolds stress components obtained in a stationary frame of reference are transformed to a spatial distribution in a relative frame of reference. Profiles of phase-averaged velocity and Reynolds stress distributions in the relative frame of reference and similarity coordinates are presented. The velocity defect and Reynolds stress distributions agree with the results of the wake development behind a stationary cylinder in the curved channel at zero streamwise pressure gradient. The phase-averaged third-order correlations, presented in the relative frame of reference and similarity coordinates, show pronounced asymmetric features.

Unifying expression scale for peptide hydrophobicity in proteomic reversed phase high-pressure liquid chromatography experiments.

PubMed

Grigoryan, Marine; Shamshurin, Dmitry; Spicer, Victor; Krokhin, Oleg V

2013-11-19

As an initial step in our efforts to unify the expression of peptide retention times in proteomic liquid chromatography-mass spectrometry (LC-MS) experiments, we aligned the chromatographic properties of a number of peptide retention standards against a collection of peptides commonly observed in proteomic experiments. The standard peptide mixtures and tryptic digests of samples of different origins were separated under the identical chromatographic condition most commonly employed in proteomics: 100 Å C18 sorbent with 0.1% formic acid as an ion-pairing modifier. Following our original approach (Krokhin, O. V.; Spicer, V. Anal. Chem. 2009, 81, 9522-9530) the retention characteristics of these standards and collection of tryptic peptides were mapped into hydrophobicity index (HI) or acetonitrile percentage units. This scale allows for direct visualization of the chromatographic outcome of LC-MS acquisitions, monitors the performance of the gradient LC system, and simplifies method development and interlaboratory data alignment. Wide adoption of this approach would significantly aid understanding the basic principles of gradient peptide RP-HPLC and solidify our collective efforts in acquiring confident peptide retention libraries, a key component in the development of targeted proteomic approaches.

Three-dimensional desirability spaces for quality-by-design-based HPLC development.

PubMed

Mokhtar, Hatem I; Abdel-Salam, Randa A; Hadad, Ghada M

2015-04-01

In this study, three-dimensional desirability spaces were introduced as a graphical representation method of design space. This was illustrated in the context of application of quality-by-design concepts on development of a stability indicating gradient reversed-phase high-performance liquid chromatography method for the determination of vinpocetine and α-tocopheryl acetate in a capsule dosage form. A mechanistic retention model to optimize gradient time, initial organic solvent concentration and ternary solvent ratio was constructed for each compound from six experimental runs. Then, desirability function of each optimized criterion and subsequently the global desirability function were calculated throughout the knowledge space. The three-dimensional desirability spaces were plotted as zones exceeding a threshold value of desirability index in space defined by the three optimized method parameters. Probabilistic mapping of desirability index aided selection of design space within the potential desirability subspaces. Three-dimensional desirability spaces offered better visualization and potential design spaces for the method as a function of three method parameters with ability to assign priorities to this critical quality as compared with the corresponding resolution spaces. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Probing the limits of the rigid-intensity-shift model in differential-phase-contrast scanning transmission electron microscopy

NASA Astrophysics Data System (ADS)

Clark, L.; Brown, H. G.; Paganin, D. M.; Morgan, M. J.; Matsumoto, T.; Shibata, N.; Petersen, T. C.; Findlay, S. D.

2018-04-01

The rigid-intensity-shift model of differential-phase-contrast imaging assumes that the phase gradient imposed on the transmitted probe by the sample causes the diffraction pattern intensity to shift rigidly by an amount proportional to that phase gradient. This behavior is seldom realized exactly in practice. Through a combination of experimental results, analytical modeling and numerical calculations, using as case studies electron microscope imaging of the built-in electric field in a p-n junction and nanoscale domains in a magnetic alloy, we explore the breakdown of rigid-intensity-shift behavior and how this depends on the magnitude of the phase gradient and the relative scale of features in the phase profile and the probe size. We present guidelines as to when the rigid-intensity-shift model can be applied for quantitative phase reconstruction using segmented detectors, and propose probe-shaping strategies to further improve the accuracy.

Simultaneous determination of related substances of telmisartan and hydrochlorothiazide in tablet dosage form by using reversed phase high performance liquid chromatographic method

PubMed Central

Mukhopadhyay, Sutirtho; Kadam, Kiran; Sawant, Laxman; Nachane, Dhanashree; Pandita, Nancy

2011-01-01

Objective: Telmisartan is a potent, long-lasting, nonpeptide antagonist of the angiotensin II type-1 (AT1) receptor that is indicated for the treatment of essential hypertension. Hydrochlorothiazide is a widely prescribed diuretic and it is indicated for the treatment of edema, control of essential hypertension and management of diabetes insipidus. In the current article a new, accurate, sensitive, precise, rapid, reversed phase high performance liquid chromatography (RP-HPLC) method was developed for determination of related substances of Telmisartan and Hydrochlorthiazide in tablet dosage form. Materials and Methods: Simultaneous determination of related substances was performed on Kromasil C18 analytical column (250 × 4.6 mm; 5μm pertical size) column at 40°C employing a gradient elution. Mobile phase consisting of solvent A (solution containing 2.0 g of potassium dihydrogen phosphate anhydrous and 1.04 g of Sodium 1- Hexane sulphonic acid monohydrate per liter of water, adjusted to pH 3.0 with orthophosphoric acid) and solvent B (mixture of Acetonitrile: Methanol in the ratio 80:20 v/v) was used at a flow rate of 1.0 ml min–1. UV detection was performed at 270 nm. Results: During method validation parameter such as precision, linearity, accuracy, specificity, limit of detection and quantification were evaluated, which remained within acceptable limits. Conclusions: HPLC analytical method is linear, accurate, precise, robust and specific, being able to separate the main drug from its degradation products. It may find application for the routine analysis of the related substances of both Telmisartan and Hydrochlorthiazide in this combination tablets. PMID:21966158

Separation and quantification of 15 carotenoids by reversed phase high performance liquid chromatography coupled to diode array detection with isosbestic wavelength approach.

PubMed

Mitrowska, Kamila; Vincent, Ursula; von Holst, Christoph

2012-04-13

The manuscript presents the development of a new reverse phase high performance liquid chromatography (RP-HPLC) photo diode array detection method allowing the separation and quantification of 15 carotenoids (adonirubin, adonixanthin, astaxanthin, astaxanthin dimethyl disuccinate, asteroidenone, beta-apo-8'-carotenal, beta-apo-8'-carotenoic acid ethyl ester, beta-carotene, canthaxanthin, capsanthin, citranaxanthin, echinenone, lutein, lycopene, and zeaxanthin), 10 of which are feed additives authorised within the European Union. The developed method allows for the reliable determination of the total carotenoid content in one run using the corresponding E-isomer as calibration standard while taking into account the E/Z-isomers composition. This is a key criterion for the application of the method, since for most of the analytes included in this study analytical standards are only available for the E-isomers. This goal was achieved by applying the isosbestic concept, in order to identify specific wavelengths, at which the absorption coefficients are identical for all stereoisomers concerned. The second target referred to the optimisation of the LC conditions. By means of an experimental design, an optimised RP-HPLC method was developed allowing for a sufficient chromatographic separation of all carotenoids. The selected method uses a Suplex pKb-100 HPLC column and applying a gradient with a mixture of acetonitrile, tert-butyl-methyl ether and water as mobile phases. The limits of detection and limits of quantification ranged from 0.06 mg L(-1) to 0.14 mg L(-1) and from 0.20 mg L(-1) to 0.48 mg L(-1), respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

A novel reverse phase high-performance liquid chromatography method for standardization of Orthosiphon stamineus leaf extracts.

PubMed

Saidan, Noor Hafizoh; Aisha, Abdalrahim F A; Hamil, Mohd Shahrul Ridzuan; Majid, Amin Malik Shah Abdul; Ismail, Zhari

2015-01-01

Orthosiphon stamineus Benth. (Lamiaceae) is a traditional medicinal plant which has been used in treating various ailments such as kidney diseases, bladder inflammation, arthritis and diabetes. The leaves contain high concentration of phenolic compounds, thus, rosmarinic acid (RA), 3'-hydroxy-5, 6, 7, 4'-tetramethoxyflavone (TMF), sinensetin (SIN) and eupatorin (EUP) were chosen as a marker compounds for standardization of various O. stamineus leaf extracts. The aim was to develop and validate a new high-performance liquid chromatography (HPLC) method for quantification of 4 marker compounds (RA, TMF, SIN, EUP) in various O. stamineus leaf extracts. The method was developed and validated using RP-HPLC-diode-array detection at 320 nm for accuracy, precision and limits of detection and was applied for quantification of it markers in five different extracts prepared in solvents with increasing polarity, using a gradient mobile phase 0.1% formic acid: Acetonitrile at a flow rate of 1 ml/min on reverse phase acclaim polar advantage II C18 column (3 μm, 3 × 150 mm) with 18 min separation time. The developed method provided satisfactory precision, and the accuracy of this method was in the range of 90.2% to 105.5%. All of 4 compounds showed good linearity at R2 > 0.999. The developed method is a simple, cost effective with shorter run time (18 min) in comparison to previous methods (30 min) and utilization of environmental-friendly solvents system. Therefore, this method has the potential to replace currently used methods in the routine standardization work of O. stamineus extracts, raw materials and its commercial products.

A novel reverse phase high-performance liquid chromatography method for standardization of Orthosiphon stamineus leaf extracts

PubMed Central

Saidan, Noor Hafizoh; Aisha, Abdalrahim F.A.; Hamil, Mohd Shahrul Ridzuan; Majid, Amin Malik Shah Abdul; Ismail, Zhari

2015-01-01

Background: Orthosiphon stamineus Benth. (Lamiaceae) is a traditional medicinal plant which has been used in treating various ailments such as kidney diseases, bladder inflammation, arthritis and diabetes. The leaves contain high concentration of phenolic compounds, thus, rosmarinic acid (RA), 3’-hydroxy-5, 6, 7, 4’-tetramethoxyflavone (TMF), sinensetin (SIN) and eupatorin (EUP) were chosen as a marker compounds for standardization of various O. stamineus leaf extracts. Objective: The aim was to develop and validate a new high-performance liquid chromatography (HPLC) method for quantification of 4 marker compounds (RA, TMF, SIN, EUP) in various O. stamineus leaf extracts. Materials and Methods: The method was developed and validated using RP-HPLC-diode-array detection at 320 nm for accuracy, precision and limits of detection and was applied for quantification of it markers in five different extracts prepared in solvents with increasing polarity, using a gradient mobile phase 0.1% formic acid: Acetonitrile at a flow rate of 1 ml/min on reverse phase acclaim polar advantage II C18 column (3 μm, 3 × 150 mm) with 18 min separation time. Results: The developed method provided satisfactory precision, and the accuracy of this method was in the range of 90.2% to 105.5%. All of 4 compounds showed good linearity at R2 > 0.999. Conclusion: The developed method is a simple, cost effective with shorter run time (18 min) in comparison to previous methods (30 min) and utilization of environmental-friendly solvents system. Therefore, this method has the potential to replace currently used methods in the routine standardization work of O. stamineus extracts, raw materials and its commercial products. PMID:25598631

Determination of a selection of anti-epileptic drugs and two active metabolites in whole blood by reversed phase UPLC-MS/MS and some examples of application of the method in forensic toxicology cases.

PubMed

Karinen, Ritva; Vindenes, Vigdis; Hasvold, Inger; Olsen, Kirsten Midtbøen; Christophersen, Asbjørg S; Øiestad, Elisabeth

2015-07-01

Quantitative determination of anti-epileptic drug concentrations is of great importance in forensic toxicology cases. Although the drugs are not usually abused, they are important post-mortem cases where the question of both lack of compliance and accidental or deliberate poisoning might be raised. In addition these drugs can be relevant for driving under the influence cases. A reversed phase ultra-performance liquid chromatography-tandem mass spectrometry method has been developed for the quantitative analysis of the anti-epileptic compounds carbamazepine, carbamazepine-10,11-epoxide, gabapentin, lamotrigine, levetiracetam, oxcarbazepine, 10-OH-carbazepine, phenobarbital, phenytoin, pregabalin, and topiramate in whole blood, using 0.1 mL sample volume with methaqualone as internal standard. Sample preparation was a simple protein precipitation with acetonitrile and methanol. The diluted supernatant was directly injected into the chromatographic system. Separation was performed on an Acquity UPLC® BEH Phenyl column with gradient elution and a mildly alkaline mobile phase. The mass spectrometric detection was performed in positive ion mode, except for phenobarbital, and multiple reaction monitoring was used for drug quantification. The limits of quantification for the different anti-epileptic drugs varied from 0.064 to 1.26 mg/L in blood, within-day and day-to-day relative standard deviations from 2.2 to 14.7% except for phenobarbital. Between-day variation for phenobarbital was 20.4% at the concentration level of 3.5 mg/L. The biases for all compounds were within ±17.5%. The recoveries ranged between 85 and 120%. The corrected matrix effects were 88-106% and 84-110% in ante-mortem and post-mortem whole blood samples, respectively. Copyright © 2014 John Wiley & Sons, Ltd.

Modeling the zonal disintegration of rocks near deep level tunnels by gradient internal variable continuous phase transition theory

NASA Astrophysics Data System (ADS)

Haoxiang, Chen; Qi, Chengzhi; Peng, Liu; Kairui, Li; Aifantis, Elias C.

2015-12-01

The occurrence of alternating damage zones surrounding underground openings (commonly known as zonal disintegration) is treated as a "far from thermodynamic equilibrium" dynamical process or a nonlinear continuous phase transition phenomenon. The approach of internal variable gradient theory with diffusive transport, which may be viewed as a subclass of Landau's phase transition theory, is adopted. The order parameter is identified with an irreversible strain quantity, the gradient of which enters into the expression for the free energy of the rock system. The gradient term stabilizes the material behavior in the post-softening regime, where zonal disintegration occurs. The results of a simplified linearized analysis are confirmed by the numerical solution of the nonlinear problem.

Glutamine/glutamate (Glx) concentration in prefrontal cortex predicts reversal learning performance in the marmoset.

PubMed

Lacreuse, Agnès; Moore, Constance M; LaClair, Matthew; Payne, Laurellee; King, Jean A

2018-07-02

This study used Magnetic Resonance Spectroscopy (MRS) to identify potential neurometabolitic markers of cognitive performance in male (n = 7) and female (n = 8) middle-aged (∼5 years old) common marmosets (Callithrix jacchus). Anesthetized marmosets were scanned with a 4.7 T/40 cm horizontal magnet equipped with 450 mT/m magnetic field gradients and a 20 G/cm magnetic field gradient insert, within 3 months of completing the CANTAB serial Reversal Learning task. Neurometabolite concentrations of N-Acetyl Asparate, Myo-Inositol, Choline, Phosphocreatine + creatine, Glutamate and Glutamine were acquired from a 3 mm 3 voxel positioned in the Prefrontal Cortex (PFC). Males acquired the reversals (but not simple discriminations) faster than the females. Higher PFC Glx (glutamate + glutamine) concentration was associated with faster acquisition of the reversals. Interestingly, the correlation between cognitive performance and Glx was significant in males, but not in females. These results suggest that MRS is a useful tool to identify biochemical markers of cognitive performance in the healthy nonhuman primate brain and that biological sex modulates the relationship between neurochemical composition and cognition. Copyright © 2018 Elsevier B.V. All rights reserved.

Sensitive determination of nitrophenol isomers by reverse-phase high-performance liquid chromatography in conjunction with liquid-liquid extraction

USDA-ARS?s Scientific Manuscript database

A method for the highly sensitive determination of 2-, 3- and 4- nitrophenols was developed using reverse-phase high-performance liquid chromatography (RP-HPLC) with a UV photodiode array detector. Using a reverse-phase column and 40% aqueous acetonitrile as an eluent (i.e. isocratic elution), the i...

Three dimensional liquid chromatography coupling ion exchange chromatography/hydrophobic interaction chromatography/reverse phase chromatography for effective protein separation in top-down proteomics.

PubMed

Valeja, Santosh G; Xiu, Lichen; Gregorich, Zachery R; Guner, Huseyin; Jin, Song; Ge, Ying

2015-01-01

To address the complexity of the proteome in mass spectrometry (MS)-based top-down proteomics, multidimensional liquid chromatography (MDLC) strategies that can effectively separate proteins with high resolution and automation are highly desirable. Although various MDLC methods that can effectively separate peptides from protein digests exist, very few MDLC strategies, primarily consisting of 2DLC, are available for intact protein separation, which is insufficient to address the complexity of the proteome. We recently demonstrated that hydrophobic interaction chromatography (HIC) utilizing a MS-compatible salt can provide high resolution separation of intact proteins for top-down proteomics. Herein, we have developed a novel 3DLC strategy by coupling HIC with ion exchange chromatography (IEC) and reverse phase chromatography (RPC) for intact protein separation. We demonstrated that a 3D (IEC-HIC-RPC) approach greatly outperformed the conventional 2D IEC-RPC approach. For the same IEC fraction (out of 35 fractions) from a crude HEK 293 cell lysate, a total of 640 proteins were identified in the 3D approach (corresponding to 201 nonredundant proteins) as compared to 47 in the 2D approach, whereas simply prolonging the gradients in RPC in the 2D approach only led to minimal improvement in protein separation and identifications. Therefore, this novel 3DLC method has great potential for effective separation of intact proteins to achieve deep proteome coverage in top-down proteomics.

Origin of bombesin-like peptides in human fetal lung.

PubMed

Yoshizaki, K; de Bock, V; Solomon, S

1984-02-27

Four different forms of bombesin-like immunoreactive peaks were detected in extracts of human fetal lung by the use of reversed-phase high performance liquid chromatography (HPLC). Peaks I, II, III and IV, (increasing retention time), were eluted using a 14-38% of acetonitrile gradient containing 0.1% trifluoroacetic acid (TFA). Peak II was the major material found in the extract of human fetal lung obtained at 16-20 weeks gestation. None of the four compounds contained in the eluted peaks had the same retention time as amphibian bombesin or porcine gastrin releasing peptide (GRP). On reversed-phase HPLC using two different solvent systems TFA or heptafluorobutyric acid (HFBA) as a hydrophobic counter ion, and in gel filtration chromatography, the chromatographic behavior of the main peak (peak II) was the same as that of the carboxyl terminal fragments of GRP, GRP18-27 or GRP19-27. This suggested that the peptide(s) in peak II resembled in composition the carboxy terminal 9 or 10 amino acids of porcine GRP. Following tryptic digestion the material in peak IV was converted to the more polar compound present in peak II. Two other peptide peaks were eluted close to peak II and these were presumed to be a modification of this main peak. One of the possible biosynthetic steps in the formation of bombesin-like peptides in human fetal lung could be a tryptic conversion of a less polar peptide to a more polar form (peak IV to II).

A new large-scale process for taxol and related taxanes from Taxus brevifolia.

PubMed

Rao, K V; Hanuman, J B; Alvarez, C; Stoy, M; Juchum, J; Davies, R M; Baxley, R

1995-07-01

In view of the demonstrated antitumor activity of taxol, ready availability of the drug is important. The current isolation methods starting from the bark of Taxus brevifolia involve multiple manipulations, leading to only taxol and in a yield of 0.01%. A new process consisting of a single reverse phase column is introduced here, and the present purpose is to determine its large scale applicability. The chloroform extractable fraction of the bark of T. brevifolia is applied directly on to a C-18 bonded silica column in 25% acetonitrile/water, with elution using a step gradient: 30-50% acetonitrile/water. On standing, eight different taxanes, including taxol, crystallize out directly from different fractions. The crystals are filtered and purified further by recrystallization. Taxol and four other taxanes are purified this way. The other three require a short silica column. Taxol is freed from cephalomannine by selective ozonolysis. The large scale process gave taxol (0.04%), 10-deacetylbaccatin III (0.02%), 10-deacetyl taxol-7-xyloside (0.1%), 10-deacetyl taxol-C-7-xyloside (0.04%), 10-deacetyl cephalomannine-7-xyloside (0.006%), taxol-7-xyloside (0.008%), 10-deacetyl taxol (0.008%) and cephalomannine (0.004%). Processing of the needles of T. brevifolia gave brevifoliol (0.17%), and that of the wood, 10-deacetyl taxol-C-7-xyloside (0.01%) and 10-deacetyl taxol-C. The reverse phase column process is simpler (one column, direct crystallization), more efficient (eight taxanes obtained simultaneously) and also gives higher yields.

Comparison of gamma-oryzanol contents in crude rice bran oils from different sources by various determination methods.

PubMed

Yoshie, Ayano; Kanda, Ayato; Nakamura, Takahiro; Igusa, Hisao; Hara, Setsuko

2009-01-01

Although there are various determination methods for gamma -oryzanol contained in rice bran oil by absorptiometry, normal-phase HPLC, and reversed-phase HPLC, their accuracies and the correlations among them have not been revealed yet. Chloroform-containing mixed solvents are widely used as mobile phases in some HPLC methods, but researchers have been apprehensive about its use in terms of safety for the human body and the environment.In the present study, a simple and accurate determination method was developed by improving the reversed-phase HPLC method. This novel HPLC method uses methanol/acetonitrile/acetic acid (52/45/3 v/v/v), a non-chlorinated solvent, as the mobile phase, and shows an excellent linearity (y = 0.9527x + 0.1241, R(2) = 0.9974) with absorptiometry. The mean relative errors among the existing 3 methods and the novel method, determined by adding fixed amounts of gamma-oryzanol into refined rice salad oil, were -4.7% for the absorptiometry, -6.8% for the existing normal-phase HPLC, +4.6% for the existing reversed-phase HPLC, and -1.6% for the novel reversed-phase HPLC method. gamma -Oryzanol content in 12 kinds of crude rice bran oils obtained from different sources were determined by the four methods. The mean content of those oils were 1.75+/-0.18% for the absorptiometry, 1.29+/-0.11% for the existing normal-phase HPLC, 1.51+/-0.10% for the existing reversed-phase HPLC, and 1.54+/-0.19% for the novel reversed-phase HPLC method.

Bacterial chemotaxis along vapor-phase gradients of naphthalene.

PubMed

Hanzel, Joanna; Harms, Hauke; Wick, Lukas Y

2010-12-15

The role of bacterial growth and translocation for the bioremediation of organic contaminants in the vadose zone is poorly understood. Whereas air-filled pores restrict the mobility of bacteria, diffusion of volatile organic compounds in air is more efficient than in water. Past research, however, has focused on chemotactic swimming of bacteria along gradients of water-dissolved chemicals. In this study we tested if and to what extent Pseudomonas putida PpG7 (NAH7) chemotactically reacts to vapor-phase gradients forming above their swimming medium by the volatilization from a spot source of solid naphthalene. The development of an aqueous naphthalene gradient by air-water partitioning was largely suppressed by means of activated carbon in the agar. Surprisingly, strain PpG7 was repelled by vapor-phase naphthalene although the steady state gaseous concentrations were 50-100 times lower than the aqueous concentrations that result in positive chemotaxis of the same strain. It is thus assumed that the efficient gas-phase diffusion resulting in a steady, and possibly toxic, naphthalene flux to the cells controlled the chemotactic reaction rather than the concentration to which the cells were exposed. To our knowledge this is the first demonstration of apparent chemotactic behavior of bacteria in response to vapor-phase effector gradients.

Acetylcholinesterase from Apis mellifera head. Evidence for amphiphilic and hydrophilic forms characterized by Triton X-114 phase separation.

PubMed Central

Belzunces, L P; Toutant, J P; Bounias, M

1988-01-01

The polymorphism of bee acetylcholinesterase was studied by sucrose-gradient-sedimentation analysis and non-denaturing electrophoretic analysis of fresh extracts. Lubrol-containing extracts exhibited only one form, which sedimented at 5 S when analysed on high-salt Lubrol-containing gradients and 6 S when analysed on low-salt Lubrol-containing gradients. The 5 S/6 S form aggregated upon removal of the detergent when sedimented on detergent-free gradients and was recovered in the detergent phase after Triton X-114 phase separation. Thus the 5 S/6 S enzyme corresponds to an amphiphilic acetylcholinesterase form. In detergent-free extracts three forms, whose apparent sedimentation coefficients are 14 S, 11 S and 7 S, were observed when sedimentations were performed on detergent-free gradients. Sedimentation analyses on detergent-containing gradients showed only a 5 S peak in high-salt detergent-free extracts and a 6 S peak, with a shoulder at about 7 S, in low-salt detergent-free extracts. Electrophoretic analysis in the presence of detergent demonstrated that the 14 S and 11 S peaks corresponded to aggregates of the 5 S/6 S form, whereas the 7 S peak corresponded to a hydrophilic acetylcholinesterase form which was recovered in the aqueous phase following Triton X-114 phase separation. The 5 S/6 S amphiphilic form could be converted into a 7.1 S hydrophilic form by phosphatidylinositol-specific phospholipase C digestion. Images Fig. 3. Fig. 6. PMID:2849414

Reversibly extracellular pH controlled cellular uptake and photothermal therapy by PEGylated mixed-charge gold nanostars.

PubMed

Wang, Shouju; Teng, Zhaogang; Huang, Peng; Liu, Dingbin; Liu, Ying; Tian, Ying; Sun, Jing; Li, Yanjun; Ju, Huangxian; Chen, Xiaoyuan; Lu, Guangming

2015-04-17

Shielding nanoparticles from nonspecific interactions with normal cells/tissues before they reach and after they leave tumors is crucial for the selective delivery of NPs into tumor cells. By utilizing the reversible protonation of weak electrolytic groups to pH changes, long-chain amine/carboxyl-terminated polyethylene glycol (PEG) decorated gold nanostars (GNSs) are designed, exhibiting reversible, significant, and sensitive response in cell affinity and therapeutic efficacy to the extracellular pH (pHe) gradient between normal tissues and tumors. This smart nanosystem shows good dispersity and unimpaired photothermal efficacy in complex bioenvironment at pH 6.4 and 7.4 even when their surface charge is neutral. One PEGylated mixed-charge GNSs with certain surface composition, GNS-N/C 4, exhibits high cell affinity and therapeutic efficacy at pH 6.4, and low affinity and almost "zero" damage to cells at pH 7.4. Remarkably, this significant and sensitive response in cell affinity and therapeutic efficacy is reversible as local pH alternated. In vivo, GNS-N/C 4 shows higher accumulation in tumors and improved photothermal therapeutic efficacy than pH-insensitive GNSs. This newly developed smart nanosystem, whose cell affinity reversibly transforms in response to pHe gradient with unimpaired biostability, provides a novel effective means of tumor-selective therapy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spiral MRI on a 9.4T Vertical-bore Superconducting Magnet Using Unshielded and Self-shielded Gradient Coils

PubMed Central

Kodama, Nao; Setoi, Ayana; Kose, Katsumi

2018-01-01

Spiral MRI sequences were developed for a 9.4T vertical standard bore (54 mm) superconducting magnet using unshielded and self-shielded gradient coils. Clear spiral images with 64-shot scan were obtained with the self-shielded gradient coil, but severe shading artifacts were observed for the spiral-scan images acquired with the unshielded gradient coil. This shading artifact was successfully corrected with a phase-correction technique using reference scans that we developed based on eddy current field measurements. We therefore concluded that spiral imaging sequences can be installed even for unshielded gradient coils if phase corrections are performed using the reference scans. PMID:28367906

Spiral MRI on a 9.4T Vertical-bore Superconducting Magnet Using Unshielded and Self-shielded Gradient Coils.

PubMed

Kodama, Nao; Setoi, Ayana; Kose, Katsumi

2018-04-10

Spiral MRI sequences were developed for a 9.4T vertical standard bore (54 mm) superconducting magnet using unshielded and self-shielded gradient coils. Clear spiral images with 64-shot scan were obtained with the self-shielded gradient coil, but severe shading artifacts were observed for the spiral-scan images acquired with the unshielded gradient coil. This shading artifact was successfully corrected with a phase-correction technique using reference scans that we developed based on eddy current field measurements. We therefore concluded that spiral imaging sequences can be installed even for unshielded gradient coils if phase corrections are performed using the reference scans.

Drug-induced regulatory overcompensation has motivational consequences: Implications for homeostatic and allostatic models of drug addiction

PubMed Central

Ramsay, Douglas S; Woods, Stephen C; Kaiyala, Karl J

2014-01-01

Initial administration of 60% nitrous oxide (N2O) at 21°C ambient temperature reduces core temperature (Tc) in rats, but tolerance develops to this hypothermic effect over several administrations. After additional N2O administrations, a hyperthermic overcompensation (sign-reversal) develops such that Tc exceeds control levels during N2O inhalation. This study investigated whether rats would employ behavioral thermoregulation to facilitate, or oppose, a previously acquired hyperthermic overcompensation during N2O administration. To establish a hyperthermic sign-reversal, male Long-Evans rats (N = 12) received 10 3-h administrations of 60% N2O while housed in a gas-tight, live-in, “inactive” thermal gradient (∼21°C). Following the tenth N2O exposure, the thermal gradient was activated (range of 10–37°C), and rats received both a control gas session and a 60% N2O test session in counterbalanced order. Mean Tc during N2O inhalation in the inactive gradient was reliably hypothermic during the first exposure but was reliably hyperthermic by the tenth exposure. When subsequently exposed to 60% N2O in the active gradient, rats selected a cooler Ta, which blunted the hyperthermic sign-reversal and lowered Tc throughout the remainder of the N2O exposure. Thus, autonomic heat production effectors mediating the hyperthermia were opposed by a behavioral effector that promoted increased heat loss via selection of a cooler ambient temperature. These data are compatible with an allostatic model of drug addiction that suggests that dysregulatory overcompensation in the drugged-state may motivate behaviors (e.g., drug taking) that oppose the overcompensation, thereby creating a vicious cycle of escalating drug consumption and recurring dysregulation. PMID:25938126

The Albite Fusion Curve Re-examined: New Experiments and the Density and Compressibility of NaAlSi3O8 Liquid With Pressure

NASA Astrophysics Data System (ADS)

Tenner, T. J.; Lange, R. A.

2005-12-01

Two half-reversals on the melting temperature of high albite (NaAlSi3O8) were determined at 2.3 GPa (1360-1370 °C) and 2.8 GPa (1383-1389 °C) in a piston-cylinder apparatus with NaAlSi3O8 glass as the starting material. A detailed thermal gradient across the sample capsule was mapped, which showed a 3.5 °C gradient across the upper third of the sample capsule and a 30 °C gradient across the lower two-thirds. A calibration against the melting curve of NaCl showed a -5 % pressure correction for the BaCO3/MgO/graphite pressure medium used in these experiments. In addition to the glass-crystal half-reversals, a crystal-glass half-reversal at 2.73 GPa was obtained (1389-1399 °C) using high albite as the starting material. All run products that quenched to a glass were analyzed by Fourier-transform infrared spectroscopy and were found to contain < 0.045 wt% H2O. Our experimental constraints on the albite fusion curve are in excellent agreement with those of Birch and LeComte (1960) and Boyd and England (1963), but deviate from those of Boettcher et al. (1982). Our new data on the albite fusion curve at high pressure are compared with the calculated melting reaction based on the best available thermodynamic data at one bar (Lange, 2003), and various values for the pressure dependence of liquid compressibility (K' = dKT,0/dP, where KT,0 = 1/βT,0) for NaAlSi3O8 liquid, using the 3rd-order Birch-Murnaghan equation of state. Our phase-equilibrium data match the fusion curve calculated with a liquid value of 10.0 ± 1.0. This allows the density of NaAlSi3O8 liquid to be calculated at 1500 °C and 3.0 GPa (2.551 ± 0.01 g/cm3), with an uncertainty that is ~0.3 %. The results of this study show that the density and compressibility of this viscous and fully polymerized liquid can be calculated to high pressure (~3 GPa) with a remarkably high precision. Owing to the absence of any coordination change in NaAlSi3O8 liquid to ~8 GPa, calculations of its density and compressibility can likely be extended to this pressure.

Salinity Gradients for Sustainable Energy: Primer, Progress, and Prospects.

PubMed

Yip, Ngai Yin; Brogioli, Doriano; Hamelers, Hubertus V M; Nijmeijer, Kitty

2016-11-15

Combining two solutions of different composition releases the Gibbs free energy of mixing. By using engineered processes to control the mixing, chemical energy stored in salinity gradients can be harnessed for useful work. In this critical review, we present an overview of the current progress in salinity gradient power generation, discuss the prospects and challenges of the foremost technologies - pressure retarded osmosis (PRO), reverse electrodialysis (RED), and capacitive mixing (CapMix) and provide perspectives on the outlook of salinity gradient power generation. Momentous strides have been made in technical development of salinity gradient technologies and field demonstrations with natural and anthropogenic salinity gradients (for example, seawater-river water and desalination brine-wastewater, respectively), but fouling persists to be a pivotal operational challenge that can significantly ebb away cost-competitiveness. Natural hypersaline sources (e.g., hypersaline lakes and salt domes) can achieve greater concentration difference and, thus, offer opportunities to overcome some of the limitations inherent to seawater-river water. Technological advances needed to fully exploit the larger salinity gradients are identified. While seawater desalination brine is a seemingly attractive high salinity anthropogenic stream that is otherwise wasted, actual feasibility hinges on the appropriate pairing with a suitable low salinity stream. Engineered solutions are foulant-free and can be thermally regenerative for application in low-temperature heat utilization. Alternatively, PRO, RED, and CapMix can be coupled with their analog separation process (reverse osmosis, electrodialysis, and capacitive deionization, respectively) in salinity gradient flow batteries for energy storage in chemical potential of the engineered solutions. Rigorous techno-economic assessments can more clearly identify the prospects of low-grade heat conversion and large-scale energy storage. While research attention is squarely focused on efficiency and power improvements, efforts to mitigate fouling and lower membrane and electrode cost will be equally important to reduce levelized cost of salinity gradient energy production and, thus, boost PRO, RED, and CapMix power generation to be competitive with other renewable technologies. Cognizance of the recent key developments and technical progress on the different technological fronts can help steer the strategic advancement of salinity gradient as a sustainable energy source.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zohar, S.; Choi, Y.; Love, D. M.

We use X-ray Excited Luminescence Microscopy to investigate the elemental and layer resolved magnetic reversal in an interlayer exchange coupled (IEC) epitaxial Fe/Cr wedge/Co heterostructure. The transition from strongly coupled parallel Co-Fe reversal for Cr thickness t(Cr) < 0.34 nm to weakly coupled layer independent reversal for t(Cr) > 1.5 nm is punctuated at 0.34 < t(Cr) < 1.5 nm by a combination of IEC guided domain wall motion and stationary zig zag domain walls. Domain walls nucleated at switching field minima are guided by IEC spatial gradients and collapse at switching field maxima.

Microwave assisted solvent extraction and coupled-column reversed-phase liquid chromatography with UV detection use of an analytical restricted-access-medium column for the efficient multi-residue analysis of acidic pesticides in soils.

PubMed

Hogendoom, E A; Huls, R; Dijkman, E; Hoogerbrugge, R

2001-12-14

A screening method has been developed for the determination of acidic pesticides in various types of soils. Methodology is based on the use of microwave assisted solvent extraction (MASE) for fast and efficient extraction of the analytes from the soils and coupled-column reversed-phase liquid chromatography (LC-LC) with UV detection at 228 nm for the instrumental analysis of uncleaned extracts. Four types of soils, including sand, clay and peat, with a range in organic matter content of 0.3-13% and ten acidic pesticides of different chemical families (bentazone, bromoxynil, metsulfuron-methyl, 2,4-D, MCPA, MCPP, 2,4-DP, 2,4,5-T, 2,4-DB and MCPB) were selected as matrices and analytes, respectively. The method developed included the selection of suitable MASE and LC-LC conditions. The latter consisted of the selection of a 5-microm GFF-II internal surface reversed-phase (ISRP, Pinkerton) analytical column (50 x 4.6 mm, I.D.) as the first column in the RAM-C18 configuration in combination with an optimised linear gradient elution including on-line cleanup of sample extracts and reconditioning of the columns. The method was validated with the analysis of freshly spiked samples and samples with aged residues (120 days). The four types of soils were spiked with the ten acidic pesticides at levels between 20 and 200 microg/kg. Weighted regression of the recovery data showed for most analyte-matrix combinations, including freshly spiked samples and aged residues, that the method provides overall recoveries between 60 and 90% with relative standard deviations of the intra-laboratory reproducibility's between 5 and 25%; LODs were obtained between 5 and 50 microg/kg. Evaluation of the data set with principal component analysis revealed that the parameters (i) increase of organic matter content of the soil samples and (ii) aged residues negatively effect the recovery of the analytes.

Rapid determination of human globin chains using reversed-phase high-performance liquid chromatography.

PubMed

Wan, Jun-Hui; Tian, Pei-Ling; Luo, Wei-Hao; Wu, Bing-Yi; Xiong, Fu; Zhou, Wan-Jun; Wei, Xiang-Cai; Xu, Xiang-Min

2012-07-15

Reversed-phase high-performance liquid chromatography (RP-HPLC) of human globin chains is an important tool for detecting thalassemias and hemoglobin variants. The challenges of this method that limit its clinical application are a long analytical time and complex sample preparation. The aim of this study was to establish a simple, rapid and high-resolution RP-HPLC method for the separation of globin chains in human blood. Red blood cells from newborns and adults were diluted in deionized water and injected directly onto a micro-jupiter C18 reversed-phase column (250 mm × 4.6 mm) with UV detection at 280 nm. Under the conditions of varying pH or the HPLC gradient, the globin chains (pre-β, β, δ, α, (G)γ and (A)γ) were denatured and separated from the heme groups in 12 min with a retention time coefficient of variation (CV) ranging from 0.11 to 1.29% and a peak area CV between 0.32% and 4.86%. Significant differences (P<0.05) among three groups (normal, Hb H and β thalassemia) were found in the area ratio of α/pre-β+β applying the rapid elution procedure, while P≥0.05 was obtained between the normal and α thalassemia silent/trait group. Based on the ANOVA results, receiver operating characteristic (ROC) curve analysis of the δ/β and α/pre-β+β area ratios showed a sensitivity of 100.0%, and a specificity of 100.0% for indicating β thalassemia carriers, and a sensitivity of 96.6% and a specificity of 89.6% for the prediction of hemoglobin H (Hb H) disease. The proposed cut-off was 0.026 of δ/β for β thalassemia carriers and 0.626 of α/pre-β+β for Hb H disease. In addition, abnormal hemoglobin hemoglobin E (Hb E) and Hb Westmead (Hb WS) were successfully identified using this RP-HPLC method. Our experience in developing this RP-HPLC method for the rapid separation of human globin chains could be of use for similar work. Copyright © 2012 Elsevier B.V. All rights reserved.

Internal transport barriers in the National Spherical Torus Experimenta)

NASA Astrophysics Data System (ADS)

Yuh, H. Y.; Levinton, F. M.; Bell, R. E.; Hosea, J. C.; Kaye, S. M.; LeBlanc, B. P.; Mazzucato, E.; Peterson, J. L.; Smith, D. R.; Candy, J.; Waltz, R. E.; Domier, C. W.; Luhmann, N. C.; Lee, W.; Park, H. K.

2009-05-01

In the National Spherical Torus Experiment [M. Ono et al., Nucl. Fusion 41, 1435 (2001)], internal transport barriers (ITBs) are observed in reversed (negative) shear discharges where diffusivities for electron and ion thermal channels and momentum are reduced. While neutral beam heating can produce ITBs in both electron and ion channels, high harmonic fast wave heating can also produce electron ITBs (e-ITBs) under reversed magnetic shear conditions without momentum input. Interestingly, the location of the e-ITB does not necessarily match that of the ion ITB (i-ITB). The e-ITB location correlates best with the magnetic shear minima location determined by motional Stark effect constrained equilibria, whereas the i-ITB location better correlates with the location of maximum E ×B shearing rate. Measured electron temperature gradients in the e-ITB can exceed critical gradients for the onset of electron thermal gradient microinstabilities calculated by linear gyrokinetic codes. A high-k microwave scattering diagnostic shows locally reduced density fluctuations at wave numbers characteristic of electron turbulence for discharges with strongly negative magnetic shear versus weakly negative or positive magnetic shear. Reductions in fluctuation amplitude are found to be correlated with the local value of magnetic shear. These results are consistent with nonlinear gyrokinetic simulations predicting a reduction in electron turbulence under negative magnetic shear conditions despite exceeding critical gradients.

Integrated electrokinetics-adsorption remediation of saline-sodic soils: effects of voltage gradient and contaminant concentration on soil electrical conductivity.

PubMed

Essa, Mohammed Hussain; Mu'azu, Nuhu Dalhat; Lukman, Salihu; Bukhari, Alaadin

2013-01-01

In this study, an integrated in situ remediation technique which couples electrokinetics with adsorption, using locally produced granular activated carbon from date palm pits in the treatment zones that are installed directly to bracket the contaminated soils at bench-scale, is investigated. Natural saline-sodic clay soil, spiked with contaminant mixture (kerosene, phenol, Cr, Cd, Cu, Zn, Pb, and Hg), was used in this study to investigate the effects of voltage gradient, initial contaminant concentration, and polarity reversal rate on the soil electrical conductivity. Box-Behnken Design (BBD) was used for the experimental design and response surface methodology (RSM) was employed to model, optimize, and interpret the results obtained using Design-Expert version 8 platform. The total number of experiments conducted was 15 with voltage gradient, polarity reversal rate, and initial contaminant concentration as variables. The main target response discussed in this paper is the soil electrical conductivity due to its importance in electrokinetic remediation process. Responses obtained were fitted to quadratic models whose R (2) ranges from 84.66% to 99.19% with insignificant lack of fit in each case. Among the investigated factors, voltage gradient and initial contaminant concentration were found to be the most significant influential factors.

Buoyancy-Marangoni convection in confined volatile binary fluids subject to a horizontal temperature gradient

NASA Astrophysics Data System (ADS)

Qin, Tongran; Grigoriev, Roman

2017-11-01

We consider convection in a layer of binary fluid with free surface subject to a horizontal temperature gradient in the presence of noncondensable gases, which is driven by a combination of three different forces: buoyancy, thermocapillarity, and solutocapillarity. Unlike buoyancy, both thermo- and solutocapillary stresses depend sensitively on the local phase equilibrium at the liquid-gas interface. In particular, thermocapillarity associated with the interfacial temperature gradient is controlled by the vapors' concentration along the interface, and solutocapillarity associated with the interfacial concentration gradient is controlled by differential phase change of two components of the liquid, which is strongly influenced by the presence of noncondensables. Therefore, flows in both phases, phase change, and effect of noncondensables all have to be considered. Numerical simulations based on a comprehensive model taking these effects into account show qualitative agreement with recent experiments which identified a number of flow regimes at various compositions of both phases. In particular,we find that the composition of both the gas and liquid phase have a significant effect on the observed convection patterns; this dependence can be understood using a simple analytical model. This material is based upon work supported by the National Science Foundation under Grant No. 1511470.

Postoperative Reverse Remodeling and Symptomatic Improvement in Normal-Flow Low-Gradient Aortic Stenosis After Aortic Valve Replacement.

PubMed

Carter-Storch, Rasmus; Møller, Jacob E; Christensen, Nicolaj L; Irmukhadenov, Akhmadjon; Rasmussen, Lars M; Pecini, Redi; Øvrehus, Kristian A; Søndergård, Eva V; Marcussen, Niels; Dahl, Jordi S

2017-12-01

Severe aortic stenosis (AS) most often presents with reduced aortic valve area (<1 cm 2 ), normal stroke volume index (≥35 mL/m 2 ), and either high mean gradient (≥40 mm Hg; normal-flow high-gradient AS) or low mean gradient (normal-flow low-gradient [NFLG] AS). The benefit of aortic valve replacement (AVR) among NFLG patients is controversial. We compared the impact of NFLG condition on preoperative left ventricular (LV) remodeling and myocardial fibrosis and postoperative remodeling and symptomatic benefit. Eighty-seven consecutive patients with reduced aortic valve area and normal stroke volume index undergoing AVR underwent echocardiography, magnetic resonance imaging, a 6-minute walk test, and measurement of natriuretic peptides before and 1 year after AVR. Myocardial fibrosis was assessed from magnetic resonance imaging. Patients were stratified as NFLG or normal-flow high-gradient. In total, 33 patients (38%) had NFLG. Before AVR, they were characterized by similar symptom burden but less severe AS measured by aortic valve area index (0.50±0.09 versus 0.40±0.08 cm 2 /m 2 ; P <0.0001), lower LV mass index (74±18 versus 90±26 g/m 2 ; P =0.01), but the same degree of myocardial fibrosis. After AVR, NFLG had a smaller reduction in LV mass index (-3±10 versus -±18 g/m 2 ; P <0.0001) and a smaller reduction in natriuretic peptides. Both groups experienced similar symptomatic improvement. Normal-flow high-gradient condition independently predicted change in LV mass index. Patients with NFLG had less severe AS and LV remodeling than patients with normal-flow high-gradient. Furthermore, NFLG patients experienced less reverse remodeling but the same symptomatic benefit. URL: http://www.clinicaltrials.gov. Unique identifier: NCT02316587. © 2017 American Heart Association, Inc.

Wake measurements in a strong adverse pressure gradient

NASA Technical Reports Server (NTRS)

Hoffenberg, R.; Sullivan, John P.; Schneider, S. P.

1994-01-01

The behavior of wakes in adverse pressure gradients is critical to the performance of high-lift systems for transport aircraft. Wake deceleration is known to lead to sudden thickening and the onset of reversed flow; this 'wake bursting' phenomenon can occur while surface flows remain attached. Although 'wake bursting' is known to be important for high-lift systems, no detailed measurements of 'burst' wakes have ever been reported. Wake bursting has been successfully achieved in the wake of a flat plate as it decelerated in a two-dimensional diffuser, whose sidewalls were forced to remain attached by use of slot blowing. Pilot probe surveys, L.D.V. measurements, and flow visualization have been used to investigate the physics of this decelerated wake, through the onset of reversed flow.

Gradient forces on double-negative particles in optical tweezers using Bessel beams in the ray optics regime.

PubMed

Ambrosio, Leonardo A; Hernández-Figueroa, Hugo E

2010-11-08

Gradient forces on double negative (DNG) spherical dielectric particles are theoretically evaluated for v-th Bessel beams supposing geometrical optics approximations based on momentum transfer. For the first time in the literature, comparisons between these forces for double positive (DPS) and DNG particles are reported. We conclude that, contrary to the conventional case of positive refractive index, the gradient forces acting on a DNG particle may not reverse sign when the relative refractive index n goes from |n|>1 to |n|<1, thus revealing new and interesting trapping properties.

LC-MS/MS-based quantification of kynurenine metabolites, tryptophan, monoamines and neopterin in plasma, cerebrospinal fluid and brain.

PubMed

Fuertig, René; Ceci, Angelo; Camus, Sandrine M; Bezard, Erwan; Luippold, Andreas H; Hengerer, Bastian

2016-09-01

The kynurenine (KYN) pathway is implicated in diseases such as cancer, psychiatric, neurodegenerative and autoimmune disorders. Measurement of KYN metabolite levels will help elucidating the involvement of the KYN pathway in the disease pathology and inform drug development. Samples of plasma, cerebrospinal fluid or brain tissue were spiked with deuterated internal standards, processed and analyzed by LC-MS/MS; analytes were chromatographically separated by gradient elution on a C18 reversed phase analytical column without derivatization. We established an LC-MS/MS method to measure 11 molecules, namely tryptophan, KYN, 3-OH-KYN, 3-OH-anthranilic acid, quinolinic acid, picolinic acid, kynurenic acid, xanthurenic acid, serotonin, dopamine and neopterin within 5.5 min, with sufficient sensitivity to quantify these molecules in small sample volumes of plasma, cerebrospinal fluid and brain tissue.

Two-dimensional numerical simulation of a Stirling engine heat exchanger

NASA Technical Reports Server (NTRS)

Ibrahim, Mounir; Tew, Roy C.; Dudenhoefer, James E.

1989-01-01

The first phase of an effort to develop multidimensional models of Stirling engine components is described. The ultimate goal is to model an entire engine working space. Parallel plate and tubular heat exchanger models are described, with emphasis on the central part of the channel (i.e., ignoring hydrodynamic and thermal end effects). The model assumes laminar, incompressible flow with constant thermophysical properties. In addition, a constant axial temperature gradient is imposed. The governing equations describing the model have been solved using the Crack-Nicloson finite-difference scheme. Model predictions are compared with analytical solutions for oscillating/reversing flow and heat transfer in order to check numerical accuracy. Excellent agreement is obtained for flow both in circular tubes and between parallel plates. The computational heat transfer results are in good agreement with the analytical heat transfer results for parallel plates.

Phase conjugation and time reversal in acoustics

NASA Astrophysics Data System (ADS)

Fink, Mathias

2000-07-01

This paper compares the different approaches used in acoustics to time reverse or to phase conjugate a wavefield. The basic principle of a time reversal mirror is an extension for broadband pulsed waves to the optical phase conjugated mirror designed for monochromatic waves. However, this equivalence is only valid mathematically and there are some fundamental differences between these two techniques that will be described in this paper.

Monolithic stationary phases with a longitudinal gradient of porosity.

PubMed

Urban, Jiří; Hájek, Tomáš; Svec, Frantisek

2017-04-01

The duration of the hypercrosslinking reaction has been used to control the extent of small pores formation in polymer-based monolithic stationary phases. Segments of five columns hypercrosslinked for 30-360 min were coupled via zero-volume unions to prepare columns with segmented porosity gradients. The steepness of the porosity gradient affected column efficiency, mass transfer resistance, and separation of both small-molecule alkylbenzenes and high-molar-mass polystyrene standards. In addition, the segmented column with the steepest porosity gradient was prepared as a single column with a continuous porosity gradient. The steepness of porosity gradient in this type column was tuned. Compared to a completely hypercrosslinked column, the column with the shallower gradient produced comparable size-exclusion separation of polystyrene standards but allowed higher column permeability. The completely hypercrosslinked column and the column with porosity gradient were successfully coupled in online two-dimensional liquid chromatography of polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Escalation of polymerization in a thermal gradient

PubMed Central

Mast, Christof B.; Schink, Severin; Gerland, Ulrich; Braun, Dieter

2013-01-01

For the emergence of early life, the formation of biopolymers such as RNA is essential. However, the addition of nucleotide monomers to existing oligonucleotides requires millimolar concentrations. Even in such optimistic settings, no polymerization of RNA longer than about 20 bases could be demonstrated. How then could self-replicating ribozymes appear, for which recent experiments suggest a minimal length of 200 nt? Here, we demonstrate a mechanism to bridge this gap: the escalated polymerization of nucleotides by a spatially confined thermal gradient. The gradient accumulates monomers by thermophoresis and convection while retaining longer polymers exponentially better. Polymerization and accumulation become mutually self-enhancing and result in a hyperexponential escalation of polymer length. We describe this escalation theoretically under the conservative assumption of reversible polymerization. Taking into account the separately measured thermophoretic properties of RNA, we extrapolate the results for primordial RNA polymerization inside a temperature gradient in pores or fissures of rocks. With a dilute, nanomolar concentration of monomers the model predicts that a pore length of 5 cm and a temperature difference of 10 K suffice to polymerize 200-mers of RNA in micromolar concentrations. The probability to generate these long RNAs is raised by a factor of >10600 compared with polymerization in a physical equilibrium. We experimentally validate the theory with the reversible polymerization of DNA blocks in a laser-driven thermal trap. The results confirm that a thermal gradient can significantly enlarge the available sequence space for the emergence of catalytically active polymers. PMID:23630280

[Application of fingerprint chromatogram in quality control of Shen-Mai injection].

PubMed

Shi, Xian-zhe; Yang, Jun; Zhao, Chun-xia; Xiong, Jian-hui; Xu, Guo-wang

2002-07-01

The theory and practice of traditional Chinese medicine require some comprehensive methods to assess quality of the Chinese herbal medication. Fingerprint chromatogram is one of the feasible approaches to evaluate the quality of Chinese herbal medication. So the fingerprint chromatogram of Shen-Mai injection was established by using reversed-phase high performance liquid chromatography. The chromatographic conditions were as follows: a Hypersil C18 column was used; the mobile phase was composed of water (A) and acetontrile (B) with linear gradient elution (0-50 min, 5%-95% B, volume fraction); the flow rate was 1.0 mL/min and the UV absorbance detection was set at 202 nm. The peak-area ratios of twenty-three fingerprint peaks and internal standard (diphenyl) were taken as the criteria for quality control. The quality differences in various batches and various manufacturers of Shen-Mai injections were investigated by projection discriminance based on principal component analysis. The results show the method developed is convenient, reliable and applicable for the quality control analysis of Shen-Mai injection.

[Simultaneous determination of five main index components and specific chromatograms analysis in Xiaochaihu granules].

PubMed

Zhuang, Yan-Shuang; Cai, Hao; Liu, Xiao; Cai, Bao-Chang

2012-01-01

Reversed phase high performance liquid chromatography with diode array detector was employed for simultaneous determination of five main index components and specific chromatograms analysis in Xiaochaihu granules with a linear gradient elution of acetonitrile-water (containing 0.1% phosphoric acid) as mobile phase. The results showed that five main index components (baicalin, baicalein, wogonoside, wogonin, enoxolone) were separated well under the analytical condition. The linear ranges of five components were 0.518 - 16.576, 0.069 - 2.197, 0.167 - 5.333, 0.009 - 0.297 and 0.006 - 0.270 mg x g(-1), respectively. The correlation coefficients were 0.999 9, and the average recoveries ranged from 95% to 105%. Twelve common peaks were selected as the specific chromatograms of Xiaochaihu granules with baicalin as the reference peak. There were good similarities between the reference and the ten batches of samples. The similarity coefficients were no less than 0.9. The analytical method established is highly sensitive with strong specificity and it can be used efficiently in the quality control of Xiaochaihu granules.

Fast analysis of capsaicinoids in Naga Jolokia extracts (Capsicum chinense) by high-performance liquid chromatography using fused core columns.

PubMed

Stipcovich, Tea; Barbero, Gerardo F; Ferreiro-González, Marta; Palma, Miguel; Barroso, Carmelo G

2018-01-15

A rapid high-performance liquid chromatography method with a C18 reverse-phase fused-core column has been developed for the determination and quantification of the main capsaicinoids (nornordihydrocapsaicin, nordihydrocapsaicin, capsaicin, dihydrocapsaicin, homocapsaicin and homodihydrocapsaicin) present in Naga Jolokia peppers. A fused-core Kinetex™ C18 column (50×2.1mm i.d.; 2.6μm) was used for the analysis. The chromatographic separation was obtained with a gradient method in which the mobile phase was water (0.1% acetic acid) as solvent A and acetonitrile (0.1% acetic acid) as solvent B. The separation of all compounds was achieved in less than 3min with a total analysis time (sample-to-sample) of 10min. The robustness of the method was evaluated. The method showed excellent repeatability and intermediate precision expressed as coefficient of variance of less than 2%. The developed method was employed for the quantification of the major capsaicinoids present in different peppers and commercial products containing chilli peppers. Copyright © 2017 Elsevier Ltd. All rights reserved.

An Improved LC-MS/MS Method for Simultaneous Determination of the Eleven Bioactive Constituents for Quality Control of Radix Angelicae Pubescentis and Its Related Preparations

PubMed Central

Li, Jin; Zhang, Qiu-Hong; He, Jun; Liu, Er-wei; Gao, Xiu-mei; Chang, Yan-xu

2015-01-01

An improved LC-MS/MS method was developed for simultaneous determination of eleven bioactive constituents of Radix Angelicae Pubescentis and its related preparations. It was the first report on the quantification of bioactive constituents in different preparations of Radix Angelicae Pubescentis by LC-MS/MS analytical method. These samples were separated with an Agilent Zorbax Extend reversed-phase C18 column (1.8 μm, 4.6 × 100 mm) by linear gradient elution using aqueous ammonium acetate and acetonitrile as mobile phase. The flow rate was 0.3 mL min−1. The eleven bioactive constituents showed good regression (R > 0.990) within test ranges and the recoveries were in the range of 87.1–110%. The limit of detections and quantifications for most of the major constituents were less than 0.5 and 1.0 ng mL−1, respectively. All results indicated that the developed method could be readily utilized as a suitable quality control method for Radix Angelicae Pubescentis and related preparations. PMID:26078992

Application of ion-trap mass spectrometry for identification and structural determination of an unknown impurity in simvastatin.

PubMed

Reddy, G V Ram; Kumar, A Praveen; Reddy, B Venkateswara; Sreeramulu, J

2009-10-01

Anhydro-simvastatin and simvastatin dimer are the two main impurities in the fermentation broth as well as in the final product of simvastatin, which is a hypolipidemic drug. An unknown impurity with m/z 451 for [(M + H)(+)] was detected in the analysis of final simvastatin drug sample. By using reverse phase high performance liquid chromatography (HPLC)-mass spectrometry (MS) and MS/MS spectra, the unknown impurity was detected and identified. Separation was achieved on ACE-5 C18 (150 x 4.6 mm, 3 microm column) at the flow rate of 1.2 ml min(-1) applying gradient elution of mobile phase A consisting of Milli-Q water of pH 3.0 with formic acid and B consisting of acetonitrile. MS/MS spectrum of the unknown impurity was obtained using HPLC-MS equipped with positive electrosoray ionization (ESI). The unknown impurity is named as 7-[7-(2,2-dimethyl-butyryloxy)-2,6-dimethyl-1,2,6,7,8,8a-hexahydro-naphthalen-1 -yl]-3-hydroxy-5-hydroxymethyl-heptanoic acid.

Ultra-Performance Liquid Chromatographic Determination of Tocopherols and Retinol in Human Plasma

PubMed Central

Bell, Edward C.; John, Mathew; Hughes, Rodney J.; Pham, Thu

2014-01-01

A rapid, selective and sensitive ultra-performance liquid chromatography method has been developed for the detection and quantification of tocopherols and retinol in human plasma. Alpha-tocopherol, gamma-tocopherol and retinol are assayed using fluorescence detection. Excitation/emission wavelengths are 295/330 nm and 325/470 nm for the analysis of both tocopherols and retinol, respectively. Retinol acetate is employed as the internal standard. The reversed-phase method incorporates gradient elution with a mobile phase consisting of methanol and acetonitrile. Separation of vitamin compounds is achieved using a bridged ethyl hybrid C18 column. The retention times for retinol, retinol acetate, gamma-tocopherol and alpha-tocopherol are 1.6, 1.8, 3.9 and 4.3 min, respectively. The limits of quantification for retinol, gamma-tocopherol and alpha-tocopherol were 0.02, 0.02 and 0.1 µg/mL, respectively. The assay method is suitable for the analysis of tocopherols and retinol in human plasma. The method may be applied following the ingestion of foods fortified with these fat-soluble vitamins. PMID:24170122

Therapeutic drug monitoring of seven psychotropic drugs and four metabolites in human plasma by HPLC-MS.

PubMed

Choong, Eva; Rudaz, Serge; Kottelat, Astrid; Guillarme, Davy; Veuthey, Jean-Luc; Eap, Chin B

2009-12-05

A simple and sensitive LC-MS method was developed and validated for the simultaneous quantification of aripiprazole (ARI), atomoxetine (ATO), duloxetine (DUL), clozapine (CLO), olanzapine (OLA), sertindole (STN), venlafaxine (VEN) and their active metabolites dehydroaripiprazole (DARI), norclozapine (NCLO), dehydrosertindole (DSTN) and O-desmethylvenlafaxine (OVEN) in human plasma. The above mentioned compounds and the internal standard (remoxipride) were extracted from 0.5 mL plasma by solid-phase extraction (mix mode support). The analytical separation was carried out on a reverse phase liquid chromatography at basic pH (pH 8.1) in gradient mode. All analytes were monitored by MS detection in the single ion monitoring mode and the method was validated covering the corresponding therapeutic range: 2-200 ng/mL for DUL, OLA, and STN, 4-200 ng/mL for DSTN, 5-1000 ng/mL for ARI, DARI and finally 2-1000 ng/mL for ATO, CLO, NCLO, VEN, OVEN. For all investigated compounds, good performance in terms of recoveries, selectivity, stability, repeatability, intermediate precision, trueness and accuracy, was obtained. Real patient plasma samples were then successfully analysed.

Evaluation of an International Pharmacopoeia method for the analysis of nelfinavir mesilate by liquid chromatography.

PubMed

Yekkala, Raja Satyanarayana; Vandenwayenberg, Stephanie; Hoogmartens, Jos; Adams, Erwin

2006-11-17

A gradient LC method for the determination of related substances in nelfinavir mesilate (NFVM) has been recently published in the International Pharmacopoeia. The method uses a base deactivated reversed phase C18 column (25 cm x 4.6 mm I.D.), 5 microm kept at a temperature of 35 degrees C. The mobile phases consist of acetonitrile, methanol, phosphate buffer pH 3.4 and water. The flow rate is 1.0 ml/min. UV detection is performed at 225 nm. A system suitability test (SST) is described to govern the quality of the separation. The separation towards NFVM components was investigated on 18 C18 columns and correlation was made with the column classification system developed in our laboratory. The method was evaluated using a Hypersil BDS C18 column (25 cm x 4.6 mm I.D.), 5 microm. A two level fractional factorial design was applied to examine the robustness of the method. The method shows good selectivity, precision, linearity and sensitivity. Seven commercial samples were examined using this method.

Supplemental and highly-elevated tocopherol doses differentially regulate allergic inflammation: reversibility of α-tocopherol and γ-tocopherol's effects

PubMed Central

McCary, Christine A.; Abdala-Valencia, Hiam; Berdnikovs, Sergejs; Cook-Mills, Joan M.

2011-01-01

We have reported that supplemental doses of the α- and γ-tocopherol isoforms of vitamin E decrease and increase, respectively, allergic lung inflammation. We have now assessed whether these effects of tocopherols are reversible. For these studies, mice were treated with antigen and supplemental tocopherols in a first phase of treatment followed by a 4 week clearance phase and then the mice received a second phase of antigen and tocopherol treatments. The pro-inflammatory effects of supplemental levels of γ-tocopherol in phase 1 were only partially reversed by supplemental α-tocopherol in phase 2 but were completely reversed by raising α-tocopherol levels 10-fold in phase 2. When γ-tocopherol levels were increased 10-fold (highly-elevated tocopherol) so that the lung tissue γ-tocopherol levels were equal to the lung tissue levels of supplemental α-tocopherol, γ-tocopherol reduced leukocyte numbers in the lung lavage fluid. In contrast to the lung lavage fluid, highly-elevated levels of γ-tocopherol increased inflammation in the lung tissue. These regulatory effects of highly-elevated tocopherols on tissue inflammation and lung lavage fluid were reversible in a second phase of antigen challenge without tocopherols. In summary, the pro-inflammatory effects of supplemental γ-tocopherol on lung inflammation were partially reversed by supplemental levels of α-tocopherol but were completely reversed by highly-elevated-levels of α-tocopherol. Also, highly-elevated levels of γ-tocopherol were inhibitory and reversible in lung lavage but, importantly, were pro-inflammatory in lung tissue sections. These results have implications for future studies with tocopherols and provide a new context in which to review vitamin E studies in the literature. PMID:21317387

Phase correction system for automatic focusing of synthetic aperture radar

DOEpatents

Eichel, Paul H.; Ghiglia, Dennis C.; Jakowatz, Jr., Charles V.

1990-01-01

A phase gradient autofocus system for use in synthetic aperture imaging accurately compensates for arbitrary phase errors in each imaged frame by locating highlighted areas and determining the phase disturbance or image spread associated with each of these highlight areas. An estimate of the image spread for each highlighted area in a line in the case of one dimensional processing or in a sector, in the case of two-dimensional processing, is determined. The phase error is determined using phase gradient processing. The phase error is then removed from the uncorrected image and the process is iteratively performed to substantially eliminate phase errors which can degrade the image.

Fabrication and microstructures of functional gradient SiBCN–Nb composite by hot pressing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Min, E-mail: lcxsunmin@163.com; Fu, Ruoyu; Chen, Jun

2016-04-15

A functional gradient material with five layers composed of SiBCN ceramic and niobium (Nb) was prepared successfully by hot pressing. The phase composition, morphology features and microstructures were investigated in each layer of the gradient material. The Nb-containing compounds involving NbC, Nb{sub 6}C{sub 5}, Nb{sub 4}C{sub 3}, Nb{sub 5}Si{sub 3} and NbN increase with the volume fraction of Nb increasing in the sub-layer. They are randomly scattered (≤ 25 vol.% Nb), then strip-like, and finally distribute continuously (≥ 75 vol.% Nb). The size of BN(C) and SiC grains in Nb-containing layers is larger than in 100% SiBCN layer due tomore » the loss of the capsule-like structures. No distinct interfaces form in the transition regions indicating the gradual changes in phase composition and microstructures. - Highlights: • A functional gradient SiBCN–Nb material was prepared successfully by hot pressing. • Phase composition, morphology features and microstructures were investigated. • Thermodynamic calculation was used to aid in the phase analysis. • No distinct interfaces form typical of the functional gradient material.« less

The development of an elastic reverse gradient garment to be used as a countermeasure for cardiovascular deconditioning

NASA Technical Reports Server (NTRS)

Annis, J. F.; Webb, P.

1973-01-01

Using a new Nomex-Lycra elastic fabric and individualized garment engineering techniques, reverse gradient garments (RGG's) were designed, constructed, and tested for effectiveness as a countermeasure against cardiovascular deconditioning. By combining torso-compensated positive pressure breathing with a distally diminishing gradient of counterpressure supplied by the elastic fabric on the limbs, the RGG acts to pool blood in the extremities of recumbent persons much as though they were standing erect in 1 g. It was theorized that through the use of a dynamic pressurization scheme, the RGG would stress the vasculature in a fashion similar to that experienced by the noramlly active man, hence preventing or limiting the development of post-weightlessness orthostatic intolerance and related conditions. Four male, college-age subjects received daily treatments with the RGG during a 15-day bedrest study. Four additional subjects also underwent the bedrest, but received no treatments; they served as controls. The design and construction of the garments are described, and results of the treatment related measurements are given.

The Phase Rule in a System Subject to a Pressure Gradient

NASA Astrophysics Data System (ADS)

Podladchikov, Yuri; Connolly, James; Powell, Roger; Aardvark, Alberto

2015-04-01

It can be shown by diligent application of Lagrange's method of undetermined multipliers that the phase rule in a system subject to a pressure gradient is: � + 赑 ≥ ρ. We explore the consequence of this important relationship for natural systems.

Interface Promoted Reversible Mg Insertion in Nanostructured Tin-Antimony Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Yingwen; Shao, Yuyan; Parent, Lucas R.

This paper demonstrates intermetallic compounds SnSb are highly active materials for reversibly hosting Mg ions. Compared with monometallic Sn and Sb, SnSb alloy exhibited exceptionally high reversible capacity (420 mAh/g), excellent rate capability and good cyclic stability. Mg insertion into pristine SnSb involves an activation process to complete, which induces particle breakdown and results in phase segregation to Sn-rich and Sb-rich phases. Both experimental analysis and DFT simulation suggest that the Sn-rich phase is particularly active and provides most of the capacity whereas the Sb-rich phase is not as active, and the interface between these two phases play a keymore » role in promoting the formation and stabilization of the cubic Sn phase that is more favorable for fast and reversible Mg insertion. We further show that activated SnSb alloy has good compatibility with simple Mg electrolytes. Overall, this work could provide new approaches for designing materials capable of reversible Mg ion insertion and new opportunities for understanding Mg electrochemistry.« less

Analysis of temporal shear stress gradients during the onset phase of flow over a backward-facing step.

PubMed

Haidekker, M A; White, C R; Frangos, J A

2001-10-01

Endothelial cells in blood vessels are exposed to bloodflow and thus fluid shear stress. In arterial bifurcations and stenoses, disturbed flow causes zones of recirculation and stagnation, which are associated with both spatial and temporal gradients of shear stress. Such gradients have been linked to the generation of atherosclerotic plaques. For in-vitro studies of endothelial cell responses, the sudden-expansion flow chamber has been widely used and described. A two-dimensional numerical simulation of the onset phase of flow through the chamber was performed. The wall shear stress action on the bottom plate was computed as a function of time and distance from the sudden expansion. The results showed that depending on the time for the flow to be established, significant temporal gradients occurred close to the second stagnation point of flow. Slowly ramping the flow over 15 s instead of 200 ms reduces the temporal gradients by a factor of 300, while spatial gradients are reduced by 23 percent. Thus, the effects of spatial and temporal gradients can be observed separately. In experiments on endothelial cells, disturbed flow stimulated cell proliferation only when flow onset was sudden. The spatial patterns of proliferation rate match the exposure to temporal gradients. This study provides information on the dynamics of spatial and temporal gradients to which the cells are exposed in a sudden-expansion flow chamber and relates them to changes in the onset phase of flow.

Interrelationship of mid-diastolic mitral valve motion, pulmonary venous flow, and transmitral flow.

PubMed

Keren, G; Meisner, J S; Sherez, J; Yellin, E L; Laniado, S

1986-07-01

This study offers a unifying mechanism of left ventricular filling dynamics to link the unexplained mid-diastolic motion of the mitral valve with an associated increase in transmitral flow, with the phasic character of pulmonary vein flow, and with changes in the atrioventricular pressure difference. M mode echograms of mitral valve motion and Doppler echocardiograms of mitral and pulmonary vein flow velocities were recorded in 12 healthy volunteers (heart rate = 60 +/- 9 beats/min). All echocardiograms showed an undulation in the mitral valve (L motion) at a relatively constant delay from the peak of the diastolic phase of pulmonary vein flow (K phase). In six subjects, the L motion was also associated with a distinct wave of mitral flow (L wave). Measured from the onset of the QRS complex, Q-K was 577 +/- 39 msec; Q-L was 703 +/- 42 msec, and K-L was 125 +/- 16 msec. Multiple measurements within each subject during respiratory variations in RR interval indicated exceptionally small differences in the temporal relationships (mean coefficient of variation 2%). Early rapid flow deceleration is caused by a reversal of the atrioventricular pressure gradient, and the L wave arises from the subsequent reestablishment of a positive gradient due to left atrial filling via the pulmonary veins. The mitral valve moves passively in response to the flowing blood and the associated pressure difference. This interpretation is confirmed by (1) a computational model, and (2) a retrospective analysis of data from patients with mitral stenosis and from conscious dogs instrumented to measure transmitral pressure-flow relationships.

Phase-field modelling of ductile fracture: a variational gradient-extended plasticity-damage theory and its micromorphic regularization

PubMed Central

Teichtmeister, S.; Aldakheel, F.

2016-01-01

This work outlines a novel variational-based theory for the phase-field modelling of ductile fracture in elastic–plastic solids undergoing large strains. The phase-field approach regularizes sharp crack surfaces within a pure continuum setting by a specific gradient damage modelling. It is linked to a formulation of gradient plasticity at finite strains. The framework includes two independent length scales which regularize both the plastic response as well as the crack discontinuities. This ensures that the damage zones of ductile fracture are inside of plastic zones, and guarantees on the computational side a mesh objectivity in post-critical ranges. PMID:27002069

Phase locking of a seven-channel continuous wave fibre laser system by a stochastic parallel gradient algorithm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Volkov, M V; Garanin, S G; Dolgopolov, Yu V

2014-11-30

A seven-channel fibre laser system operated by the master oscillator – multichannel power amplifier scheme is the phase locked using a stochastic parallel gradient algorithm. The phase modulators on lithium niobate crystals are controlled by a multichannel electronic unit with the microcontroller processing signals in real time. The dynamic phase locking of the laser system with the bandwidth of 14 kHz is demonstrated, the time of phasing is 3 – 4 ms. (fibre and integrated-optical structures)

Rapid Development and Validation of Improved Reversed-Phase High-performance Liquid Chromatography Method for the Quantification of Mangiferin, a Polyphenol Xanthone Glycoside in Mangifera indica

PubMed Central

Naveen, P.; Lingaraju, H. B.; Prasad, K. Shyam

2017-01-01

Mangiferin, a polyphenolic xanthone glycoside from Mangifera indica, is used as traditional medicine for the treatment of numerous diseases. The present study was aimed to develop and validate a reversed-phase high-performance liquid chromatography (RP-HPLC) method for the quantification of mangiferin from the bark extract of M. indica. RP-HPLC analysis was performed by isocratic elution with a low-pressure gradient using 0.1% formic acid: acetonitrile (87:13) as a mobile phase with a flow rate of 1.5 ml/min. The separation was done at 26°C using a Kinetex XB-C18 column as stationary phase and the detection wavelength at 256 nm. The proposed method was validated for linearity, precision, accuracy, limit of detection, limit of quantification, and robustness by the International Conference on Harmonisation guidelines. In linearity, the excellent correlation coefficient more than 0.999 indicated good fitting of the curve and also good linearity. The intra- and inter-day precision showed < 1% of relative standard deviation of peak area indicated high reliability and reproducibility of the method. The recovery values at three different levels (50%, 100%, and 150%) of spiked samples were found to be 100.47, 100.89, and 100.99, respectively, and low standard deviation value < 1% shows high accuracy of the method. In robustness, the results remain unaffected by small variation in the analytical parameters, which shows the robustness of the method. Liquid chromatography–mass spectrometry analysis confirmed the presence of mangiferin with M/Z value of 421. The assay developed by HPLC method is a simple, rapid, and reliable for the determination of mangiferin from M. indica. SUMMARY The present study was intended to develop and validate an RP-HPLC method for the quantification of mangiferin from the bark extract of M. indica. The developed method was validated for linearity, precision, accuracy, limit of detection, limit of quantification and robustness by International Conference on Harmonization guidelines. This study proved that the developed assay by HPLC method is a simple, rapid and reliable for the quantification of the mangiferin from M. indica. Abbreviations Used: M. indica: Mangifera indica, RP-HPLC: Reversed-phase high-performance liquid chromatography, M/Z: Mass to charge ratio, ICH: International conference on harmonization, % RSD: Percentage of relative standard deviation, ppm: Parts per million, LOD: Limit of detection, LOQ: Limit of quantification. PMID:28539748

Rapid Development and Validation of Improved Reversed-Phase High-performance Liquid Chromatography Method for the Quantification of Mangiferin, a Polyphenol Xanthone Glycoside in Mangifera indica.

PubMed

Naveen, P; Lingaraju, H B; Prasad, K Shyam

2017-01-01

Mangiferin, a polyphenolic xanthone glycoside from Mangifera indica , is used as traditional medicine for the treatment of numerous diseases. The present study was aimed to develop and validate a reversed-phase high-performance liquid chromatography (RP-HPLC) method for the quantification of mangiferin from the bark extract of M. indica . RP-HPLC analysis was performed by isocratic elution with a low-pressure gradient using 0.1% formic acid: acetonitrile (87:13) as a mobile phase with a flow rate of 1.5 ml/min. The separation was done at 26°C using a Kinetex XB-C18 column as stationary phase and the detection wavelength at 256 nm. The proposed method was validated for linearity, precision, accuracy, limit of detection, limit of quantification, and robustness by the International Conference on Harmonisation guidelines. In linearity, the excellent correlation coefficient more than 0.999 indicated good fitting of the curve and also good linearity. The intra- and inter-day precision showed < 1% of relative standard deviation of peak area indicated high reliability and reproducibility of the method. The recovery values at three different levels (50%, 100%, and 150%) of spiked samples were found to be 100.47, 100.89, and 100.99, respectively, and low standard deviation value < 1% shows high accuracy of the method. In robustness, the results remain unaffected by small variation in the analytical parameters, which shows the robustness of the method. Liquid chromatography-mass spectrometry analysis confirmed the presence of mangiferin with M/Z value of 421. The assay developed by HPLC method is a simple, rapid, and reliable for the determination of mangiferin from M. indica . The present study was intended to develop and validate an RP-HPLC method for the quantification of mangiferin from the bark extract of M. indica . The developed method was validated for linearity, precision, accuracy, limit of detection, limit of quantification and robustness by International Conference on Harmonization guidelines. This study proved that the developed assay by HPLC method is a simple, rapid and reliable for the quantification of the mangiferin from M. indica . Abbreviations Used: M. indica : Mangifera indica , RP-HPLC: Reversed-phase high-performance liquid chromatography, M/Z: Mass to charge ratio, ICH: International conference on harmonization, % RSD: Percentage of relative standard deviation, ppm: Parts per million, LOD: Limit of detection, LOQ: Limit of quantification.

Reverse Transcriptase-Containing Particles Induced in Rous Sarcoma Virus-Transformed Rat Cells by Arginine Deprivation

PubMed Central

Kotler, Moshe; Weinberg, Eynat; Haspel, Osnat; Becker, Yechiel

1972-01-01

Incubation of rat cells transformed by Rous sarcoma virus (RSV) in an arginine-deficient medium resulted in accumulation of particles in the culture medium. Such particles did not appear when the transformed rat cells were incubated in a complete medium nor in the medium of primary rat cells which were incubated either in arginine-deficient or complete media. The particles which were released from the arginine-deprived transformed rat cells resemble C-type particles in their properties. These particles band in sucrose gradients at a density of 1.16 g/ml and contain 35S ribonucleic acid (RNA) molecules and a reverse transcriptase activity. Analysis of the cytoplasm of transformed and primary rat cells, deprived and undeprived of arginine, revealed the presence of reverse transcriptase-containing particles which banded in sucrose gradients at a density of 1.14 g/ml. These particles differed from the particles released into the medium by the arginine-deprived RSV-transformed rat cells. The deoxyribonucleic acid (DNA) molecules synthesized in vitro by the reverse transcriptase present in the particles isolated from the medium of arginine-deprived cells hybridized to RSV RNA, whereas the DNA synthesized by the cell-bound enzyme had no homology to RSV RNA. PMID:4116137

A complementary mobile phase approach based on the peak count concept oriented to the full resolution of complex mixtures.

PubMed

Ortín, A; Torres-Lapasió, J R; García-Álvarez-Coque, M C

2011-08-26

Situations of minimal resolution are often found in liquid chromatography, when samples that contain a large number of compounds, or highly similar in terms of structure and/or polarity, are analysed. This makes full resolution with a single separation condition (e.g., mobile phase, gradient or column) unfeasible. In this work, the optimisation of the resolution of such samples in reversed-phase liquid chromatography is approached using two or more isocratic mobile phases with a complementary resolution behaviour (complementary mobile phases, CMPs). Each mobile phase is dedicated to the separation of a group of compounds. The CMPs are selected in such a way that, when the separation is considered globally, all the compounds in the sample are satisfactorily resolved. The search of optimal CMPs can be carried out through a comprehensive examination of the mobile phases in a selected domain. The computation time of this search has been reported to be substantially reduced by application of a genetic algorithm with local search (LOGA). A much simpler approach is here described, which is accessible to non-experts in programming, and offers solutions of the same quality as LOGA, with a similar computation time. The approach makes a sequential search of CMPs based on the peak count concept, which is the number of peaks exceeding a pre-established resolution threshold. The new approach is described using as test sample a mixture of 30 probe compounds, 23 of them with an ionisable character, and the pH and organic solvent contents as experimental factors. Copyright © 2011 Elsevier B.V. All rights reserved.

Edge Pushing is Equivalent to Vertex Elimination for Computing Hessians

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Mu; Pothen, Alex; Hovland, Paul

We prove the equivalence of two different Hessian evaluation algorithms in AD. The first is the Edge Pushing algorithm of Gower and Mello, which may be viewed as a second order Reverse mode algorithm for computing the Hessian. In earlier work, we have derived the Edge Pushing algorithm by exploiting a Reverse mode invariant based on the concept of live variables in compiler theory. The second algorithm is based on eliminating vertices in a computational graph of the gradient, in which intermediate variables are successively eliminated from the graph, and the weights of the edges are updated suitably. We provemore » that if the vertices are eliminated in a reverse topological order while preserving symmetry in the computational graph of the gradient, then the Vertex Elimination algorithm and the Edge Pushing algorithm perform identical computations. In this sense, the two algorithms are equivalent. This insight that unifies two seemingly disparate approaches to Hessian computations could lead to improved algorithms and implementations for computing Hessians. Read More: http://epubs.siam.org/doi/10.1137/1.9781611974690.ch11« less

Charge-reversal nanoparticles: novel targeted drug delivery carriers.

PubMed

Chen, Xinli; Liu, Lisha; Jiang, Chen

2016-07-01

Spurred by significant progress in materials chemistry and drug delivery, charge-reversal nanocarriers are being developed to deliver anticancer formulations in spatial-, temporal- and dosage-controlled approaches. Charge-reversal nanoparticles can release their drug payload in response to specific stimuli that alter the charge on their surface. They can elude clearance from the circulation and be activated by protonation, enzymatic cleavage, or a molecular conformational change. In this review, we discuss the physiological basis for, and recent advances in the design of charge-reversal nanoparticles that are able to control drug biodistribution in response to specific stimuli, endogenous factors (changes in pH, redox gradients, or enzyme concentration) or exogenous factors (light or thermos-stimulation).

High-efficiency polarization conversion phase gradient metasurface for wideband anomalous reflection

NASA Astrophysics Data System (ADS)

Zhang, Jiameng; Yang, Lan; Li, Linpeng; Zhang, Tong; Li, Haihong; Wang, Qingmin; Hao, Yanan; Lei, Ming; Bi, Ke

2017-07-01

An ultra-wideband polarization conversion metasurface based on S-shaped metallic structure is designed and prepared. The simulation results show that the polarization conversion bandwidth is 14 GHz for linearly polarized normally incident electromagnetic waves and the cross-polarized reflectance is more than 99% in the range of 10.3 GHz-20.5 GHz. On the premise of high reflection efficiency, the reflective phase can be regulated by changing the geometrical parameter of the S-shaped metallic structure. A phase gradient metasurface composed of six periodically arrayed S-shaped unit cells is proposed and further demonstrated both numerically and experimentally. The specular cross-polarization reflection of the phase gradient metasurface is below -10 dB, which shows a good performance on manipulating the direction of the reflected electromagnetic waves.

Optimized distortion correction technique for echo planar imaging.

PubMed

Chen , N K; Wyrwicz, A M

2001-03-01

A new phase-shifted EPI pulse sequence is described that encodes EPI phase errors due to all off-resonance factors, including B(o) field inhomogeneity, eddy current effects, and gradient waveform imperfections. Combined with the previously proposed multichannel modulation postprocessing algorithm (Chen and Wyrwicz, MRM 1999;41:1206-1213), the encoded phase error information can be used to effectively remove geometric distortions in subsequent EPI scans. The proposed EPI distortion correction technique has been shown to be effective in removing distortions due to gradient waveform imperfections and phase gradient-induced eddy current effects. In addition, this new method retains advantages of the earlier method, such as simultaneous correction of different off-resonance factors without use of a complicated phase unwrapping procedure. The effectiveness of this technique is illustrated with EPI studies on phantoms and animal subjects. Implementation to different versions of EPI sequences is also described. Magn Reson Med 45:525-528, 2001. Copyright 2001 Wiley-Liss, Inc.

Optimizing separate phase light hydrocarbon recovery from contaminated unconfined aquifers

NASA Astrophysics Data System (ADS)

Cooper, Grant S.; Peralta, Richard C.; Kaluarachchi, Jagath J.

A modeling approach is presented that optimizes separate phase recovery of light non-aqueous phase liquids (LNAPL) for a single dual-extraction well in a homogeneous, isotropic unconfined aquifer. A simulation/regression/optimization (S/R/O) model is developed to predict, analyze, and optimize the oil recovery process. The approach combines detailed simulation, nonlinear regression, and optimization. The S/R/O model utilizes nonlinear regression equations describing system response to time-varying water pumping and oil skimming. Regression equations are developed for residual oil volume and free oil volume. The S/R/O model determines optimized time-varying (stepwise) pumping rates which minimize residual oil volume and maximize free oil recovery while causing free oil volume to decrease a specified amount. This S/R/O modeling approach implicitly immobilizes the free product plume by reversing the water table gradient while achieving containment. Application to a simple representative problem illustrates the S/R/O model utility for problem analysis and remediation design. When compared with the best steady pumping strategies, the optimal stepwise pumping strategy improves free oil recovery by 11.5% and reduces the amount of residual oil left in the system due to pumping by 15%. The S/R/O model approach offers promise for enhancing the design of free phase LNAPL recovery systems and to help in making cost-effective operation and management decisions for hydrogeologists, engineers, and regulators.

Accurate prediction of retention in hydrophilic interaction chromatography by back calculation of high pressure liquid chromatography gradient profiles.

PubMed

Wang, Nu; Boswell, Paul G

2017-10-20

Gradient retention times are difficult to project from the underlying retention factor (k) vs. solvent composition (φ) relationships. A major reason for this difficulty is that gradients produced by HPLC pumps are imperfect - gradient delay, gradient dispersion, and solvent mis-proportioning are all difficult to account for in calculations. However, we recently showed that a gradient "back-calculation" methodology can measure these imperfections and take them into account. In RPLC, when the back-calculation methodology was used, error in projected gradient retention times is as low as could be expected based on repeatability in the k vs. φ relationships. HILIC, however, presents a new challenge: the selectivity of HILIC columns drift strongly over time. Retention is repeatable in short time, but selectivity frequently drifts over the course of weeks. In this study, we set out to understand if the issue of selectivity drift can be avoid by doing our experiments quickly, and if there any other factors that make it difficult to predict gradient retention times from isocratic k vs. φ relationships when gradient imperfections are taken into account with the back-calculation methodology. While in past reports, the accuracy of retention projections was >5%, the back-calculation methodology brought our error down to ∼1%. This result was 6-43 times more accurate than projections made using ideal gradients and 3-5 times more accurate than the same retention projections made using offset gradients (i.e., gradients that only took gradient delay into account). Still, the error remained higher in our HILIC projections than in RPLC. Based on the shape of the back-calculated gradients, we suspect the higher error is a result of prominent gradient distortion caused by strong, preferential water uptake from the mobile phase into the stationary phase during the gradient - a factor our model did not properly take into account. It appears that, at least with the stationary phase we used, column distortion is an important factor to take into account in retention projection in HILIC that is not usually important in RPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of first dimension phase selectivity in online comprehensive two dimensional liquid chromatography (LC × LC)

PubMed Central

Gu, Haiwei; Huang, Yuan; Filgueira, Marcelo; Carr, Peter W.

2012-01-01

In this study, we examined the effect of first dimension column selectivity in reversed phase (RP) online comprehensive two dimensional liquid chromatography (LC × LC). The second dimension was always a carbon clad metal oxide reversed phase material. The hydrophobic subtraction model (HSM) and the related phase selective triangles were used to guide the selection of six different RP first dimension columns. Various kinds of samples were investigated and thus two different elution conditions were needed to cause full elution from the first dimension columns. We compared LC × LC chromatograms, contours plots, and fcoverage plots by measuring peak capacities, peak numbers, relative spatial coverage, correlation values, etc. The major finding of this study is that the carbon phase due to its rather different selectivity from other reversed phases is reasonably orthogonal to a variety of common types of bonded reversed phases. Thus quite surprisingly the six different first dimension stationary phases all showed generally similar separation patterns when paired to the second dimension carbon phase. This result greatly simplifies the task of choosing the correct pair of phases for RP × RP. PMID:21840009

Separation and purification of hydrolyzable tannin from Geranium wilfordii Maxim by reversed-phase and normal-phase high-speed counter-current chromatography.

PubMed

Liu, Dan; Su, Zhiguo; Wang, Changhai; Gu, Ming; Xing, Siliang

2010-08-01

Three hydrolyzable tannins, geraniin, corilagin and gallic acid, main active components of Geranium wilfordii Maxim, have been separated and purified in one-step by both reversed-phase and normal-phase high-speed counter-current chromatography. Gallic acid, corilagin and geraniin were purified from 70% aqueous acetone extract of G. wilfordii Maxim with solvent system n-hexane-ethyl acetate-methanol-acetic acid-water (1:10:0.2:0.2:20) by reversed-phase high-speed counter-current chromatography at purities of 94.2, 91.0 and 91.3%, at yields of 89.3, 82.9 and 91.7%, respectively. Gallic acid, corilagin and geraniin were purified with solvent system n-hexane-ethyl acetate-methanol-acetic acid-water (0.2:10:2:1:5) by normal-phase high-speed counter-current chromatography at purities of 85.9, 92.2 and 87.6%, at yields of 87.4, 94.6 and 94.3%, respectively. It was successful for both reversed-phase and normal-phase high-speed counter-current chromatography to separate high-polarity of low-molecular-weight substances.

Some Peculiarities of Water Transport through Plasticized Nonporous Membranes

PubMed Central

Marian, S.; Jagur-Grodzinski, J.; Kedem, O.; Vofsi, D.

1970-01-01

“Liquid” and “plasticized” solvent membranes are of interest as possible analogues of biological systems. Semipermeable homogeneous films are prepared by plasticizing polyvinylchloride with organic phosphates. Water permeability of such films is relatively high. For a material containing 70% of 1.4-dihydroxyphenyl-bis(dibutylphosphate), the diffusion coefficient of water at room temperature was estimated to be about 1 × 10-6 cm2/sec. Conditioning of a plasticized membrane, under the osmotic gradient of solution of sodium nitrate, leads to profound changes in its morphology and to a drastic increase of its water permeability. The induced changes are reversible to a large extent. Their reversibility in various solutions may be correlated with the respective differences in permselectivity. The structure of expanded membranes and the mechanism of changes taking place under the osmotic gradients are discussed. ImagesFigure 2 PMID:5496907

Ultrasensitivity by Molecular Titration in Spatially Propagating Enzymatic Reactions

PubMed Central

Semenov, Sergey N.; Markvoort, Albert J.; Gevers, Wouter B.L.; Piruska, Aigars; de Greef, Tom F.A.; Huck, Wilhelm T.S.

2013-01-01

Delineating design principles of biological systems by reconstitution of purified components offers a platform to gauge the influence of critical physicochemical parameters on minimal biological systems of reduced complexity. Here we unravel the effect of strong reversible inhibitors on the spatiotemporal propagation of enzymatic reactions in a confined environment in vitro. We use micropatterned, enzyme-laden agarose gels which are stamped on polyacrylamide films containing immobilized substrates and reversible inhibitors. Quantitative fluorescence imaging combined with detailed numerical simulations of the reaction-diffusion process reveal that a shallow gradient of enzyme is converted into a steep product gradient by addition of strong inhibitors, consistent with a mathematical model of molecular titration. The results confirm that ultrasensitive and threshold effects at the molecular level can convert a graded input signal to a steep spatial response at macroscopic length scales. PMID:23972857

Effects of digital phase-conjugate light intensity on time-reversal imaging through animal tissue.

PubMed

Toda, Sogo; Kato, Yuji; Kudo, Nobuki; Shimizu, Koichi

2018-04-01

For transillumination imaging of animal tissues, we have attempted to suppress the scattering effect in a turbid medium using the time-reversal principle of phase-conjugate light. We constructed a digital phase-conjugate system to enable intensity modulation and phase modulation. Using this system, we clarified the effectiveness of the intensity information for restoration of the original light distribution through a turbid medium. By varying the scattering coefficient of the medium, we clarified the limit of time-reversal ability with intensity information of the phase-conjugate light. Experiment results demonstrated the applicability of the proposed technique to animal tissue.

Gradient Pre-Emphasis to Counteract First-Order Concomitant Fields on Asymmetric MRI Gradient Systems

PubMed Central

Tao, Shengzhen; Weavers, Paul T.; Trzasko, Joshua D.; Shu, Yunhong; Huston, John; Lee, Seung-Kyun; Frigo, Louis M.; Bernstein, Matt A.

2016-01-01

PURPOSE To develop a gradient pre-emphasis scheme that prospectively counteracts the effects of the first-order concomitant fields for any arbitrary gradient waveform played on asymmetric gradient systems, and to demonstrate the effectiveness of this approach using a real-time implementation on a compact gradient system. METHODS After reviewing the first-order concomitant fields that are present on asymmetric gradients, a generalized gradient pre-emphasis model assuming arbitrary gradient waveforms is developed to counteract their effects. A numerically straightforward, simple to implement approximate solution to this pre-emphasis problem is derived, which is compatible with the current hardware infrastructure used on conventional MRI scanners for eddy current compensation. The proposed method was implemented on the gradient driver sub-system, and its real-time use was tested using a series of phantom and in vivo data acquired from 2D Cartesian phase-difference, echo-planar imaging (EPI) and spiral acquisitions. RESULTS The phantom and in vivo results demonstrate that unless accounted for, first-order concomitant fields introduce considerable phase estimation error into the measured data and result in images exhibiting spatially dependent blurring/distortion. The resulting artifacts are effectively prevented using the proposed gradient pre-emphasis. CONCLUSION An efficient and effective gradient pre-emphasis framework is developed to counteract the effects of first-order concomitant fields of asymmetric gradient systems. PMID:27373901

Wavefront image sensor chip

PubMed Central

Cui, Xiquan; Ren, Jian; Tearney, Guillermo J.; Yang, Changhuei

2010-01-01

We report the implementation of an image sensor chip, termed wavefront image sensor chip (WIS), that can measure both intensity/amplitude and phase front variations of a light wave separately and quantitatively. By monitoring the tightly confined transmitted light spots through a circular aperture grid in a high Fresnel number regime, we can measure both intensity and phase front variations with a high sampling density (11 µm) and high sensitivity (the sensitivity of normalized phase gradient measurement is 0.1 mrad under the typical working condition). By using WIS in a standard microscope, we can collect both bright-field (transmitted light intensity) and normalized phase gradient images. Our experiments further demonstrate that the normalized phase gradient images of polystyrene microspheres, unstained and stained starfish embryos, and strongly birefringent potato starch granules are improved versions of their corresponding differential interference contrast (DIC) microscope images in that they are artifact-free and quantitative. Besides phase microscopy, WIS can benefit machine recognition, object ranging, and texture assessment for a variety of applications. PMID:20721059

HPLC Determination of Esculin and Esculetin in Rat Plasma for Pharmacokinetic Studies.

PubMed

Rehman, Shaheed Ur; Kim, In Sook; Kang, Ki Sung; Yoo, Hye Hyun

2015-09-01

An optimized, sensitive and validated reversed-phase high-performance liquid chromatography (RP-HPLC) method with UV detection is described for simultaneous determination of esculin and its aglycone, esculetin, in rat plasma. After addition of internal standard (chrysin), plasma samples were pretreated by solid-phase extraction and introduced into the HPLC system. Analytes were separated on a RP C18 column with a mobile phase of 0.075% acetic acid in water (solvent A) and 90% acetonitrile in solvent A (solvent B) using gradient elution at a flow rate of 1.0 mL/min. The wavelength for UV detection was set at 338 nm. Calibration curves for esculin and esculetin were constructed over a range of 10-1,000 ng/mL. The developed method was found to be specific, precise and accurate. The method was successfully applied to study the pharmacokinetics of esculin and esculetin in rats. After oral administration of 120 mg/kg, the mean Cmax values were 340.3 and 316.5 ng/mL and the AUClast values were 377.3 and 1276.5 h ng/mL for esculin and esculetin, respectively. The bioavailability of esculin was calculated to be 0.62%. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Simultaneous quantification of major flavonoids in "Bawanghua", the edible flower of Hylocereus undatus using pressurised liquid extraction and high performance liquid chromatography.

PubMed

Yi, Yan; Zhang, Qing-Wen; Li, Song-Lin; Wang, Ying; Ye, Wen-Cai; Zhao, Jing; Wang, Yi-Tao

2012-11-15

A pressurised liquid extraction (PLE) and high performance liquid chromatography (HPLC) method was developed for simultaneous quantification of six major flavonoids in edible flower of Hylocereus undatus. In order to achieve the baseline separation of two pairs of isomers, the HPLC conditions were optimised with different kind of reversed phase columns and mobile phase gradient programs. In addition, the solvent concentration, extraction temperature, extraction time and flush cycle for PLE were also optimised. Zorbax SB-C8 (100×2.1 mm, 1.8 μm) column was chosen with acetonitrile and water containing 0.1% trifluoroacetic acid as mobile phase, the six analytes were eluted with baseline separation. The calibration curves showed good linearity (r(2)>0.9994) with LODs and LOQs less than 0.90 and 3.60 ng respectively. The RSDs for intra- and inter-day repeatability was not more than 1.09% and 1.79% respectively. The overall recovery of the assay was 96.9-105.2%. The sample was stable for at least 12 h. The newly established method was successfully applied to quantify six flavonoids in different parts of "Bawanghua", and the commercial samples from different locations. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effect of the laser heat treatment on the formation of the gradient structures in alloys based on Fe - Cr - Ni system

NASA Astrophysics Data System (ADS)

Andreev, A. O.; Bykovskiy, D. P.; Osintsev, A. V.; Petrovskiy, V. N.; Ryashko, I. I.; Blinova, E. N.; Libman, M. A.; Glezer, A. M.

2017-12-01

The possibility of producing gradient materials, i.e. materials with pre-set distribution of areas having fundamentally different physical and mechanical characteristics, with the help of laser heat treatment was investigated. Using as an example austenitic-martensitic alloys of iron-chromium-nickel, subjected to cold plastic deformation led to formation of martensite, we show that using laser at the temperature higher than the temperature of reverse martensite transformation leads to the formation of areas of high-strength austenite having predetermined form inside the martensite matrix. Influence of austenite areas geometry on mechanical properties of gradient material was studied.

The educational gradient in marital disruption: a meta-analysis of European research findings.

PubMed

Matysiak, Anna; Styrc, Marta; Vignoli, Daniele

2014-01-01

A large number of empirical studies have investigated the effects of women's education on union dissolution in Europe, but results have varied substantially. This paper seeks to assess the relationship between educational attainment and the incidence of marital disruption by systematizing the existing empirical evidence. A quantitative literature review (a meta-analysis) was conducted to investigate the temporal change in the relationship, net of inter-study differences. The results point to a weakening of the positive educational gradient in marital disruption over time and even to a reversal in the direction of this gradient in some countries. The findings also show that the change in the educational gradient can be linked to an increase in access to divorce. Finally, the results suggest that women's empowerment has played an important role in changing the educational gradient, while the liberalization of divorce laws has not.

Design and fabrication of a metamaterial gradient index diffraction grating at infrared wavelengths.

PubMed

Tsai, Yu-Ju; Larouche, Stéphane; Tyler, Talmage; Lipworth, Guy; Jokerst, Nan M; Smith, David R

2011-11-21

We demonstrate the design, fabrication and characterization of an artificially structured, gradient index metamaterial with a linear index variation of Δn ~ 3.0. The linear gradient profile is repeated periodically to form the equivalent of a blazed grating, with the gradient occurring across a spatial distance of 61 μm. The grating, which operates at a wavelength of 10.6 μm, is composed of non-resonant, progressively modified "I-beam" metamaterial elements and approximates a linear phase shift gradient using 61 distinguishable phase levels. The grating structure consists of four layers of lithographically patterned metallic I-beam elements separated by dielectric layers of SiO(2). The index gradient is confirmed by comparing the measured magnitudes of the -1, 0 and +1 diffracted orders to those obtained from full wave simulations incorporating all material properties of the metals and dielectrics of the structures. The large index gradient has the potential to enable compact infrared diffractive and gradient index optics, as well as more exotic transformation optical media. © 2011 Optical Society of America

A New Rapid and Sensitive Stability-Indicating UPLC Assay Method for Tolterodine Tartrate: Application in Pharmaceuticals, Human Plasma and Urine Samples.

PubMed

Yanamandra, Ramesh; Vadla, Chandra Sekhar; Puppala, Umamaheshwar; Patro, Balaram; Murthy, Yellajyosula L N; Ramaiah, Parimi Atchuta

2012-01-01

A new rapid, simple, sensitive, selective and accurate reversed-phase stability-indicating Ultra Performance Liquid Chromatography (RP-UPLC) technique was developed for the assay of Tolterodine Tartrate in pharmaceutical dosage form, human plasma and urine samples. The developed UPLC method is superior in technology to conventional HPLC with respect to speed, solvent consumption, resolution and cost of analysis. Chromatographic run time was 6 min in reversed-phase mode and ultraviolet detection was carried out at 220 nm for quantification. Efficient separation was achieved for all the degradants of Tolterodine Tartrate on BEH C18 sub-2-μm Acquity UPLC column using Trifluoroacetic acid and acetonitrile as organic solvent in a linear gradient program. The active pharmaceutical ingredient was extracted from tablet dosage form using a mixture of acetonitrile and water as diluent. The calibration graphs were linear and the method showed excellent recoveries for bulk and tablet dosage form. The test solution was found to be stable for 40 days when stored in the refrigerator between 2 and 8 °C. The developed UPLC method was validated and meets the requirements delineated by the International Conference on Harmonization (ICH) guidelines with respect to linearity, accuracy, precision, specificity and robustness. The intra-day and inter-day variation was found be less than 1%. The method was reproducible and selective for the estimation of Tolterodine Tartrate. Because the method could effectively separate the drug from its degradation products, it can be employed as a stability-indicating one.

A New Rapid and Sensitive Stability-Indicating UPLC Assay Method for Tolterodine Tartrate: Application in Pharmaceuticals, Human Plasma and Urine Samples

PubMed Central

Yanamandra, Ramesh; Vadla, Chandra Sekhar; Puppala, Umamaheshwar; Patro, Balaram; Murthy, Yellajyosula. L. N.; Ramaiah, Parimi Atchuta

2012-01-01

A new rapid, simple, sensitive, selective and accurate reversed-phase stability-indicating Ultra Performance Liquid Chromatography (RP-UPLC) technique was developed for the assay of Tolterodine Tartrate in pharmaceutical dosage form, human plasma and urine samples. The developed UPLC method is superior in technology to conventional HPLC with respect to speed, solvent consumption, resolution and cost of analysis. Chromatographic run time was 6 min in reversed-phase mode and ultraviolet detection was carried out at 220 nm for quantification. Efficient separation was achieved for all the degradants of Tolterodine Tartrate on BEH C18 sub-2-μm Acquity UPLC column using Trifluoroacetic acid and acetonitrile as organic solvent in a linear gradient program. The active pharmaceutical ingredient was extracted from tablet dosage form using a mixture of acetonitrile and water as diluent. The calibration graphs were linear and the method showed excellent recoveries for bulk and tablet dosage form. The test solution was found to be stable for 40 days when stored in the refrigerator between 2 and 8 °C. The developed UPLC method was validated and meets the requirements delineated by the International Conference on Harmonization (ICH) guidelines with respect to linearity, accuracy, precision, specificity and robustness. The intra-day and inter-day variation was found be less than 1%. The method was reproducible and selective for the estimation of Tolterodine Tartrate. Because the method could effectively separate the drug from its degradation products, it can be employed as a stability-indicating one. PMID:22396907

Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

PubMed

Bhushan, Ravi; Dixit, Shuchi

2012-04-01

Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

Phase-field modelling of ductile fracture: a variational gradient-extended plasticity-damage theory and its micromorphic regularization.

PubMed

Miehe, C; Teichtmeister, S; Aldakheel, F

2016-04-28

This work outlines a novel variational-based theory for the phase-field modelling of ductile fracture in elastic-plastic solids undergoing large strains. The phase-field approach regularizes sharp crack surfaces within a pure continuum setting by a specific gradient damage modelling. It is linked to a formulation of gradient plasticity at finite strains. The framework includes two independent length scales which regularize both the plastic response as well as the crack discontinuities. This ensures that the damage zones of ductile fracture are inside of plastic zones, and guarantees on the computational side a mesh objectivity in post-critical ranges. © 2016 The Author(s).

Controlling propagation and coupling of waveguide modes using phase-gradient metasurfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhaoyi; Kim, Myoung -Hwan; Wang, Cheng

Here, research on two-dimensional designer optical structures, or metasurfaces, has mainly focused on controlling the wavefronts of light propagating in free space. Here, we show that gradient metasurface structures consisting of phased arrays of plasmonic or dielectric nanoantennas can be used to control guided waves via strong optical scattering at subwavelength intervals. Based on this design principle, we experimentally demonstrate waveguide mode converters, polarization rotators and waveguide devices supporting asymmetric optical power transmission. We also demonstrate all-dielectric on-chip polarization rotators based on phased arrays of Mie resonators with negligible insertion losses. Our gradient metasurfaces can enable small-footprint, broadband and low-lossmore » photonic integrated devices.« less

Controlling propagation and coupling of waveguide modes using phase-gradient metasurfaces

DOE PAGES

Li, Zhaoyi; Kim, Myoung -Hwan; Wang, Cheng; ...

2017-04-17

Here, research on two-dimensional designer optical structures, or metasurfaces, has mainly focused on controlling the wavefronts of light propagating in free space. Here, we show that gradient metasurface structures consisting of phased arrays of plasmonic or dielectric nanoantennas can be used to control guided waves via strong optical scattering at subwavelength intervals. Based on this design principle, we experimentally demonstrate waveguide mode converters, polarization rotators and waveguide devices supporting asymmetric optical power transmission. We also demonstrate all-dielectric on-chip polarization rotators based on phased arrays of Mie resonators with negligible insertion losses. Our gradient metasurfaces can enable small-footprint, broadband and low-lossmore » photonic integrated devices.« less

Geologic and geophysical data for wells drilled at Raft River Valley, Cassia County, Idaho, in 1977-1978 and data for wells drilled previously

USGS Publications Warehouse

Nathenson, Manuel; Urban, Thomas C.; Covington, Harry R.

2014-01-01

For purposes of defining the thermal anomaly for the geothermal system, temperature gradients are calculated over long depth intervals on the basis of the appearance of reasonable linear segments on a temperature versus plot depth.  Temperature versus depth data for some drill holes can be represented by a single gradient, whereas others require multiple gradients to match the data.  Data for some drill holes clearly reflect vertical flows of water in the formation surrounding the drill holes, and water velocities are calculated for these drill holes.  Within The Narrows area, temperature versus depth data show reversals at different depth in different drill holes.  In the main thermal area, temperatures in intermediate-depth drill holes vary approximately linearly but with very high values of temperature gradient.  Temperature gradients on a map of the area can be reasonable divided into a large area of regional gradients and smaller areas defining the thermal anomalies.

A macrocyclic polyamine as an anion receptor in the capillary electrochromatographic separation of carbohydrates.

PubMed

Liu, Chuen-Ying; Chen, Tse-Hsien; Misra, Tarun Kumar

2007-06-22

An analytical approach of the 32-membered macrocyclic polyamine, 1,5,9,13,17,21,25,29-octaazacyclodotriacontane ([32]ane-N8) was described for the capillary electrochromatographic (CEC) separation of derivatized mono- and disaccharides. The column displayed reversal electroosmotic flow (EOF) at pH below 7.0, while a cathodic EOF was shown at pH above 7.0. The reductive amination of saccharides was carried out with p-aminobenzoic acid. Some parameters that affect the CEC separations were investigated. Several competitive ligands, such as Tris, EDTA and phosphate were also examined for the effect on the performance. We achieved a complete separation of all compounds as well as the excess derivatizing agent by using borate buffer (pH 9.0) in a mode of concentration gradient (60 mM inlet side and 70 mM outlet side). The relative standard deviation of the retention time measured for each sample was less than 4% in six continuous runs, suggesting that the bonded phase along with the gradient formed inside the column was quite stable. With the mixing modes of anion coordination, anion exchange, and shape discrimination, the interaction adequately accomplishes the separation of carbohydrates which are epimers or have different glycosidic linkage, although the electrophoretic migration is also involved in the separation mechanism.

Development of a 45kpsi ultrahigh pressure liquid chromatography instrument for gradient separations of peptides using long microcapillary columns and sub-2μm particles.

PubMed

Grinias, Kaitlin M; Godinho, Justin M; Franklin, Edward G; Stobaugh, Jordan T; Jorgenson, James W

2016-10-21

Commercial chromatographic instrumentation for bottom-up proteomics is often inadequate to resolve the number of peptides in many samples. This has inspired a number of complex approaches to increase peak capacity, including various multidimensional approaches, and reliance on advancements in mass spectrometry. One-dimensional reversed phase separations are limited by the pressure capabilities of commercial instruments and prevent the realization of greater separation power in terms of speed and resolution inherent to smaller sorbents and ultrahigh pressure liquid chromatography. Many applications with complex samples could benefit from the increased separation performance of long capillary columns packed with sub-2μm sorbents. Here, we introduce a system that operates at a constant pressure and is capable of separations at pressures up to 45kpsi. The system consists of a commercially available capillary liquid chromatography instrument, for sample management and gradient creation, and is modified with a storage loop and isolated pneumatic amplifier pump for elevated separation pressure. The system's performance is assessed with a complex peptide mixture and a range of microcapillary columns packed with sub-2μm C18 particles. Copyright © 2016 Elsevier B.V. All rights reserved.

Phase retrieval with the reverse projection method in the presence of object's scattering

NASA Astrophysics Data System (ADS)

Wang, Zhili; Gao, Kun; Wang, Dajiang

2017-08-01

X-ray grating interferometry can provide substantially increased contrast over traditional attenuation-based techniques in biomedical applications, and therefore novel and complementary information. Recently, special attention has been paid to quantitative phase retrieval in X-ray grating interferometry, which is mandatory to perform phase tomography, to achieve material identification, etc. An innovative approach, dubbed ;Reverse Projection; (RP), has been developed for quantitative phase retrieval. The RP method abandons grating scanning completely, and is thus advantageous in terms of higher efficiency and reduced radiation damage. Therefore, it is expected that this novel method would find its potential in preclinical and clinical implementations. Strictly speaking, the reverse projection method is applicable for objects exhibiting only absorption and refraction. In this contribution, we discuss the phase retrieval with the reverse projection method for general objects with absorption, refraction and scattering simultaneously. Especially, we investigate the influence of the object's scattering on the retrieved refraction signal. Both theoretical analysis and numerical experiments are performed. The results show that the retrieved refraction signal is the product of object's refraction and scattering signals for small values. In the case of a strong scattering, the reverse projection method cannot provide reliable phase retrieval. Those presented results will guide the use of the reverse projection method for future practical applications, and help to explain some possible artifacts in the retrieved images and/or reconstructed slices.

Molecular-level characterization of crude oil compounds combining reversed-phase high-performance liquid chromatography with off-line high-resolution mass spectrometry

USGS Publications Warehouse

Sim, Arum; Cho, Yunju; Kim, Daae; Witt, Matthias; Birdwell, Justin E.; Kim, Byung Ju; Kim, Sunghwan

2014-01-01

A reversed-phase separation technique was developed in a previous study (Loegel et al., 2012) and successfully applied to the de-asphalted fraction of crude oil. However, to the best of our knowledge, the molecular-level characterization of oil fractions obtained by reversed-phase high-performance liquid chromatography (HPLC) coupled with high-resolution mass spectrometry (MS) has not yet been reported. A detailed characterization of the oil fractions prepared by reversed-phase HPLC was performed in this study. HPLC fractionation was carried out on conventional crude oil and an oil shale pyrolysate. The analyses of the fractions showed that the carbon number of alkyl chains and the double bond equivalent (DBE) value were the major factors determining elution order. The compounds with larger DBE (presumably more condensed aromatic structures) and smaller carbon number (presumably compounds with short side chains) were eluted earlier but those compounds with lower DBE values (presumably less aromatic structures) and higher carbon number (presumably compounds with longer alkyl chains) eluted later in the chromatograms. This separation behavior is in good agreement with that expected from the principles of reversed-phase separation. The data presented in this study show that reversed-phase chromatography is effective in separating crude oil compounds and can be combined with ultrahigh-resolution MS data to better understand natural oils and oil shale pyrolysates.

Transitional Boundary Layers Under the Influence of High Free Stream Turbulence, Intensive Wall Cooling and High Pressure Gradients in Hot Gas Circulation. Ph.D. Thesis - Technische Hochschule, Karlsruhe, 1985

NASA Technical Reports Server (NTRS)

Rued, Klaus

1987-01-01

The requirements for fundamental experimental studies of the influence of free stream turbulence, pressure gradients and wall cooling are discussed. Under turbine-like free stream conditions, comprehensive tests of transitional boundary layers with laminar, reversing and turbulent flow increments were performed to decouple the effects of the parameters and to determine the effects during mutual interaction.

Reversible, on-demand generation of aqueous two-phase microdroplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collier, Charles Patrick; Retterer, Scott Thomas; Boreyko, Jonathan Barton

The present invention provides methods of on-demand, reversible generation of aqueous two-phase microdroplets core-shell microbeads, microparticle preparations comprising the core-shell microbeads, and drug delivery formulation comprising the microparticle preparations. Because these aqueous microdroplets have volumes comparable to those of cells, they provide an approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Hence, the present methods generate femtoliter aqueous two-phase droplets within a microfluidic oil channel using gated pressure pulses to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phasemore » transitions between single-phase, two-phase, and core-shell microbead states are obtained via evaporation-induced dehydration and water rehydration.« less

Experimental study of the heated contact line region for a pure fluid and binary fluid mixture in microgravity.

PubMed

Nguyen, Thao T T; Kundan, Akshay; Wayner, Peter C; Plawsky, Joel L; Chao, David F; Sicker, Ronald J

2017-02-15

Understanding the dynamics of phase change heat and mass transfer in the three-phase contact line region is a critical step toward improving the efficiency of phase change processes. Phase change becomes especially complicated when a fluid mixture is used. In this paper, a wickless heat pipe was operated on the International Space Station (ISS) to study the contact line dynamics of a pentane/isohexane mixture. Different interfacial regions were identified, compared, and studied. Using high resolution (50×), interference images, we calculated the curvature gradient of the liquid-vapor interface at the contact line region along the edges of the heat pipe. We found that the curvature gradient in the evaporation region increases with increasing heat flux magnitude and decreasing pentane concentration. The curvature gradient for the mixture case is larger than for the pure pentane case. The difference between the two cases increases as pentane concentration decreases. Our data showed that the curvature gradient profile within the evaporation section is separated into two regions with the boundary between the two corresponding to the location of a thick, liquid, "central drop" region at the point of maximum internal local heat flux. We found that the curvature gradients at the central drop and on the flat surfaces where condensation begins are one order of magnitude smaller than the gradients in the corner meniscus indicating the driving forces for fluid flow are much larger in the corners. Copyright © 2016 Elsevier Inc. All rights reserved.

Slow equilibration of reversed-phase columns for the separation of ionized solutes.

PubMed

Marchand, D H; Williams, L A; Dolan, J W; Snyder, L R

2003-10-10

Reversed-phase columns that have been stored in buffer-free solvents can exhibit pronounced retention-time drift when buffered, low-pH mobile phases are used with ionized solutes. Whereas non-ionized compounds exhibit constant retention times within 20 min of the beginning of mobile phase flow, the retention of ionized compounds can continue to change (by 20% or more) for several hours. If mobile phase pH is changed from low to high and back again, an even longer time may be required before the column reaches equilibration at low pH. The speed of column equilibration for ionized solutes can vary significantly among different reversed-phase columns and is not affected by flow rate.

Why do disk galaxies present a common gas-phase metallicity gradient?

NASA Astrophysics Data System (ADS)

Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

2017-03-01

CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

Texturing of high T(sub c) superconducting polycrystalline fibers/wires by laser-driven directional solidification in an thermal gradient

NASA Technical Reports Server (NTRS)

Varshney, Usha; Eichelberger, B. Davis, III

1995-01-01

This paper summarizes the technique of laser-driven directional solidification in a controlled thermal gradient of yttria stabilized zirconia core coated Y-Ba-Cu-O materials to produce textured high T(sub c) superconducting polycrystalline fibers/wires with improved critical current densities in the extended range of magnetic fields at temperatures greater than 77 K. The approach involves laser heating to minimize phase segregation by heating very rapidly through the two-phase incongruent melt region to the single phase melt region and directionally solidifying in a controlled thermal gradient to achieve highly textured grains in the fiber axis direction. The technique offers a higher grain growth rate and a lower thermal budget compared with a conventional thermal gradient and is amenable as a continuous process for improving the J(sub c) of high T(sub c) superconducting polycrystalline fibers/wires. The technique has the advantage of suppressing weak-link behavior by orientation of crystals, formation of dense structures with enhanced connectivity, formation of fewer and cleaner grain boundaries, and minimization of phase segregation in the incongruent melt region.

Theory and applications of a novel ion exchange chromatographic technology using controlled pH gradients for separating proteins on anionic and cationic stationary phases.

PubMed

Tsonev, Latchezar I; Hirsh, Allen G

2008-07-25

pISep is a major new advance in low ionic strength ion exchange chromatography. It enables the formation of externally controlled pH gradients over the very broad pH range from 2 to 12. The gradients can be generated on either cationic or anionic exchangers over arbitrary pH ranges wherein the stationary phases remain totally charged. Associated pISep software makes possible the calculation of either linear, nonlinear or combined, multi-step, multi-slope pH gradients. These highly reproducible pH gradients, while separating proteins and glycoproteins in the order of their electrophoretic pIs, provide superior chromatographic resolution compared to salt. This paper also presents a statistical mechanical model for protein binding to ion exchange stationary phases enhancing the electrostatic interaction theory for the general dependence of retention factor k, on both salt and pH simultaneously. It is shown that the retention factors computed from short time isocratic salt elution data of a model protein can be used to accurately predict its salt elution concentration in varying slope salt elution gradients formed at varying isocratic pH as well as the pH at which it will be eluted from an anionic exchange column by a pISep pH gradient in the absence of salt.

Sheared-flow induced confinement transition in a linear magnetized plasma

NASA Astrophysics Data System (ADS)

Zhou, S.; Heidbrink, W. W.; Boehmer, H.; McWilliams, R.; Carter, T. A.; Vincena, S.; Friedman, B.; Schaffner, D.

2012-01-01

A magnetized plasma cylinder (12 cm in diameter) is induced by an annular shape obstacle at the Large Plasma Device [W. Gekelman, H. Pfister, Z. Lucky, J. Bamber, D. Leneman, and J. Maggs, Rev. Sci. Instrum. 62, 2875 (1991)]. Sheared azimuthal flow is driven at the edge of the plasma cylinder through edge biasing. Strong fluctuations of density and potential (δn /n~eδφ/kTe~0.5) are observed at the plasma edge, accompanied by a large density gradient (Ln=|∇lnn |-1~2cm) and shearing rate (γ ~300kHz). Edge turbulence and cross-field transport are modified by changing the bias voltage (Vbias) on the obstacle and the axial magnetic field (Bz) strength. In cases with low Vbias and large Bz, improved plasma confinement is observed, along with steeper edge density gradients. The radially sheared flow induced by E ×B drift dramatically changes the cross-phase between density and potential fluctuations, which causes the wave-induced particle flux to reverse its direction across the shear layer. In cases with higher bias voltage or smaller Bz, large radial transport and rapid depletion of the central plasma density are observed. Two-dimensional cross-correlation measurement shows that a mode with azimuthal mode number m =1 and large radial correlation length dominates the outward transport in these cases. Linear analysis based on a two-fluid Braginskii model suggests that the fluctuations are driven by both density gradient (drift wave like) and flow shear (Kelvin-Helmholtz like) at the plasma edge.

Characterization of thermotropism in primary roots of maize: dependence on temperature and temperature gradient, and interaction with gravitropism

NASA Technical Reports Server (NTRS)

Poff, K. L.

1991-01-01

Thermotropism in primary roots of Zea mays L. was studied with respect to gradient strength (degrees C cm-1), temperature of exposure within a gradient, pre-treatment temperature, and gravitropic stimulation. The magnitude of the response decreased with gradient strength. Maximum thermotropism was independent of gradient strength and pre-treatment temperature. The range of temperature for positive and negative thermotropism did not change with pre-treatment temperature. However, the exact range of temperatures for positive and negative thermotropism varied with gradient strengths. In general, temperatures of exposure lower than 25 degrees C resulted in positive tropic responses while temperatures of exposure of 39 degrees C or more resulted in negative tropic responses. Thermotropism was shown to modify and reverse the normal gravitropic curvature of a horizontal root when thermal gradients were applied opposite the 1 g vector. It is concluded that root thermotropism is a consequence of thermal sensing and that the curvature of the primary root results from the interaction of the thermal and gravitational sensing systems.

B0 concomitant field compensation for MRI systems employing asymmetric transverse gradient coils.

PubMed

Weavers, Paul T; Tao, Shengzhen; Trzasko, Joshua D; Frigo, Louis M; Shu, Yunhong; Frick, Matthew A; Lee, Seung-Kyun; Foo, Thomas K-F; Bernstein, Matt A

2018-03-01

Imaging gradients result in the generation of concomitant fields, or Maxwell fields, which are of increasing importance at higher gradient amplitudes. These time-varying fields cause additional phase accumulation, which must be compensated for to avoid image artifacts. In the case of gradient systems employing symmetric design, the concomitant fields are well described with second-order spatial variation. Gradient systems employing asymmetric design additionally generate concomitant fields with global (zeroth-order or B 0 ) and linear (first-order) spatial dependence. This work demonstrates a general solution to eliminate the zeroth-order concomitant field by applying the correct B 0 frequency shift in real time to counteract the concomitant fields. Results are demonstrated for phase contrast, spiral, echo-planar imaging (EPI), and fast spin-echo imaging. A global phase offset is reduced in the phase-contrast exam, and blurring is virtually eliminated in spiral images. The bulk image shift in the phase-encode direction is compensated for in EPI, whereas signal loss, ghosting, and blurring are corrected in the fast-spin echo images. A user-transparent method to compensate the zeroth-order concomitant field term by center frequency shifting is proposed and implemented. This solution allows all the existing pulse sequences-both product and research-to be retained without any modifications. Magn Reson Med 79:1538-1544, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

Identification and measurement of beta-lactam antibiotic residues in milk: integration of screening kits with liquid chromatography.

PubMed

Harik-Khan, R; Moats, W A

1995-01-01

A procedure for identifying and quantitating violative beta-lactams in milk is described. This procedure integrates beta-lactam residue detection kits with the multiresidue automated liquid chromatographic (LC) cleanup method developed in our laboratory. Spiked milk was deproteinized, extracted, and subjected to reversed-phase LC using a gradient program that concentrated the beta-lactams. Amoxicillin, ampicillin, cephapirin, ceftiofur, cloxacillin, and penicillin G were, thus, separated into 5 fractions that were subsequently tested for activity by using 4 kits. beta-lactams in the positive fractions were quantitated by analytical LC methods developed in our laboratory. The LC cleanup method separated beta-lactam antibiotics from each other and from interferences in the matrix and also concentrated the antibiotics, thus increasing the sensitivity of the kits to the beta-lactam antibiotics. The procedure facilitated the task of identifying and measuring the beta-lactam antibiotics that may be present in milk samples.

Salton Sea Project, Phase 1. [solar pond power plant

NASA Technical Reports Server (NTRS)

Peelgren, M. L.

1982-01-01

A feasibility study was made for a salt gradient solar pond power plant in or near the Salton Sea of California. The conclusions support continuance 5-MWe proof-of-concept experiment, and ultimate construction by an electric utility company of a 600-MWe plant. The Solar Pond concept would be an environmental benefit to the Salton Sea by reversing the increasing salinity trend. The greatest cost drivers are the lake dike construction and pond sealing. Problems to be resolved include method of brine production from Salton Sea water for the first unit (which requires evaporation pond area and time), the high turbidity and color content of the Salton Sea water (which requires pretreatment), and other questions related to pond permeability, bio-activity and soil/brine chemical reactions. All technical and environmental problems appear solvable and/or manageable if care is taken in mitigating impacts.

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

Criss, R.E.; Gregory, R.T.; Taylor, H.P.

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Two-dimensional numerical simulation of a Stirling engine heat exchanger

NASA Technical Reports Server (NTRS)

Ibrahim, Mounir B.; Tew, Roy C.; Dudenhoefer, James E.

1989-01-01

The first phase of an effort to develop multidimensional models of Stirling engine components is described; the ultimate goal is to model an entire engine working space. More specifically, parallel plate and tubular heat exchanger models with emphasis on the central part of the channel (i.e., ignoring hydrodynamic and thermal end effects) are described. The model assumes: laminar, incompressible flow with constant thermophysical properties. In addition, a constant axial temperature gradient is imposed. The governing equations, describing the model, were solved using Crank-Nicloson finite-difference scheme. Model predictions were compared with analytical solutions for oscillating/reversing flow and heat transfer in order to check numerical accuracy. Excellent agreement was obtained for the model predictions with analytical solutions available for both flow in circular tubes and between parallel plates. Also the heat transfer computational results are in good agreement with the heat transfer analytical results for parallel plates.

Contour integral method for obtaining the self-energy matrices of electrodes in electron transport calculations

NASA Astrophysics Data System (ADS)

Iwase, Shigeru; Futamura, Yasunori; Imakura, Akira; Sakurai, Tetsuya; Tsukamoto, Shigeru; Ono, Tomoya

2018-05-01

We propose an efficient computational method for evaluating the self-energy matrices of electrodes to study ballistic electron transport properties in nanoscale systems. To reduce the high computational cost incurred in large systems, a contour integral eigensolver based on the Sakurai-Sugiura method combined with the shifted biconjugate gradient method is developed to solve an exponential-type eigenvalue problem for complex wave vectors. A remarkable feature of the proposed algorithm is that the numerical procedure is very similar to that of conventional band structure calculations. We implement the developed method in the framework of the real-space higher-order finite-difference scheme with nonlocal pseudopotentials. Numerical tests for a wide variety of materials validate the robustness, accuracy, and efficiency of the proposed method. As an illustration of the method, we present the electron transport property of the freestanding silicene with the line defect originating from the reversed buckled phases.

Quantitation of chlorophylls and 22 of their colored degradation products in culinary aromatic herbs by HPLC-DAD-MS and correlation with color changes during the dehydration process.

PubMed

Lafeuille, Jean-Louis; Lefèvre, Stéphane; Lebuhotel, Julie

2014-02-26

Chlorophylls and their green and olive-brown derivatives were successfully separated from culinary herb extracts by HPLC with photodiode-array and mass spectrometry detection. The method involved a ternary gradient elution and reverse-phase separation conditions capable of resolving 24 different pigments (2 chlorophylls and 22 of their derivatives) of different polarities within 28 min. The method was applied to monitor color changes in 50 samples of culinary aromatic herbs subjected to five different drying treatments. Of the 24 pigments, 14 were key to understanding the differences between the primary degradation pathways of chlorophyll a and chlorophyll b in culinary herbs during drying processes. A color degradation ladder based on the total molar percentage of all the remaining green pigments was also proposed as a tool to measure the impact of drying treatments on aromatic herb visual aspects.

Reverse lyotropic liquid crystals from europium nitrate and P123 with enhanced luminescence efficiency.

PubMed

Yi, Sijing; Li, Qintang; Liu, Hongguo; Chen, Xiao

2014-10-02

Fabrication of lyotropic aggregates containing the lanthanide ions is becoming a preferable way to prepare novel functional materials. Here, the lyotropic liquid crystals (LLCs) of reverse hexagonal, reverse bicontinuous cubic, and lamellar phases have been constructed in sequence directly from the mixtures of Eu(NO3)3·6H2O and Pluronic P123 amphiphilc block copolymer with increasing the salt proportion. Their phase types and structural characteristics were analyzed using polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS) measurements. The driving forces of reverse LLC phase formation were investigated using Fourier-transformed infrared spectroscopy (FTIR) and rheological measurements. The hydrated europium salt was found to act not only as a solvent here, but also as the bridge to form hydrogen bonding between coordinated water molecules and PEO blocks, which played a key role in the reverse LLCs formation. Compared to those in aqueous solutions and solid state, the enhanced luminescence quantum yields and prolonged excited state lifetimes were observed in two europium containing reverse mesophases. The luminescence quenching effect of lanthanide ions was efficiently suppressed, probably due to the substitution of coordinated water molecules by oxyethyl groups of P123 and ordered phase structures of LLCs, where the coordinated europium ions were confined and isolated by PEO blocks. The optimum luminescence performance was then found to exist in the reverse hexagonal phase. The obtained results on such lanthanide-induced reverse LLCs should be referable for designing new luminescent soft materials construction to expand their application fields.

Random Combinatorial Gradient Metasurface for Broadband, Wide-Angle and Polarization-Independent Diffusion Scattering.

PubMed

Zhuang, Yaqiang; Wang, Guangming; Liang, Jiangang; Cai, Tong; Tang, Xiao-Lan; Guo, Tongfeng; Zhang, Qingfeng

2017-11-29

This paper proposes an easy, efficient strategy for designing broadband, wide-angle and polarization-independent diffusion metasurface for radar cross section (RCS) reduction. A dual-resonance unit cell, composed of a cross wire and cross loop (CWCL), is employed to enhance the phase bandwidth covering the 2π range. Both oblique-gradient and horizontal-gradient phase supercells are designed for illustration. The numerical results agree well with the theoretical ones. To significantly reduce backward scattering, the random combinatorial gradient metasurface (RCGM) is subsequently constructed by collecting eight supercells with randomly distributed gradient directions. The proposed metasurface features an enhanced specular RCS reduction performance and less design complexity compared to other candidates. Both simulated and measured results show that the proposed RCGM can significantly suppress RCS and exhibits broadband, wide-angle and polarization independence features.

Gradient pre-emphasis to counteract first-order concomitant fields on asymmetric MRI gradient systems.

PubMed

Tao, Shengzhen; Weavers, Paul T; Trzasko, Joshua D; Shu, Yunhong; Huston, John; Lee, Seung-Kyun; Frigo, Louis M; Bernstein, Matt A

2017-06-01

To develop a gradient pre-emphasis scheme that prospectively counteracts the effects of the first-order concomitant fields for any arbitrary gradient waveform played on asymmetric gradient systems, and to demonstrate the effectiveness of this approach using a real-time implementation on a compact gradient system. After reviewing the first-order concomitant fields that are present on asymmetric gradients, we developed a generalized gradient pre-emphasis model assuming arbitrary gradient waveforms to counteract their effects. A numerically straightforward, easily implemented approximate solution to this pre-emphasis problem was derived that was compatible with the current hardware infrastructure of conventional MRI scanners for eddy current compensation. The proposed method was implemented on the gradient driver subsystem, and its real-time use was tested using a series of phantom and in vivo data acquired from two-dimensional Cartesian phase-difference, echo-planar imaging, and spiral acquisitions. The phantom and in vivo results demonstrated that unless accounted for, first-order concomitant fields introduce considerable phase estimation error into the measured data and result in images with spatially dependent blurring/distortion. The resulting artifacts were effectively prevented using the proposed gradient pre-emphasis. We have developed an efficient and effective gradient pre-emphasis framework to counteract the effects of first-order concomitant fields of asymmetric gradient systems. Magn Reson Med 77:2250-2262, 2017. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

Propulsion of Active Colloids by Self-Induced Field Gradients.

PubMed

Boymelgreen, Alicia; Yossifon, Gilad; Miloh, Touvia

2016-09-20

Previously, metallodielectric Janus particles have been shown to travel with their dielectric hemisphere forward under low frequency applied electric fields as a result of asymmetric induced-charge electroosmotic flow. Here, it is demonstrated that at high frequencies, well beyond the charge relaxation time of the electric double layer induced around the particle, rather than the velocity decaying to zero, the Janus particles reverse direction, traveling with their metallic hemisphere forward. It is proposed that such motion is the result of a surface force, arising from localized nonuniform electric field gradients, induced by the dual symmetry-breaking of an asymmetric particle adjacent to a wall, which act on the induced dipole of the particle to drive net motion even in a uniform AC field. Although the field is external, since the driving gradient is induced on the particle level, it may be considered an active colloid. We have thus termed this propulsion mechanism "self-dielectrophoresis", to distinguish from traditional dielectrophoresis where the driving nonuniform field is externally fixed and the particle direction is restricted. It is demonstrated theoretically and experimentally that the critical frequency at which the particle reverses direction can be characterized by a nondimensional parameter which is a function of electrolyte concentration and particle size.

Gradient-type modeling of the effects of plastic recovery and surface passivation in thin films

NASA Astrophysics Data System (ADS)

Liu, Jinxing; Kah Soh, Ai

2016-08-01

The elasto-plastic responses of thin films subjected to cyclic tension-compression loading and bending are studied, with a focus on Bauschinger and size effects. For this purpose, a model is established by incorporating plastic recovery into the strain gradient plasticity theory we proposed recently. Elastic and plastic parts of strain and strain gradient, which are determined by the elasto-plastic decomposition according to the associative rule, are assumed to have a degree of material-dependent reversibility. Based on the above assumption, a dislocation reversibility-dependent rule is built to describe evolutions of different deformation components under cyclic loadings. Furthermore, a simple strategy is provided to implement the passivated boundary effects by introducing a gradual change to relevant material parameters in the yield function. Based on this theory, both bulge and bending tests under cyclic loading conditions are investigated. By comparing the present predictions with the existing experimental data, it is found that the yield function is able to exhibit the size effect, the Bauschinger effect, the influence of surface passivation and the hysteresis-loop phenomenon. Thus, the proposed model is deemed helpful in studying plastic deformations of micron-scale films.

SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY REVERSE PHASE CHROMATOGRAPHY

EPA Science Inventory

The method for determination of T-MAZ ethoxylated sorbitan fatty acid esters is described. This work demonstrates that with a less retentive C8 alkyl bonded phase packing, reverse phase chromatography can be used to analyze nonionic polymer mixtures with a molecular weight range ...

The effects of blocking in the subtropics on the phase speed of the MJO

NASA Astrophysics Data System (ADS)

Roundy, P. E.

2016-12-01

The phase speed of the MJO might be regulated by many different factors. Previous works have suggested that moist processes govern the phase speed, and our results show that intensification of convection is associated with reduction of phase speed down to about 5 ms-1. However, convection and rainfall decline with declining phase speeds below 5 ms-1. This presentation shows that increased Rossby wave breaking and blocking east of MJO deep convection is associated with reduced phase speed below about 6 ms-1. A wavelet filter is applied to extract time series characterized by selected zonal wavenumbers and frequencies at select equatorial base longitudes over the Indian and West Pacific Oceans. Results show that anomalies of active convection characterized by wavenumber 2 (the dominant scale of MJO convection over the warm pool) are associated with meridional potential vorticity (PV) gradients across the tropics to the east of the active convection that are near climatology for events moving east at 5 ms-1. These gradients are much weaker for slower events. The slowest phase speed events have almost no meridional PV gradients across the tropics between the mean latitudes of the subtropical jet streams, suggesting that jet exit regions occur immediately east of the deep convection, dumping mass in the upper troposphere over the region of suppressed convection. In the absence of PV gradients, synoptic to planetary scale waves moving into that environment break or cease to propagate linearly.

Linking seafloor volcanism to rising carbon dioxide after the last ice age: observations from the Gulf of California

NASA Astrophysics Data System (ADS)

Rafter, P. A.; Herguera, J. C.; Carriquiry, J. D.; Solomon, E. A.; Southon, J. R.

2017-12-01

Seafloor volcanism at ocean spreading centers may have played an important role in late Pleistocene glacial terminations by increasing the global inventory of the greenhouse gas carbon dioxide (CO2). Gulf of California geology and hydrography offer a unique opportunity to quantify this carbon contribution because CO2 from local seafloor volcanism will reduce/reverse the vertical gradient of seawater radiocarbon (14C). We reconstructed this surface-to-deep gradient by measuring the 14C content of seafloor- and surface-dwelling foraminifera and find several surface-deep 14C reversals during the most recent deglaciation—a 14C distribution that has no analog in the modern ocean. We interpret these observations as representing increased CO2 efflux from the seafloor during deglaciation, linking plate tectonics with the carbon cycle and global climate via enhanced seafloor volcanism.

L-Cysteine ethyl ester reverses the deleterious effects of morphine on, arterial blood-gas chemistry in tracheotomized rats.

PubMed

Mendoza, James; Passafaro, Rachael; Baby, Santhosh; Young, Alex P; Bates, James N; Gaston, Benjamin; Lewis, Stephen J

2013-10-01

This study determined whether the membrane-permeable ventilatory stimulant, L-cysteine ethylester (L-CYSee), reversed the deleterious actions of morphine on arterial blood-gas chemistry in isoflurane-anesthetized rats. Morphine (2 mg/kg, i.v.) elicited sustained decreases in arterial blood pH, pO₂ and sO₂, and increases in pCO₂ (all responses indicative of hypoventilation) and alveolar-arterial gradient (indicative of ventilation-perfusion mismatch). Injections of L-CYSee (100 μmol/kg, i.v.) reversed the effects of morphine in tracheotomized rats but were minimally active in non-tracheotomized rats. L-cysteine or L-serine ethylester (100 μmol/kg, i.v.) were without effect. It is evident that L-CYSee can reverse the negative effects of morphine on arterial blood-gas chemistry and alveolar-arterial gradient but that this positive activity is negated by increases in upper-airway resistance. Since L-cysteine and L-serine ethylester were ineffective, it is evident that cell penetrability and the sulfur moiety of L-CYSee are essential for activity. Due to its ready penetrability into the lungs, chest wall muscle and brain, the effects of L-CYSee on morphine-induced changes in arterial blood-gas chemistry are likely to involve both central and peripheral sites of action. Copyright © 2013 Elsevier B.V. All rights reserved.

On the lorentzian versus Gaussian character of time-domain spin-echo signals from the brain as sampled by means of gradient-echoes: Implications for quantitative transverse relaxation studies.

PubMed

Mulkern, Robert V; Balasubramanian, Mukund; Mitsouras, Dimitrios

2014-07-30

To determine whether Lorentzian or Gaussian intra-voxel frequency distributions are better suited for modeling data acquired with gradient-echo sampling of single spin-echoes for the simultaneous characterization of irreversible and reversible relaxation rates. Clinical studies (e.g., of brain iron deposition) using such acquisition schemes have typically assumed Lorentzian distributions. Theoretical expressions of the time-domain spin-echo signal for intra-voxel Lorentzian and Gaussian distributions were used to fit data from a human brain scanned at both 1.5 Tesla (T) and 3T, resulting in maps of irreversible and reversible relaxation rates for each model. The relative merits of the Lorentzian versus Gaussian model were compared by means of quality of fit considerations. Lorentzian fits were equivalent to Gaussian fits primarily in regions of the brain where irreversible relaxation dominated. In the multiple brain regions where reversible relaxation effects become prominent, however, Gaussian fits were clearly superior. The widespread assumption that a Lorentzian distribution is suitable for quantitative transverse relaxation studies of the brain should be reconsidered, particularly at 3T and higher field strengths as reversible relaxation effects become more prominent. Gaussian distributions offer alternate fits of experimental data that should prove quite useful in general. Magn Reson Med, 2014. © 2014 Wiley Periodicals, Inc. © 2014 Wiley Periodicals, Inc.

A broadband high-transmission gradient phase discontinuity metasurface

NASA Astrophysics Data System (ADS)

Liu, Yahong; Liu, Congcong; Song, Kun; Li, Meize; Zhao, Xiaopeng

2018-03-01

Metasurfaces have attracted significant attention due to the control of the electromagnetic waves that they enable. In this paper, we demonstrate a high-transmission gradient phase discontinuity metasurface composed of metallic rods and cylindrical dielectric resonators operating at a broadband microwave frequency from 8 GHz to 9.8 GHz, with a fractional bandwidth of 20.2%. The proposed gradient phase discontinuity metasurface can achieve complete 2π transmission phase coverage with π/4 phase intervals by varying the geometric parameters of the dielectric resonators and metallic rods. It is shown that the proposed metasurface can refract a normally incident plane wave to an angle of 30°. The broadband metasurface is flexible, and the refracted angle can be adjusted easily by varying the lattice constant. Besides the broadband anomalous refraction, we also demonstrate the metasurface can produce an interesting vortex and wave-focusing in the wide frequency range from 8 GHz to 9.8 GHz. Finally, we demonstrate that the present metasurface can tailor interference wavefronts to plane wavefronts.

Selectivity optimization in green chromatography by gradient stationary phase optimized selectivity liquid chromatography.

PubMed

Chen, Kai; Lynen, Frédéric; De Beer, Maarten; Hitzel, Laure; Ferguson, Paul; Hanna-Brown, Melissa; Sandra, Pat

2010-11-12

Stationary phase optimized selectivity liquid chromatography (SOSLC) is a promising technique to optimize the selectivity of a given separation by using a combination of different stationary phases. Previous work has shown that SOSLC offers excellent possibilities for method development, especially after the recent modification towards linear gradient SOSLC. The present work is aimed at developing and extending the SOSLC approach towards selectivity optimization and method development for green chromatography. Contrary to current LC practices, a green mobile phase (water/ethanol/formic acid) is hereby preselected and the composition of the stationary phase is optimized under a given gradient profile to obtain baseline resolution of all target solutes in the shortest possible analysis time. With the algorithm adapted to the high viscosity property of ethanol, the principle is illustrated with a fast, full baseline resolution for a randomly selected mixture composed of sulphonamides, xanthine alkaloids and steroids. Copyright © 2010 Elsevier B.V. All rights reserved.

Attractive interactions between reverse aggregates and phase separation in concentrated malonamide extractant solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erlinger, C.; Belloni, L.; Zemb, T.

1999-03-30

Using small angle X-ray scattering, conductivity, and phase behavior determination, the authors show that concentrated solutions of malonamide extractants, dimethyldibutyltetradecylmalonamide (DMDBTDMA), are organized in reverse oligomeric aggregates which have many features in common with reverse micelles. The aggregation numbers of these reverse globular aggregates as well as their interaction potential are determined from absolute scattering curves. An attractive interaction is responsible for the demixing of the oil phase when in equilibrium with excess oil. Prediction of conductivity as well as the formation conditions for the third phase is possible using standard liquid theory applied to the extractant aggregates. The interactions,more » modeled with the sticky sphere model proposed by Baster, are shown to be due to steric interactions resulting from the hydrophobic tails of the extractant molecule and van der Waals forces between the highly polarizable water core of the reverse micelles. The attractive interaction in the oil phase, equilibrated with water, is determined as a function of temperature, extractant molecule concentration, and proton and neodynium(III) cation concentration. It is shown that van der Waals interactions, with an effective Hamaker constant of 3kT, quantitatively explain the behavior of DMDBTDMA in n-dodecane in terms of scattering as well as phase stability limits.« less

Comparison of the response of four aerosol detectors used with ultra high pressure liquid chromatography.

PubMed

Hutchinson, Joseph P; Li, Jianfeng; Farrell, William; Groeber, Elizabeth; Szucs, Roman; Dicinoski, Greg; Haddad, Paul R

2011-03-25

The responses of four different types of aerosol detectors have been evaluated and compared to establish their potential use as a universal detector in conjunction with ultra high pressure liquid chromatography (UHPLC). Two charged-aerosol detectors, namely Corona CAD and Corona Ultra, and also two different types of light-scattering detectors (an evaporative light scattering detector, and a nano-quantity analyte detector [NQAD]) were evaluated. The responses of these detectors were systematically investigated under changing experimental and instrumental parameters, such as the mobile phase flow-rate, analyte concentration, mobile phase composition, nebulizer temperature, evaporator temperature, evaporator gas flow-rate and instrumental signal filtering after detection. It was found that these parameters exerted non-linear effects on the responses of the aerosol detectors and must therefore be considered when designing analytical separation conditions, particularly when gradient elution is performed. Identical reversed-phase gradient separations were compared on all four aerosol detectors and further compared with UV detection at 200 nm. The aerosol detectors were able to detect all 11 analytes in a test set comprising species having a variety of physicochemical properties, whilst UV detection was applicable only to those analytes containing chromophores. The reproducibility of the detector response for 11 analytes over 10 consecutive separations was found to be approximately 5% for the charged-aerosol detectors and approximately 11% for the light-scattering detectors. The tested analytes included semi-volatile species which exhibited a more variable response on the aerosol detectors. Peak efficiencies were generally better on the aerosol detectors in comparison to UV detection and particularly so for the light-scattering detectors which exhibited efficiencies of around 110,000 plates per metre. Limits of detection were calculated using different mobile phase compositions and the NQAD detector was found to be the most sensitive (LOD of 10 ng/mL), followed by the Corona CAD (76 ng/mL), then UV detection at 200 nm (178 ng/mL) using an injection volume of 25 μL. Copyright © 2011 Elsevier B.V. All rights reserved.

Three filters for visualization of phase objects with large variations of phase gradients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sagan, Arkadiusz; Antosiewicz, Tomasz J.; Szoplik, Tomasz

2009-02-20

We propose three amplitude filters for visualization of phase objects. They interact with the spectra of pure-phase objects in the frequency plane and are based on tangent and error functions as well as antisymmetric combination of square roots. The error function is a normalized form of the Gaussian function. The antisymmetric square-root filter is composed of two square-root filters to widen its spatial frequency spectral range. Their advantage over other known amplitude frequency-domain filters, such as linear or square-root graded ones, is that they allow high-contrast visualization of objects with large variations of phase gradients.

All-angle Negative Reflection with An Ultrathin Acoustic Gradient Metasurface: Floquet-Bloch Modes Perspective and Experimental Verification.

PubMed

Liu, Bingyi; Zhao, Jiajun; Xu, Xiaodong; Zhao, Wenyu; Jiang, Yongyuan

2017-10-23

Metasurface with gradient phase response offers new alternative for steering the propagation of waves. Conventional Snell's law has been revised by taking the contribution of local phase gradient into account. However, the requirement of momentum matching along the metasurface sets its nontrivial beam manipulation functionality within a limited-angle incidence. In this work, we theoretically and experimentally demonstrate that the acoustic gradient metasurface supports the negative reflection for all-angle incidence. The mode expansion theory is developed to help understand how the gradient metasurface tailors the incident beams, and the all-angle negative reflection occurs when the first negative order Floquet-Bloch mode dominates inside the metasurface slab. The coiling-up space structures are utilized to build desired acoustic gradient metasurface, and the all-angle negative reflections have been perfectly verified by experimental measurements. Our work offers the Floquet-Bloch modes perspective for qualitatively understanding the reflection behaviors of the acoustic gradient metasurface, and the all-angle negative reflection characteristic possessed by acoustic gradient metasurface could enable a new degree of the acoustic wave manipulating and be applied in the functional diffractive acoustic elements, such as the all-angle acoustic back reflector.

Using machine-learning to optimize phase contrast in a low-cost cellphone microscope

PubMed Central

Wartmann, Rolf; Schadwinkel, Harald; Heintzmann, Rainer

2018-01-01

Cellphones equipped with high-quality cameras and powerful CPUs as well as GPUs are widespread. This opens new prospects to use such existing computational and imaging resources to perform medical diagnosis in developing countries at a very low cost. Many relevant samples, like biological cells or waterborn parasites, are almost fully transparent. As they do not exhibit absorption, but alter the light’s phase only, they are almost invisible in brightfield microscopy. Expensive equipment and procedures for microscopic contrasting or sample staining often are not available. Dedicated illumination approaches, tailored to the sample under investigation help to boost the contrast. This is achieved by a programmable illumination source, which also allows to measure the phase gradient using the differential phase contrast (DPC) [1, 2] or even the quantitative phase using the derived qDPC approach [3]. By applying machine-learning techniques, such as a convolutional neural network (CNN), it is possible to learn a relationship between samples to be examined and its optimal light source shapes, in order to increase e.g. phase contrast, from a given dataset to enable real-time applications. For the experimental setup, we developed a 3D-printed smartphone microscope for less than 100 $ using off-the-shelf components only such as a low-cost video projector. The fully automated system assures true Koehler illumination with an LCD as the condenser aperture and a reversed smartphone lens as the microscope objective. We show that the effect of a varied light source shape, using the pre-trained CNN, does not only improve the phase contrast, but also the impression of an improvement in optical resolution without adding any special optics, as demonstrated by measurements. PMID:29494620

On the role and value of β in incompressible MHD simulations

NASA Astrophysics Data System (ADS)

Chahine, Robert; Bos, Wouter J. T.

2018-04-01

The parameter β, defined as the ratio of the pressure to the square of the magnetic field, is widely used to characterize astrophysical and fusion plasmas. However, in the dynamics of a plasma flow, it is the pressure gradient which is important rather than the value of the pressure itself. It is shown that if one is interested in the influence of the pressure gradient on the dynamics of a plasma, it is not the quantity β which should be considered, but a similar quantity depending on the pressure gradient. The scaling of this newly defined quantity is investigated using incompressible magnetohydrodynamic simulations in a periodic cylinder in the Reversed Field Pinch flow regime.

A rapid screening procedure for drugs and poisons in gastric contents by direct injection-HPLC analysis.

PubMed

Politi, Lucia; Groppi, Angelo; Polettini, Aldo; Montagna, Maria

2004-05-10

A high performance liquid chromatographic method for toxicological drug screening of gastric content has been developed. The samples were diluted (1:3-1:30) in 0.01 N hydrochloric acid and injected into a reverse phase column for separation by gradient elution. Mobile phase consisted of solvent A (acetonitrile/water 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid) and solvent B (water/acetonitrile 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid); the gradient was programmed from 20 to 80% A in 30 min. The flow was kept constant at 1.5 ml/min. Two home-made internal standards, butyrylsalicylic acid and diacetyltubocurarine with retention times of 5.6 and 21.4 min, respectively, were used. Drugs are identified by matching their relative retention times and UV spectra (200-400 nm) with those contained in a home made library of more than 340 reference compounds (9 analgesics, 22 antidepressants, 30 antihistamines, 14 antihypertensives, 21 antirheumatics, 15 beta-blockers, 9 bronchodilators, 10 Ca antagonists, 14 diuretics, 26 neuroleptics, 25 tranquilizers, and other significant xenobiotic compounds). The fluorometric (FLD) emission spectrum (280-700 nm; excitation wavelength, 230 nm) was used as a further identification. At 50mg/l analyte concentrations, the injection of gastric content after dilution (1:3) produced S/N ratios in the range 8-140. The method is simple, rapid, rather inexpensive and proved to be a useful means of investigation if used in combination with GC-MS screening in blood. On the other hand, the system suffers from a relatively limited sensitivity for compounds with a low UV absorption and from interferences due to the presence in the matrix of some highly UV- and FL-responsive compounds (e.g. tryptophan).

Regularized lattice Boltzmann model for immiscible two-phase flows with power-law rheology

NASA Astrophysics Data System (ADS)

Ba, Yan; Wang, Ningning; Liu, Haihu; Li, Qiang; He, Guoqiang

2018-03-01

In this work, a regularized lattice Boltzmann color-gradient model is developed for the simulation of immiscible two-phase flows with power-law rheology. This model is as simple as the Bhatnagar-Gross-Krook (BGK) color-gradient model except that an additional regularization step is introduced prior to the collision step. In the regularization step, the pseudo-inverse method is adopted as an alternative solution for the nonequilibrium part of the total distribution function, and it can be easily extended to other discrete velocity models no matter whether a forcing term is considered or not. The obtained expressions for the nonequilibrium part are merely related to macroscopic variables and velocity gradients that can be evaluated locally. Several numerical examples, including the single-phase and two-phase layered power-law fluid flows between two parallel plates, and the droplet deformation and breakup in a simple shear flow, are conducted to test the capability and accuracy of the proposed color-gradient model. Results show that the present model is more stable and accurate than the BGK color-gradient model for power-law fluids with a wide range of power-law indices. Compared to its multiple-relaxation-time counterpart, the present model can increase the computing efficiency by around 15%, while keeping the same accuracy and stability. Also, the present model is found to be capable of reasonably predicting the critical capillary number of droplet breakup.

Gyrofluid Simulations of Intrinsic Rotation Generation in Reversed Shear Plasmas with Internal Transport Barriers

NASA Astrophysics Data System (ADS)

Jhang, Hogun; Kim, S. S.; Kwon, J. M.; Terzolo, L.; Kim, J. Y.; Diamond, P. H.

2010-11-01

It is accepted that the intrinsic rotation is generated via the residual stress, which is non-diffusive components of the turbulent Reynolds stress, without external momentum input. The physics leading to the onset of intrinsic rotation in L- and H- mode plasmas have been elucidated elsewhere. However, the physics responsible for the generation and transport of the intrinsic rotation and its relationship to the formation of internal transport barriers (ITBs) in reversed shear (RS) plasmas have not been explored in detail, which is the main subject in the present work. The revised version of the global gyrofluid code TRB is used for this study. It is found that the large intrinsic rotation (˜10-30% of the ion sound speed depending on ITB characteristics) is generated near the ITB region and propagates into the core. The intrinsic rotation increases linearly as the temperature gradient at ITB position increases, albeit not indefinitely. Key parameters related to the symmetry breaking, such as turbulent intensity and its gradient, the flux surface averaged parallel wavenumber are evaluated dynamically during the ITB formation. In particular, the role of reversed shear and the q-profile curvature is presented in relation to the symmetry breaking in RS plasmas.

Intrinsic Rotation and Momentum Transport in Reversed Shear Plasmas with Internal Transport Barriers

NASA Astrophysics Data System (ADS)

Jhang, Hogun; Kim, S. S.; Diamond, P. H.

2010-11-01

The intrinsic rotation in fusion plasmas is believed to be generated via the residual stress without external momentum input. The physical mechanism responsible for the generation and transport of intrinsic rotation in L- and H-mode tokamak plasmas has been studied extensively. However, it is noted that the physics of intrinsic rotation generation and its relationship to the formation of internal transport barriers (ITBs) in reversed shear (RS) tokamak plasmas have not been explored in detail, which is the main subject in the present work. A global gyrofluid code TRB is used for this study. It is found that the large intrinsic rotation (˜10-30% of the ion sound speed depending on ITB characteristics) is generated near the ITB region and propagates into the core. The intrinsic rotation increases linearly as the temperature gradient at ITB position increases, albeit not indefinitely. Key parameters related to the symmetry breaking, such as turbulent intensity and its gradient, the flux surface averaged parallel wavenumber are evaluated dynamically during the ITB formation. The role of reversed shear and the q-profile curvature is presented in relation to the symmetry breaking mechanism in RS plasmas.

The Evolution of Tropospheric Temperature Field and its Relationship With The Onset of Asian Summer Monsoon

NASA Technical Reports Server (NTRS)

He, H.; Sui, C-H.; Jian, M.; Wen, Z.

2000-01-01

The mean state and year-to-year variations of the tropospheric temperature fields and their relationship with the establishment of the summertime East Asian monsoon (EAM) and the Indian monsoon (INM) are studied using the NCEP reanalysis data of 15 years (1982-1996). The results show that the seasonal shift of the South Asian High in the upper troposphere and the establishment of the EAM and the INM are closely related to the seasonal warming which causes a reversal of the meridional gradient of upper tropospheric mean temperature over the monsoon regions. On the average of 15 years, the reversal time of the temperature gradient in the EAM region (INM region) is concurrent with (one pentad earlier than) the onset time of the summer monsoon. In most years of the 15-year period, the reversal of temperature gradient coincides or precedes the onset time of the summer monsoon in both the EAM region and the INM region. The results suggest an important role of thermal processes on the establishment of the Asian monsoon. The contributors to the upper tropospheric warming over the EAM region are the strong horizontal warm advection and the diabetic heating against the adiabatic cooling due to upward motion. In the INM region, strong adiabatic heating by subsidence and the diabetic heating are major warming processes against the strong horizontal cold advection related to the persistent northwestlies to the southwestern periphery of the Tibetan Plateau. It appears that the early or late establishment of the Asian summer monsoon is not directly related to the differential warming near the surface.

Phase space gradient of dissipated work and information: A role of relative Fisher information

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamano, Takuya, E-mail: yamano@amy.hi-ho.ne.jp

2013-11-15

We show that an information theoretic distance measured by the relative Fisher information between canonical equilibrium phase densities corresponding to forward and backward processes is intimately related to the gradient of the dissipated work in phase space. We present a universal constraint on it via the logarithmic Sobolev inequality. Furthermore, we point out that a possible expression of the lower bound indicates a deep connection in terms of the relative entropy and the Fisher information of the canonical distributions.

SEPARATION OF SOME RARE EARTHS BY REVERSED-PHASE PARTITION CHROMATOGRAPHY. Report No. 129/V; Rozdzielenie Niektorych Ziem Rzadkich za Pomoca Chromatografii Podzialowej z Odwroconymi Fazami

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siekierski, S.; Fidelis, I.

1960-01-01

The reversed phase partition chromatography was applied to the separation of small amounts of some rare earths. As a stationary phase TBP was used. and the elution was carried out with concentrated HNO/sub 3/. (auth)

Using reversed phase high performance liquid chromatography to study the complexation of anthocyanins with β-cyclodextrin

NASA Astrophysics Data System (ADS)

Deineka, V. I.; Lapshova, M. S.; Deineka, L. A.

2014-06-01

It is shown by means of reversed phase high performance liquid chromatography (RP HPLC) with mobile phases containing additions of β-cyclodextrin that 5-glucosides of cyanidin and pelargonidin form stronger inclusion complexes than 3-glucosides; this is explained by the steric interference of the glucoside radical.

Convective flows in enclosures with vertical temperature or concentration gradients

NASA Technical Reports Server (NTRS)

Wang, L. W.; Chai, A. T.; Sun, D. J.

1988-01-01

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Convective flows in enclosures with vertical temperature or concentration gradients

NASA Technical Reports Server (NTRS)

Wang, L. W.; Chai, A. T.; Sun, D. J.

1989-01-01

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Reversible Phase Transition with Ultralarge Dielectric Relaxation Behaviors in Succinimide Lithium(I) Hybrids.

PubMed

Tang, Yun-Zhi; Wang, Bin; Zhou, Hai-Tao; Chen, Shao-Peng; Tan, Yu-Hui; Wang, Chang-Feng; Yang, Chang-Shan; Wen, He-Rui

2018-02-05

Dielectric relaxations have widely applied on high permittivity capacitors, dielectric switches, ferroelectrics, pyroelectrics, and electrical insulating materials. However, few investigations of large dielectric relaxation behaviors on organic-inorganic hybrid materials have been documented before. Here we present a novel two-dimensional succinimide lithium(I) hybrid compound, [Li(PDD) 2 ClO 4 ] n , 1, (PDD = 2,5-pyrrolidinedione = succinimide) which shows reversible phase transition behavior in the vicinity of 228 K accompanied by an unusual symmetry breaking from I4 1 /amd to C2/c. X-ray single crystal diffractions analysis indicates the twist motion of pyrrolidine heterocycles, and order-disorder motion of ClO 4 - anions triggered the reversible phase transition. By means of an intuitive crystallographic model (rattling ion model), we further illustrated the mechanism of the interesting reversible phase transition. Particularly, 1 shows ultralarge dielectric relaxation behavior in the vicinity of the phase transition by its dielectric constant dependence on temperatures and frequencies as well as its Cole-Cole relation.

Iterated unscented Kalman filter for phase unwrapping of interferometric fringes.

PubMed

Xie, Xianming

2016-08-22

A fresh phase unwrapping algorithm based on iterated unscented Kalman filter is proposed to estimate unambiguous unwrapped phase of interferometric fringes. This method is the result of combining an iterated unscented Kalman filter with a robust phase gradient estimator based on amended matrix pencil model, and an efficient quality-guided strategy based on heap sort. The iterated unscented Kalman filter that is one of the most robust methods under the Bayesian theorem frame in non-linear signal processing so far, is applied to perform simultaneously noise suppression and phase unwrapping of interferometric fringes for the first time, which can simplify the complexity and the difficulty of pre-filtering procedure followed by phase unwrapping procedure, and even can remove the pre-filtering procedure. The robust phase gradient estimator is used to efficiently and accurately obtain phase gradient information from interferometric fringes, which is needed for the iterated unscented Kalman filtering phase unwrapping model. The efficient quality-guided strategy is able to ensure that the proposed method fast unwraps wrapped pixels along the path from the high-quality area to the low-quality area of wrapped phase images, which can greatly improve the efficiency of phase unwrapping. Results obtained from synthetic data and real data show that the proposed method can obtain better solutions with an acceptable time consumption, with respect to some of the most used algorithms.

Canceling the Gravity Gradient Phase Shift in Atom Interferometry.

PubMed

D'Amico, G; Rosi, G; Zhan, S; Cacciapuoti, L; Fattori, M; Tino, G M

2017-12-22

Gravity gradients represent a major obstacle in high-precision measurements by atom interferometry. Controlling their effects to the required stability and accuracy imposes very stringent requirements on the relative positioning of freely falling atomic clouds, as in the case of precise tests of Einstein's equivalence principle. We demonstrate a new method to exactly compensate the effects introduced by gravity gradients in a Raman-pulse atom interferometer. By shifting the frequency of the Raman lasers during the central π pulse, it is possible to cancel the initial position- and velocity-dependent phase shift produced by gravity gradients. We apply this technique to simultaneous interferometers positioned along the vertical direction and demonstrate a new method for measuring local gravity gradients that does not require precise knowledge of the relative position between the atomic clouds. Based on this method, we also propose an improved scheme to determine the Newtonian gravitational constant G towards the 10 ppm relative uncertainty.

Canceling the Gravity Gradient Phase Shift in Atom Interferometry

NASA Astrophysics Data System (ADS)

D'Amico, G.; Rosi, G.; Zhan, S.; Cacciapuoti, L.; Fattori, M.; Tino, G. M.

2017-12-01

Gravity gradients represent a major obstacle in high-precision measurements by atom interferometry. Controlling their effects to the required stability and accuracy imposes very stringent requirements on the relative positioning of freely falling atomic clouds, as in the case of precise tests of Einstein's equivalence principle. We demonstrate a new method to exactly compensate the effects introduced by gravity gradients in a Raman-pulse atom interferometer. By shifting the frequency of the Raman lasers during the central π pulse, it is possible to cancel the initial position- and velocity-dependent phase shift produced by gravity gradients. We apply this technique to simultaneous interferometers positioned along the vertical direction and demonstrate a new method for measuring local gravity gradients that does not require precise knowledge of the relative position between the atomic clouds. Based on this method, we also propose an improved scheme to determine the Newtonian gravitational constant G towards the 10 ppm relative uncertainty.

Determination of the four major surfactant classes in cleaning products by reversed-phase liquid chromatography using serially connected UV and evaporative light-scattering detection.

PubMed

Escrig-Doménech, Aarón; Simó-Alfonso, Ernesto F; Ramis-Ramos, Guillermo

2016-08-17

A method for the simultaneous determination of the most frequently used surfactant families -linear alkyl benzenesulphonates (LAS), alkyl ether sulphates (AES), fatty alcohol ethoxylates (FAE) and oleins (soaps, fatty acid salts) - in cleaning products, has been developed. The common reversed phase octyl (C8), pentafluorophenyl and biphenyl columns were not capable of separating the anionic LAS and AES classes; however, since only LAS absorbs in the UV, these two classes were independently quantified using a C8 column and serially connected UV and ELSD detection. The best compromise to resolve the four surfactant classes and the oligomers within the classes was achieved with a C8 column and an ACN/water gradient. To enhance retention of the anionic surfactants, ammonium acetate, as an ion-pairing agent compatible with ELSD detection, was used. Also, to shift the olein peaks with respect to that of the FAE oligomers, acetic acid was used. In the optimized method, modulation of the mobile phase, using ammonium acetate during elution of LAS and AES, and acetic acid after elution of LAS and AES, was provided. Quantitation of the overlapped LAS and AES classes was achieved by using the UV detector to quantitate LAS and the ELSD to determine AES by difference. Accuracy in the determination of AES was achieved by using a quadratic model, and by correcting the predicted AES concentration according to the LAS concentration previously established using the UV chromatogram. Another approach also leading to accurate predictions of the AES concentration was to increase the AES concentrations in the samples by adding a standard solution. In the samples reinforced with AES, correction of the predicted AES concentration was not required. FAE and olein were quantified using also quadratic calibration. Copyright © 2016 Elsevier B.V. All rights reserved.

Continuous gradient temperature Raman spectroscopy of oleic and linoleic acids from -100 to 50°C

USDA-ARS?s Scientific Manuscript database

Gradient Temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we apply GTRS and DS...

Characterization and applications of reversed-phase column selectivity based on the hydrophobic-subtraction model.

PubMed

Marchand, D H; Snyder, L R; Dolan, J W

2008-05-16

A total of 371 reversed-phase columns have now been characterized in terms of selectivity, based on five solute-column interactions (the hydrophobic-subtraction model). The present study illustrates the use of these data for interpreting peak-tailing and column stability. New insights are also provided concerning column selectivity as a function of ligand and silica type, and the selection of columns for orthogonal separations is re-examined. Some suggestions for the quality control of reversed-phase columns during manufacture are offered.

Ultra-performance liquid chromatographic determination of tocopherols and retinol in human plasma.

PubMed

Bell, Edward C; John, Mathew; Hughes, Rodney J; Pham, Thu

2014-10-01

A rapid, selective and sensitive ultra-performance liquid chromatography method has been developed for the detection and quantification of tocopherols and retinol in human plasma. Alpha-tocopherol, gamma-tocopherol and retinol are assayed using fluorescence detection. Excitation/emission wavelengths are 295/330 nm and 325/470 nm for the analysis of both tocopherols and retinol, respectively. Retinol acetate is employed as the internal standard. The reversed-phase method incorporates gradient elution with a mobile phase consisting of methanol and acetonitrile. Separation of vitamin compounds is achieved using a bridged ethyl hybrid C18 column. The retention times for retinol, retinol acetate, gamma-tocopherol and alpha-tocopherol are 1.6, 1.8, 3.9 and 4.3 min, respectively. The limits of quantification for retinol, gamma-tocopherol and alpha-tocopherol were 0.02, 0.02 and 0.1 µg/mL, respectively. The assay method is suitable for the analysis of tocopherols and retinol in human plasma. The method may be applied following the ingestion of foods fortified with these fat-soluble vitamins. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Modification of turbulence and turbulent transport associated with a confinement transition in LAPD

NASA Astrophysics Data System (ADS)

Carter, Troy

2009-11-01

Azimuthal flow is driven in the edge of the Large Plasma Device (LAPD) through biasing a section of the vacuum vessel relative to the plasma source cathode. As the applied bias exceeds a threshold, a transition in radial particle confinement is observed, evidenced by a dramatic steepening in the density profile, similar to the L- to H-mode transition in toroidal confinement devices. The threshold behavior and dynamic behavior of radial transport is related to flow penetration and the degree of spatial overlap between the flow shear and density gradient profiles. An investigation of the changes in turbulence and turbulent particle transport associated with the confinement transition is presented. Two-dimensional cross-correlation measurements show that the spatial coherence of edge turbulence in LAPD changes significantly with biasing. The azimuthal correlation in the turbulence increases dramatically, while the radial correlation length is little altered. Turbulent amplitude is reduced at the transition, particularly in electric field fluctuations, but the dominant change observed is in the cross-phase between density and electric field fluctuations. The changes in cross-phase lead to a suppression and then apparent reversal of turbulent particle flux as the threshold is exceeded.

Determination of polymethoxylated flavones in peels of selected Jamaican and Mexican citrus (Citrus spp.) cultivars by high-performance liquid chromatography.

PubMed

Green, Curtis O; Wheatley, Andrew O; Osagie, Anthony U; St A Morrison, Errol Y; Asemota, Helen N

2007-01-01

The concentrations of the polymethoxylated flavones (PMFs) in peels of selected citrus cultivars grown in Jamaica and Mexico were determined. The PMFs were extracted from sun-dried citrus peels with reagent-grade methanol. Analyses were carried out by reverse-phase HPLC and UV detection. The column used was a C(18) 5 microm (150 x 4.6 mm) Discovery column. Elution was in the gradient mode, using a ternary mobile phase. The results showed that all the citrus cultivars used contained at least three of the six major PMFs quantified. Ortanique peel contained the highest quantity of PMFs (34,393 +/- 272 ppm), followed by tangerine (28,389 +/- 343 ppm) and Mexican sweet orange (sample 1; 21,627 +/- 494 ppm). The major PMFs, i.e. sinensetin, nobiletin, tangeretin, heptamethoxyflavone, tetramethylscutellarein and hexamethyl-o-quercetagetin, present in the peels of 20 citrus cultivars, was quantified. The results were compared with those of Florida citrus peels. A large amount of citrus peels and byproducts are produced in the Caribbean which could provide a cheap and convenient source of PMFs. Copyright 2006 John Wiley & Sons, Ltd.

Development of a precolumn derivatization HPLC method with diode-array detection for the determination of amino sugars in peat and soil humic acids.

PubMed

Beňo, Erik; Góra, Róbert; Hutta, Milan

2018-02-01

The work is focused on the development of a high-performance liquid chromatography method with diode-array detection for the separation and quantitation of the three most abundant amino sugars; d-glucosamine, d-galactosamine, and d-mannosamine. The high-performance liquid chromatography separation was carried out by reversed-phase chromatography on Chromolith Performance RP-18e monolithic column after acid hydrolysis (5 M HCl) and precolumn derivatization of samples using diethyl ethoxymethylenemalonate. Gradient elution and a mobile phase composed of ammonium formate buffer solution (10 mmol/L, pH 3.60) and methanol with flow rate of 1.0 mL/min were used. The monitoring wavelength was set at 280 nm. The limits of detection and quantitation for analytes ranged from 0.017 to 0.122 mg/L and from 0.057 to 0.407 mg/L, respectively. The proposed method was successfully applied for the determination of amino sugars in samples of humic acids isolated from different soils and peat. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring groundwater-surface water interaction and its effect on wetland stream benthic productivity, Trout Lake watershed, northern Wisconsin, USA

USGS Publications Warehouse

Hunt, R.J.; Strand, M.; Walker, J.F.

2006-01-01

Measurements of groundwater-surface water exchange at three wetland stream sites were related to patterns in benthic productivity as part of the US Geological Survey's Northern Temperate Lakes-Water, Energy and Biogeochemical Budgets (NTL-WEBB) project. The three sites included one high groundwater discharge (HGD) site, one weak groundwater discharge (WGD) site, and one groundwater recharge (GR) site. Large upward vertical gradients at the HGD site were associated with smallest variation in head below the stream and fewest gradient reversals between the stream and the groundwater beneath the stream, and the stream and the adjacent streambank. The WGD site had the highest number of gradient reversals reflecting the average condition being closest to zero vertical gradient. The duration of groundwater discharge events was related to the amount of discharge, where the HGD site had the longest strong-gradient durations for both horizontal and vertical groundwater flow. Strong groundwater discharge also controlled transient temperature and chemical hyporheic conditions by limiting the infiltration of surface water. Groundwater-surface water interactions were related to highly significant patterns in benthic invertebrate abundance, taxonomic richness, and periphyton respiration. The HGD site abundance was 35% greater than in the WGD site and 53% greater than the GR site; richness and periphyton respiration were also significantly greater (p???0.001, 31 and 44%, respectively) in the HGD site than in the GR site. The WGD site had greater abundance (27%), richness (19%) and periphyton respiration (39%) than the GR site. This work suggests groundwater-surface water interactions can strongly influence benthic productivity, thus emphasizing the importance of quantitative hydrology for management of wetland-stream ecosystems in the northern temperate regions. ?? 2005 Elsevier B.V. All rights reserved.

Separation of Chloroplast Pigments Using Reverse Phase Chromatography.

ERIC Educational Resources Information Center

Reese, R. Neil

1997-01-01

Presents a protocol that uses reverse phase chromatography for the separation of chloroplast pigments. Provides a simple and relatively safe procedure for use in teaching laboratories. Discusses pigment extraction, chromatography, results, and advantages of the process. (JRH)

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets

PubMed Central

Wang, Yonggang; Zhu, Jinlong; Yang, Wenge; Wen, Ting; Pravica, Michael; Liu, Zhenxian; Hou, Mingqiang; Fei, Yingwei; Kang, Lei; Lin, Zheshuai; Jin, Changqing; Zhao, Yusheng

2016-01-01

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure–structure relationship and the role of flexible VOx polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials. PMID:27426219

Four reversible and reconfigurable structures for three-phase emulsions: extended morphologies and applications

NASA Astrophysics Data System (ADS)

Ge, Xue-Hui; Geng, Yu-Hao; Zhang, Qiao-Chu; Shao, Meng; Chen, Jian; Luo, Guang-Sheng; Xu, Jian-Hong

2017-02-01

Here in this article, we classify and conclude the four morphologies of three-phase emulsions. Remarkably, we achieve the reversible transformations between every shape. Through theoretical analysis, we choose four liquid systems to form these four morphologies. Then monodispersed droplets with these four morphologies are formed through a microfluidic device and captured in a petri-dish. By replacing their ambient solution of the captured emulsions, in-situ morphology transformations between each shape are achieved. The process is well recorded through photographs and videos and they are systematical and reversible. Finally, we use the droplets structure to form an on-off switch to start and shut off the evaporation of one volatile phase to achieve the process monitoring. This could be used to initiate and quench a reaction, which offers a novel idea to achieve the switchable and reversible reaction control in multiple-phase reactions.

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets.

PubMed

Wang, Yonggang; Zhu, Jinlong; Yang, Wenge; Wen, Ting; Pravica, Michael; Liu, Zhenxian; Hou, Mingqiang; Fei, Yingwei; Kang, Lei; Lin, Zheshuai; Jin, Changqing; Zhao, Yusheng

2016-07-18

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure-structure relationship and the role of flexible VOx polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials.

Reversible Quantum Brownian Heat Engines for Electrons

NASA Astrophysics Data System (ADS)

Humphrey, T. E.; Newbury, R.; Taylor, R. P.; Linke, H.

2002-08-01

Brownian heat engines use local temperature gradients in asymmetric potentials to move particles against an external force. The energy efficiency of such machines is generally limited by irreversible heat flow carried by particles that make contact with different heat baths. Here we show that, by using a suitably chosen energy filter, electrons can be transferred reversibly between reservoirs that have different temperatures and electrochemical potentials. We apply this result to propose heat engines based on mesoscopic semiconductor ratchets, which can quasistatically operate arbitrarily close to Carnot efficiency.

Reversible quantum heat engines for electrons

NASA Astrophysics Data System (ADS)

Linke, Heiner; Humphrey, Tammy E.; Newbury, Richard; Taylor, Richard P.

2002-03-01

Brownian heat engines use local temperature gradients in asymmetric potentials to move particles against an external force. The energy efficiency of such machines is generally limited by irreversible heat flow carried by particles that make contact with different heat baths. Here we show that, by using a suitably chosen energy filter, electrons can be transferred reversibly between reservoirs that have different temperatures and electrochemical potentials. We apply this result to propose heat engines based on quantum ratchets, which can quasistatically operate at Carnot efficiency.

Development and validation of a reversed phase liquid chromatographic method for analysis of oxytetracycline and related impurities.

PubMed

Kahsay, Getu; Shraim, Fairouz; Villatte, Philippe; Rotger, Jacques; Cassus-Coussère, Céline; Van Schepdael, Ann; Hoogmartens, Jos; Adams, Erwin

2013-03-05

A simple, robust and fast high-performance liquid chromatographic method is described for the analysis of oxytetracycline and its related impurities. The principal peak and impurities are all baseline separated in 20 min using an Inertsil C₈ (150 mm × 4.6 mm, 5 μm) column kept at 50 °C. The mobile phase consists of a gradient mixture of mobile phases A (0.05% trifluoroacetic acid in water) and B (acetonitrile-methanol-tetrahydrofuran, 80:15:5, v/v/v) pumped at a flow rate of 1.3 ml/min. UV detection was performed at 254 nm. The developed method was validated for its robustness, sensitivity, precision and linearity in the range from limit of quantification (LOQ) to 120%. The limits of detection (LOD) and LOQ were found to be 0.08 μg/ml and 0.32 μg/ml, respectively. This method allows the separation of oxytetracycline from all known and 5 unknown impurities, which is better than previously reported in the literature. Moreover, the simple mobile phase composition devoid of non-volatile buffers made the method suitable to interface with mass spectrometry for further characterization of unknown impurities. The developed method has been applied for determination of related substances in oxytetracycline bulk samples available from four manufacturers. The validation results demonstrate that the method is reliable for quantification of oxytetracycline and its impurities. Copyright © 2012 Elsevier B.V. All rights reserved.

Formulation of strongly non-local, non-isothermal dynamics for heterogeneous solids based on the GENERIC with application to phase-field modeling

NASA Astrophysics Data System (ADS)

Hütter, Markus; Svendsen, Bob

2017-12-01

The purpose of the current work is the formulation of models for conservative and non-conservative dynamics in solid systems with the help of the General Equation for the Non-Equilibrium Reversible-Irreversible Coupling (GENERIC: e.g., Grmela and Öttinger, Phys. Rev. E 56(6), 6620 (1997); Öttinger and Grmela, Phys. Rev. E 56(6), 6633 (1997)). In this context, the resulting models are inherently spatially strongly non-local (i.e., functional) and non-isothermal in character. They are applicable in particular to the modeling of phase transitions as well as mass and heat transport in multiphase, multicomponent solids. In the last part of the work, the strongly non-local model formulation is reduced to weakly non-local form with the help of generalized gradient approximation of the energy and entropy functionals. On this basis, the current model formulation is shown to be consistent with and reduce to a recent non-isothermal generalization (Gladkov et al., J. Non-Equilib. Thermodyn. 41(2), 131 (2016)) of the well-known phase-field models of Cahn and Hilliard (J. Chem. Phys. 28(2), 258 (1958)) for conservative dynamics and of Allen and Cahn (Acta Metall. 27(6), 1085 (1979)) for non-conservative dynamics. Finally, the current approach is applied to derive a non-isothermal generalization of a phase-field crystal model for binary alloys (see, e.g., Elder et al., Phys. Rev. B 75(6), 064107 (2007)).

Combining the absorptive and radiative loss in metasurfaces for multi-spectral shaping of the electromagnetic scattering.

PubMed

Pan, Wenbo; Huang, Cheng; Pu, Mingbo; Ma, Xiaoliang; Cui, Jianhua; Zhao, Bo; Luo, Xiangang

2016-02-19

The absorptive and radiative losses are two fundamental aspects of the electromagnetic responses, which are widely occurring in many different systems such as waveguides, solar cells, and antennas. Here we proposed a metasurface to realize the control of the absorptive and radiative loss and to reduce the radar cross section (RCS) in multi-frequency bands. The anti-phase gradient and absorptive metasurfaces were designed that consists of metallic square patch and square loop structure inserted with resistors, acting as an phase gradient material in the X and Ku band, while behaving as an absorber in the S band. The simulation and experiment results verified the double-band, wideband and polarization-independent RCS reduction by the absorptive and anti-phase gradient metasurfaces.

PHYSICAL EFFECTS OCCURRING DURING GENERATION AND AMPLIFICATION OF LASER RADIATION: Reversal of the contrast of optical radiation in round-trip amplifiers with a phase conjugation mirror

NASA Astrophysics Data System (ADS)

Afanas'ev, Anatolii A.; Samson, B. A.

1989-02-01

A description is given of a method for inversion of the contrast of optical radiation in a round-trip amplifier with a phase conjugation mirror and a phase nonreciprocal element. The system can be used to achieve high powers of contrast-reversed radiation because of compensation of phase distortions introduced by amplification.

New methods for interpretation of magnetic vector and gradient tensor data II: application to the Mount Leyshon anomaly, Queensland, Australia

NASA Astrophysics Data System (ADS)

Clark, David A.

2013-04-01

Acquisition of magnetic gradient tensor data is anticipated to become routine in the near future. In the meantime, modern ultrahigh resolution conventional magnetic data can be used, with certain important caveats, to calculate magnetic vector components and gradient tensor elements from total magnetic intensity (TMI) or TMI gradient surveys. An accompanying paper presented new methods for inverting gradient tensor data to obtain source parameters for several elementary, but useful, models. These include point dipole (sphere), vertical line of dipoles (narrow vertical pipe), line of dipoles (horizontal cylinder), thin dipping sheet, and contact models. A key simplification is the use of eigenvalues and associated eigenvectors of the tensor. The normalised source strength (NSS), calculated from the eigenvalues, is a particularly useful rotational invariant that peaks directly over 3D compact sources, 2D compact sources, thin sheets, and contacts, independent of magnetisation direction. Source locations can be inverted directly from the NSS and its vector gradient. Some of these new methods have been applied to analysis of the magnetic signature of the Early Permian Mount Leyshon gold-mineralised system, Queensland. The Mount Leyshon magnetic anomaly is a prominent TMI low that is produced by rock units with strong reversed remanence acquired during the Late Palaeozoic Reverse Superchron. The inferred magnetic moment for the source zone of the Mount Leyshon magnetic anomaly is ~1010Am2. Its direction is consistent with petrophysical measurements. Given estimated magnetisation from samples and geological information, this suggests a volume of ~1.5km×1.5km×2km (vertical). The inferred depth of the centre of magnetisation is ~900m below surface, suggesting that the depth extent of the magnetic zone is ~1800m. Some of the deeper, undrilled portion of the magnetic zone could be a mafic intrusion similar to the nearby coeval Fenian Diorite, representing part of the parent magma chamber beneath the Mount Leyshon Intrusive Complex.

Aortic-Brachial Pulse Wave Velocity Ratio: A Measure of Arterial Stiffness Gradient Not Affected by Mean Arterial Pressure.

PubMed

Fortier, Catherine; Desjardins, Marie-Pier; Agharazii, Mohsen

2018-03-01

Aortic stiffness, measured by carotid-femoral pulse wave velocity (cf-PWV), is used for the prediction of cardiovascular risk. This mini-review describes the nonlinear relationship between cf-PWV and operational blood pressure, presents the proposed methods to adjust for this relationship, and discusses a potential place for aortic-brachial PWV ratio (a measure of arterial stiffness gradient) as a blood pressure-independent measure of vascular aging. PWV is inherently dependent on the operational blood pressure. In cross-sectional studies, PWV adjustment for mean arterial pressure (MAP) is preferred, but still remains a nonoptimal approach, as the relationship between PWV and blood pressure is nonlinear and varies considerably among individuals due to heterogeneity in genetic background, vascular tone, and vascular remodeling. Extrapolations from the blood pressure-independent stiffness parameter β (β 0 ) have led to the creation of stiffness index β, which can be used for local stiffness. A similar approach has been used for cardio-ankle PWV to generate a blood pressure-independent cardio-ankle vascular index (CAVI). It was recently demonstrated that stiffness index β and CAVI remain slightly blood pressure-dependent, and a more appropriate formula has been proposed to make the proper adjustments. On the other hand, the negative impact of aortic stiffness on clinical outcomes is thought to be mediated through attenuation or reversal of the arterial stiffness gradient, which can also be influenced by a reduction in peripheral medium-sized muscular arteries in conditions that predispose to accelerate vascular aging. Arterial stiffness gradient, assessed by aortic-brachial PWV ratio, is emerging to be at least as good as cf-PWV for risk prediction, but has the advantage of not being affected by operating MAP. The negative impacts of aortic stiffness on clinical outcomes are proposed to be mediated through attenuation or reversal of arterial stiffness gradient. Aortic-brachial PWV ratio, a measure of arterial stiffness gradient, is independent of MAP.

Ionic requirements of proximal tubular sodium transport. I. Bicarbonate and chloride.

PubMed

Green, R; Giebisch, G

1975-11-01

Simultaneous perfusion of peritubular capillaries and proximal convoluted tubules was used to study the effect of varying transepithelial ionic gradients on ionic fluxes. Results show that net sodium influx and volume flux was one-third of normal when bicarbonate was absent, no chloride gradient existed, and glucose and amino acids were absent. Addition of bicarbonate to the luminal fluid did not restore the flux to normal, but peritubular bicarbonate did restore it. A chloride gradient imposed when no bicarbonate was present could only increase the fluxes slightly, but his flux was significant even after cyanide had poisoned transport. Reversing the chloride concentration gradient decreased the net sodium and volume fluxes whether bicarbonate was present or not. Glucose had no effect on fluxes, but substitution of Na by choline abolished them entirely. It is concluded that sodium is actively transported, that a chloride concentration gradient from lumen to plasma could account for up to 20% of net transport, and that peritubular bicarbonate is necessary for normal rates of sodium and fluid absorption.

Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Trent R.; Renslow, Ryan; Govind, Niranjan

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFTmore » based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.« less

Development and Optimization of HPLC Analysis of Metronidazole, Diloxanide, Spiramycin and Cliquinol in Pharmaceutical Dosage Forms Using Experimental Design.

PubMed

Elkhoudary, Mahmoud M; Abdel Salam, Randa A; Hadad, Ghada M

2016-11-01

A new simple, sensitive, rapid and accurate gradient reversed-phase high-performance liquid chromatography with photodiode array detector (RP-HPLC-DAD) was developed and validated for simultaneous analysis of Metronidazole (MNZ), Spiramycin (SPY), Diloxanidefuroate (DIX) and Cliquinol (CLQ) using statistical experimental design. Initially, a resolution V fractional factorial design was used in order to screen five independent factors: the column temperature (°C), pH, phosphate buffer concentration (mM), flow rate (ml/min) and the initial fraction of mobile phase B (%). pH, flow rate and initial fraction of mobile phase B were identified as significant, using analysis of variance. The optimum conditions of separation determined with the aid of central composite design were: (1) initial mobile phase concentration: phosphate buffer/methanol (50/50, v/v), (2) phosphate buffer concentration (50 mM), (3) pH (4.72), (4) column temperature 30°C and (5) mobile phase flow rate (0.8 ml min -1 ). Excellent linearity was observed for all of the standard calibration curves, and the correlation coefficients were above 0.9999. Limits of detection for all of the analyzed compounds ranged between 0.02 and 0.11 μg ml -1 ; limits of quantitation ranged between 0.06 and 0.33 μg ml -1 The proposed method showed good prediction ability. The optimized method was validated according to ICH guidelines. Three commercially available tablets were analyzed showing good % recovery and %RSD. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Electron cyclotron heating can drastically alter reversed shear Alfvén eigenmode activity in DIII-D through finite pressure effects

NASA Astrophysics Data System (ADS)

Van Zeeland, M. A.; Heidbrink, W. W.; Sharapov, S. E.; Spong, D.; Cappa, A.; Chen, Xi; Collins, C.; García-Muñoz, M.; Gorelenkov, N. N.; Kramer, G. J.; Lauber, P.; Lin, Z.; Petty, C.

2016-11-01

A recent DIII-D experiment investigating the impact of electron cyclotron heating (ECH) on neutral beam driven reversed shear Alfvén eigenmode (RSAE) activity is presented. The experiment includes variations of ECH injection location and timing, current ramp rate, beam injection geometry (on/off-axis), and neutral beam power. Essentially all variations carried out in this experiment were observed to change the impact of ECH on AE activity significantly. In some cases, RSAEs were observed to be enhanced with ECH near the off-axis minimum in magnetic safety factor ({{q}\\min} ), in contrast to the original DIII-D experiments where the modes were absent when ECH was deposited near {{q}\\min} . It is found that during intervals when the geodesic acoustic mode (GAM) frequency at {{q}\\min} is elevated and the calculated RSAE minimum frequency, including contributions from thermal plasma gradients, is very near or above the nominal TAE frequency (f TAE), RSAE activity is not observed or RSAEs with a much reduced frequency sweep range are found. This condition is primarily brought about by ECH modification of the local electron temperature (T e) which can raise both the local T e at {{q}\\min} as well as its gradient. A q-evolution model that incorporates this reduction in RSAE frequency sweep range is in agreement with the observed spectra and appears to capture the relative balance of TAE or RSAE-like modes throughout the current ramp phase of over 38 DIII-D discharges. Detailed ideal MHD calculations using the NOVA code show both modification of plasma pressure and pressure gradient at {{q}\\min} play an important role in modifying the RSAE activity. Analysis of the ECH injection near the {{q}\\min} case where no frequency sweeping RSAEs are observed shows the typical RSAE is no longer an eigenmode of the system. What remains is an eigenmode with poloidal harmonic content reminiscent of the standard RSAE, but absent of the typical frequency sweeping behavior. The remaining eigenmode is also often strongly coupled to gap TAEs. Analysis with the non-perturbative gyro fluid code TAEFL confirms this change in RSAE activity and also shows a large drop in the resultant mode growth rates.

Electron cyclotron heating can drastically alter reversed shear Alfvén eigenmode activity in DIII-D through finite pressure effects

DOE PAGES

Van Zeeland, M. A.; Heidbrink, W. W.; Sharapov, S. E.; ...

2016-07-22

Here, a recent DIII-D experiment investigating the impact of electron cyclotron heating (ECH) on neutral beam driven reversed shear Alfvén eigenmode (RSAE) activity is presented. The experiment includes variations of ECH injection location and timing, current ramp rate, beam injection geometry (on/off-axis), and neutral beam power. Essentially all variations carried out in this experiment were observed to change the impact of ECH on AE activity significantly. In some cases, RSAEs were observed to be enhanced with ECH near the off-axis minimum in magnetic safety factor (more » $${{q}_{\\min}}$$ ), in contrast to the original DIII-D experiments where the modes were absent when ECH was deposited near $${{q}_{\\min}}$$ . It is found that during intervals when the geodesic acoustic mode (GAM) frequency at $${{q}_{\\min}}$$ is elevated and the calculated RSAE minimum frequency, including contributions from thermal plasma gradients, is very near or above the nominal TAE frequency (f TAE), RSAE activity is not observed or RSAEs with a much reduced frequency sweep range are found. This condition is primarily brought about by ECH modification of the local electron temperature (T e) which can raise both the local T e at $${{q}_{\\min}}$$ as well as its gradient. A q-evolution model that incorporates this reduction in RSAE frequency sweep range is in agreement with the observed spectra and appears to capture the relative balance of TAE or RSAE-like modes throughout the current ramp phase of over 38 DIII-D discharges. Detailed ideal MHD calculations using the NOVA code show both modification of plasma pressure and pressure gradient at $${{q}_{\\min}}$$ play an important role in modifying the RSAE activity. Analysis of the ECH injection near the $${{q}_{\\min}}$$ case where no frequency sweeping RSAEs are observed shows the typical RSAE is no longer an eigenmode of the system. What remains is an eigenmode with poloidal harmonic content reminiscent of the standard RSAE, but absent of the typical frequency sweeping behavior. The remaining eigenmode is also often strongly coupled to gap TAEs. Analysis with the non-perturbative gyro fluid code TAEFL confirms this change in RSAE activity and also shows a large drop in the resultant mode growth rates.« less

Phase gradient metasurface with broadband anomalous reflection based on cross-shaped units

NASA Astrophysics Data System (ADS)

Chen, Zhaobin; Deng, Hui; Xiong, Qingxu; Liu, Chen

2018-03-01

It has been pointed out by many documents that a phase gradient metasurface with wideband characteristics can be designed by the unit with a low-quality factor ( Q value). In this paper, a cross-shaped unit with a low-quality factor Q is proposed. By changing the variable parameters of the unit, it is found that the reflection phase of the unit can achieve a stable distribution of phase gradient in the frequency range of 8.0-20.0 GHz. we analyze variation of the electromagnetic field distribution on the unit with frequency and find that the size along electrical field polarization of electromagnetic field distribution area changes with frequency. Based on our design, effective size of electromagnetic field distribution area keeps meeting the subwavelength condition, thus stable phase distribution is gained across broadened bandwidth. It is found by the analysis of the phase gradient metasurface composed of seven units that the metasurface can exhibit anomalous reflection in the wide frequency band of 8.0-20.0 GHz, and the efficiency of abnormal reflection is higher in the range of 10.0-18.0 GHz. The error between the simulation results of abnormal reflection angle and the theoretical result is only - 1.5° to 0.5° after the work of comparison. Therefore, the metasurface designed by the new cross-shaped unit has a good control on the deflection direction of the reflected wave, and shows obvious advantages in widening the bandwidth.

Cell-Surface Bound Nonreceptors and Signaling Morphogen Gradients

PubMed Central

Wan, Frederic Y.M.

2013-01-01

The patterning of many developing tissues is orchestrated by gradients of signaling morphogens. Included among the molecular events that drive the formation of morphogen gradients are a variety of elaborate regulatory interactions. Such interactions are thought to make gradients robust, i.e. insensitive to change in the face of genetic or environmental perturbations. But just how this is accomplished is a major unanswered question. Recently extensive numerical simulations suggest that robustness of signaling gradients can be achieved through morphogen degradation mediated by cell surface bound non-signaling receptor molecules (or nonreceptors for short) such as heparan sulfate proteoglycans (HSPG). The present paper provides a mathematical validation of the results from the aforementioned numerical experiments. Extension of a basic extracellular model to include reversible binding with nonreceptors synthesized at a prescribed rate and mediated morphogen degradation shows that the signaling gradient diminishes with increasing concentration of cell-surface nonreceptors. Perturbation and asymptotic solutions obtained for i) low (receptor and nonreceptor) occupancy, and ii) high nonreceptor concntration permit more explicit delineation of the effects of nonreceptors on signaling gradients and facilitate the identification of scenarios in which the presence of nonreceptors may or may not be effective in promoting robustness. PMID:25232201

Trends in the educational gradient of mortality among US adults aged 45 to 84 years: bringing regional context into the explanation.

PubMed

Montez, Jennifer Karas; Berkman, Lisa F

2014-01-01

We investigated trends in the educational gradient of US adult mortality, which has increased at the national level since the mid-1980s, within US regions. We used data from the 1986-2006 National Health Interview Survey Linked Mortality File on non-Hispanic White and Black adults aged 45 to 84 years (n = 498,517). We examined trends in the gradient within 4 US regions by race-gender subgroup by using age-standardized death rates. Trends in the gradient exhibited a few subtle regional differences. Among women, the gradient was often narrowest in the Northeast. The region's distinction grew over time mainly because low-educated women in the Northeast did not experience a significant increase in mortality like their counterparts in other regions (particularly for White women). Among White men, the gradient narrowed to a small degree in the West. The subtle regional differences indicate that geographic context can accentuate or suppress trends in the gradient. Studies of smaller areas may provide insights into the specific contextual characteristics (e.g., state tax policies) that have shaped the trends, and thus help explain and reverse the widening mortality disparities among US adults.

Difference in the craniocaudal gradient of the maximum pixel value change rate between chronic obstructive pulmonary disease patients and normal subjects using sub-mGy dynamic chest radiography with a flat panel detector system.

PubMed

Yamada, Yoshitake; Ueyama, Masako; Abe, Takehiko; Araki, Tetsuro; Abe, Takayuki; Nishino, Mizuki; Jinzaki, Masahiro; Hatabu, Hiroto; Kudoh, Shoji

2017-07-01

To compare the craniocaudal gradients of the maximum pixel value change rate (MPCR) during tidal breathing between chronic obstructive pulmonary disease (COPD) patients and normal subjects using dynamic chest radiography. This prospective study was approved by the institutional review board and all participants provided written informed consent. Forty-three COPD patients (mean age, 71.6±8.7 years) and 47 normal subjects (non-smoker healthy volunteers) (mean age, 54.8±9.8 years) underwent sequential chest radiographs during tidal breathing in a standing position using dynamic chest radiography with a flat panel detector system. We evaluated the craniocaudal gradient of MPCR. The results were analyzed using an unpaired t-test and the Tukey-Kramer method. The craniocaudal gradients of MPCR in COPD patients were significantly lower than those in normal subjects (right inspiratory phase, 75.5±48.1 vs. 108.9±42.0s -1 cm -1 , P<0.001; right expiratory phase, 66.4±40.6 vs. 89.8±31.6s -1 cm -1 , P=0.003; left inspiratory phase, 75.5±48.2 vs. 108.2±47.2s -1 cm -1 , P=0.002; left expiratory phase, 60.9±38.2 vs. 84.3±29.5s -1 cm -1 , P=0.002). No significant differences in height, weight, or BMI were observed between COPD and normal groups. In the sub-analysis, the gradients in severe COPD patients (global initiative for chronic obstructive lung disease [GOLD] 3 or 4, n=26) were significantly lower than those in mild COPD patients (GOLD 1 or 2, n=17) for both right and left inspiratory/expiratory phases (all P≤0.005). A decrease of the craniocaudal gradient of MPCR was observed in COPD patients. The craniocaudal gradient was lower in severe COPD patients than in mild COPD patients. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Non-invasive assessment of pulsatile intracranial pressure with phase-contrast magnetic resonance imaging

PubMed Central

Lindstrøm, Erika Kristina; Vatnehol, Svein Are Sirirud; Mardal, Kent-André; Emblem, Kyrre Eeg; Eide, Per Kristian

2017-01-01

Invasive monitoring of pulsatile intracranial pressure can accurately predict shunt response in patients with idiopathic normal pressure hydrocephalus, but may potentially cause complications such as bleeding and infection. We tested how a proposed surrogate parameter for pulsatile intracranial pressure, the phase-contrast magnetic resonance imaging derived pulse pressure gradient, compared with its invasive counterpart. In 22 patients with suspected idiopathic normal pressure hydrocephalus, preceding invasive intracranial pressure monitoring, and any surgical shunt procedure, we calculated the pulse pressure gradient from phase-contrast magnetic resonance imaging derived cerebrospinal fluid flow velocities obtained at the upper cervical spinal canal using a simplified Navier-Stokes equation. Repeated measurements of the pulse pressure gradient were also undertaken in four healthy controls. Of 17 shunted patients, 16 responded, indicating high proportion of “true” normal pressure hydrocephalus in the patient cohort. However, there was no correlation between the magnetic resonance imaging derived pulse pressure gradient and pulsatile intracranial pressure (R = -.18, P = .43). Pulse pressure gradients were also similar in patients and healthy controls (P = .26), and did not differ between individuals with pulsatile intracranial pressure above or below established thresholds for shunt treatment (P = .97). Assessment of pulse pressure gradient at level C2 was therefore not found feasible to replace invasive monitoring of pulsatile intracranial pressure in selection of patients with idiopathic normal pressure hydrocephalus for surgical shunting. Unlike invasive, overnight monitoring, the pulse pressure gradient from magnetic resonance imaging comprises short-term pressure fluctuations only. Moreover, complexity of cervical cerebrospinal fluid flow and -pulsatility at the upper cervical spinal canal may render the pulse pressure gradient a poor surrogate marker for intracranial pressure pulsations. PMID:29190788

Non-invasive assessment of pulsatile intracranial pressure with phase-contrast magnetic resonance imaging.

PubMed

Ringstad, Geir; Lindstrøm, Erika Kristina; Vatnehol, Svein Are Sirirud; Mardal, Kent-André; Emblem, Kyrre Eeg; Eide, Per Kristian

2017-01-01

Invasive monitoring of pulsatile intracranial pressure can accurately predict shunt response in patients with idiopathic normal pressure hydrocephalus, but may potentially cause complications such as bleeding and infection. We tested how a proposed surrogate parameter for pulsatile intracranial pressure, the phase-contrast magnetic resonance imaging derived pulse pressure gradient, compared with its invasive counterpart. In 22 patients with suspected idiopathic normal pressure hydrocephalus, preceding invasive intracranial pressure monitoring, and any surgical shunt procedure, we calculated the pulse pressure gradient from phase-contrast magnetic resonance imaging derived cerebrospinal fluid flow velocities obtained at the upper cervical spinal canal using a simplified Navier-Stokes equation. Repeated measurements of the pulse pressure gradient were also undertaken in four healthy controls. Of 17 shunted patients, 16 responded, indicating high proportion of "true" normal pressure hydrocephalus in the patient cohort. However, there was no correlation between the magnetic resonance imaging derived pulse pressure gradient and pulsatile intracranial pressure (R = -.18, P = .43). Pulse pressure gradients were also similar in patients and healthy controls (P = .26), and did not differ between individuals with pulsatile intracranial pressure above or below established thresholds for shunt treatment (P = .97). Assessment of pulse pressure gradient at level C2 was therefore not found feasible to replace invasive monitoring of pulsatile intracranial pressure in selection of patients with idiopathic normal pressure hydrocephalus for surgical shunting. Unlike invasive, overnight monitoring, the pulse pressure gradient from magnetic resonance imaging comprises short-term pressure fluctuations only. Moreover, complexity of cervical cerebrospinal fluid flow and -pulsatility at the upper cervical spinal canal may render the pulse pressure gradient a poor surrogate marker for intracranial pressure pulsations.

Separation and quantitative determination of 6α-hydroxycortisol and 6β-hydroxycortisol in human urine by high-performance liquid chromatography with ultraviolet absorption detection.

PubMed

Shibasaki, Hiromi; Okamoto, Sawako; Inoue, Risako; Okita, Misato; Yokokawa, Akitomo; Furuta, Takashi

2012-03-01

The present study developed an high-performance liquid chromatography (HPLC) method for the simultaneous determination of urinary metabolites of endogenous cortisol, 6α-hydroxycortisol (6α-OHF) and 6β-hydroxycortisol (6β-OHF), in human urine, using 6α-hydroxycorticosterone as internal standard. 6α-OHF and 6β-OHF were extracted from urine with ethyl acetate by using a Sep-Pak C(18) plus cartridge. Separation of the stereoisomers was achieved on a reversed-phase hybrid column by a gradient elution of (A) 0.05 M KH(2)PO(4)-0.01 M CH(3)COOH (pH 3.77) and (B) 0.05 M KH(2)PO(4)-0.01 M CH(3)COOH/acetonitrile (2:3, v/v). 6α-OHF and 6β-OHF were well separated on an XTerra MS C(18) 5 μm column using two types of stepwise gradient elution program (programs 2 and 3). Resolutions of 6α-OHF and 6β-OHF were Rs = 4.41 for program 2 and Rs = 4.60 for program 3. The analysis was performed within 23~26 min, monitored by UV absorbance at 239 nm. The lower limits of detection of 6α-OHF and 6β-OHF were 0.80 ng per injection (s/n = ca. 8), and the lower limits of quantification were 5.02 ng/ml for 6α-OHF and 41.08 ng/ml for 6β-OHF, respectively. The within-day reproducibilities in the amounts of 6α-OHF and 6β-OHF determined were in good agreement with the actual amounts added, the relative errors being -5.37% and -3.73% (gradient 2) and -5.69% and -3.96% (gradient 3) for both 6α-OHF and 6β-OHF, respectively. The inter-assay precisions (RSDs) for 6α-OHF and 6β-OHF were less than 1.99% (gradient 2) and 2.61% (gradient 3), respectively. The present HPLC method was applied to the measurement of 6α-OHF and 6β-OHF in urine to evaluate the time courses of 6α-hydroxylation and 6β-hydroxylation clearances of cortisol during 40 days for phenotyping CYP3A in a healthy subject.

Development and validation of an high-performance liquid chromatography-diode array detector method for the simultaneous determination of six phenolic compounds in abnormal savda munziq decoction

PubMed Central

Tian, Shuge; Liu, Wenxian; Liu, Feng; Zhang, Xuejia; Upur, Halmuart

2015-01-01

Aims: Given the high-effectiveness and low-toxicity of abnormal savda munziq (ASMQ), its herbal formulation has long been used in traditional Uyghur medicine to treat complex diseases, such as cancer, diabetes, and cardiovascular diseases. Settings and Design: ASMQ decoction by reversed-phase high-performance liquid chromatography coupled with a diode array detector was successfully developed for the simultaneous quality assessment of gallic acid, protocatechuic acid, caffeic acid, rutin, rosmarinic acid, and luteolin. The six phenolic compounds were separated on an Agilent TC-C18 reversed-phase analytical column (4.6 × 250 mm, 5 μm) by gradient elution using 0.3% aqueous formic acid (v/v) and 0.3% methanol formic acid (v/v) at 1.0 mL/min. Materials and Methods: The plant material was separately ground and mixed at the following ratios (10): Cordia dichotoma (10.6), Anchusa italic (10.6), Euphorbia humifusa (4.9), Adiantum capillus-veneris (4.9), Ziziphus jujube (4.9), Glycyrrhiza uralensis (7.1), Foeniculum vulgare (4.9), Lavandula angustifolia (4.9), Dracocephalum moldavica L. (4.9), and Alhagi pseudoalhagi (42.3). Statistical Analysis Used: The precisions of all six compounds were <0.60%, and the average recoveries ranged from 99.39% to 104.85%. Highly significant linear correlations were found between component concentrations and specific chromatographic peak areas (R2 > 0.999). Results: The proposed method was successfully applied to determine the levels of six active components in ASMQ. Conclusions: Given the simplicity, precision, specificity, and sensitivity of the method, it can be utilized as a quality control approach to simultaneously determining the six phenolic compounds in AMSQ. PMID:25709227

Signal enhancement for gradient reverse-phase high-performance liquid chromatography-electrospray ionization mass spectrometry analysis with trifluoroacetic and other strong acid modifiers by postcolumn addition of propionic acid and isopropanol.

PubMed

Kuhlmann, F E; Apffel, A; Fischer, S M; Goldberg, G; Goodley, P C

1995-12-01

Trifluoroacetic acid (TFA) and other volatile strong acids, used as modifiers in reverse-phase high-performance liquid chromatography, cause signal suppression for basic compounds when analyzed by electrospray ionization mass spectrometry (ESI-MS). Evidence is presented that signal suppression is caused by strong ion pairing between the TFA anion and the protonated sample cation of basic sample molecules. The ion-pairing process "masks" the protonated sample cations from the ESI-MS electric fields by rendering them "neutral. " Weakly basic molecules are not suppressed by this process. The TFA signal suppression effect is independent from the well-known spray problem that electrospray has with highly aqueous solutions that contain TFA. This previously reported spray problem is caused by the high conductivity and surface tension of aqueous TFA solutions. A practical method to enhance the signal for most basic analytes in the presence of signal-suppressing volatile strong acids has been developed. The method employs postcolumn addition of a solution of 75% propionic acid and 25% isopropanol in a ratio 1:2 to the column flow. Signal enhancement is typically 10-50 times for peptides and other small basic molecules. Thus, peptide maps that use ESI-MS for detection can be performed at lower levels, with conventional columns, without the need to use capillary chromatography or reduced mass spectral resolution to achieve satisfactory sensitivity. The method may be used with similar results for heptafluorobutyric acid and hydrochloric acid. A mechanism for TFA signal suppression and signal enhancement by the foregoing method, is proposed.

Fourier domain preconditioned conjugate gradient algorithm for atmospheric tomography.

PubMed

Yang, Qiang; Vogel, Curtis R; Ellerbroek, Brent L

2006-07-20

By 'atmospheric tomography' we mean the estimation of a layered atmospheric turbulence profile from measurements of the pupil-plane phase (or phase gradients) corresponding to several different guide star directions. We introduce what we believe to be a new Fourier domain preconditioned conjugate gradient (FD-PCG) algorithm for atmospheric tomography, and we compare its performance against an existing multigrid preconditioned conjugate gradient (MG-PCG) approach. Numerical results indicate that on conventional serial computers, FD-PCG is as accurate and robust as MG-PCG, but it is from one to two orders of magnitude faster for atmospheric tomography on 30 m class telescopes. Simulations are carried out for both natural guide stars and for a combination of finite-altitude laser guide stars and natural guide stars to resolve tip-tilt uncertainty.

Why do high-redshift galaxies show diverse gas-phase metallicity gradients?

NASA Astrophysics Data System (ADS)

Ma, Xiangcheng; Hopkins, Philip F.; Feldmann, Robert; Torrey, Paul; Faucher-Giguère, Claude-André; Kereš, Dušan

2017-04-01

Recent spatially resolved observations of galaxies at z ˜ 0.6-3 reveal that high-redshift galaxies show complex kinematics and a broad distribution of gas-phase metallicity gradients. To understand these results, we use a suite of high-resolution cosmological zoom-in simulations from the Feedback in Realistic Environments project, which include physically motivated models of the multiphase interstellar medium, star formation and stellar feedback. Our simulations reproduce the observed diversity of kinematic properties and metallicity gradients, broadly consistent with observations at z ˜ 0-3. Strong negative metallicity gradients only appear in galaxies with a rotating disc, but not all rotationally supported galaxies have significant gradients. Strongly perturbed galaxies with little rotation always have flat gradients. The kinematic properties and metallicity gradient of a high-redshift galaxy can vary significantly on short time-scales, associated with starburst episodes. Feedback from a starburst can destroy the gas disc, drive strong outflows and flatten a pre-existing negative metallicity gradient. The time variability of a single galaxy is statistically similar to the entire simulated sample, indicating that the observed metallicity gradients in high-redshift galaxies reflect the instantaneous state of the galaxy rather than the accretion and growth history on cosmological time-scales. We find weak dependence of metallicity gradient on stellar mass and specific star formation rate (sSFR). Low-mass galaxies and galaxies with high sSFR tend to have flat gradients, likely due to the fact that feedback is more efficient in these galaxies. We argue that it is important to resolve feedback on small scales in order to produce the diverse metallicity gradients observed.

Synthesis and evaluation of porous polymethylsilsesquioxane microspheres as low silanol activity chromatographic stationary phase for basic compound separation.

PubMed

Huo, Zhixia; Wan, Qianhong; Chen, Lei

2018-06-08

Polymethylsilsesquioxanes (PMSQ) are potentially useful materials for liquid chromatography owing to their unique chemical, electrical and mechanical properties. Surprisingly however, no systematic studies on the use of spherical PMSQ particles as chromatographic packing have been reported. Accordingly, we present a comprehensive study aimed to characterize the chromatographic properties of this material in high performance liquid chromatography (HPLC) and to compare them with those observed on methyl (C 1 ) bonded silica phase under comparable conditions. Porous spherical particles were synthesized by a two-step hydrolysis and condensation procedure from methyltrimethoxysilane (MTMS) as a sole precursor. The as-synthesized microspheres possess spherical shape, narrow size distribution, mesoporous structure, high surface area (817 m 2  g -1 ) and reasonable carbon load (16.6%). They can be used directly as the HPLC stationary phase without the need for size classification. The PMSQ phase exhibits typical reversed-phase chromatographic properties with higher methylene selectivity and low silanol activity compared with the C 1 column. The retention mechanism for basic compounds was systematically evaluated by studying the effect of pH, ionic and solvent strength of the mobile phase. Basic compounds displayed lower retention factor and symmetric peak shape on the PMSQ column whereas longer retention and strong tailing peaks were observed on the C 1 column. The difference in retention behavior between the two columns is explained in terms of different principal retention mechanisms. Because of the low silanol activity, retention of basic compounds on the PMSQ column is governed solely by a reversed-phase mechanism. By contrast, multiple interactions including reversed-phase, cation exchange and simultaneous reversed-phase/cationic exchange interaction contribute to the retention on the C 1 column, as previously observed on other silica based reversed-phases. Furthermore, the PMSQ phase exhibited significantly enhanced stability under alkaline conditions compared with its silica-based counterpart. Taken together, the favorable morphology and pore structure combined with the benefits of low silanol activity, high pH stability and prolonged column lifetime make the newly developed PMSQ phase a promising and viable alternative to silica based reversed-phase packings for separation of basic compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Higher Nucleoporin-Importinβ Affinity at the Nuclear Basket Increases Nucleocytoplasmic Import

PubMed Central

Azimi, Mohammad; Mofrad, Mohammad R. K.

2013-01-01

Several in vitro studies have shown the presence of an affinity gradient in nuclear pore complex proteins for the import receptor Importinβ, at least partially contributing to nucleocytoplasmic transport, while others have historically argued against the presence of such a gradient. Nonetheless, the existence of an affinity gradient has remained an uncharacterized contributing factor. To shed light on the affinity gradient theory and better characterize how the existence of such an affinity gradient between the nuclear pore and the import receptor may influence the nucleocytoplasmic traffic, we have developed a general-purpose agent based modeling (ABM) framework that features a new method for relating rate constants to molecular binding and unbinding probabilities, and used our ABM approach to quantify the effects of a wide range of forward and reverse nucleoporin-Importinβ affinity gradients. Our results indicate that transport through the nuclear pore complex is maximized with an effective macroscopic affinity gradient of 2000 µM, 200 µM and 10 µM in the cytoplasmic, central channel and nuclear basket respectively. The transport rate at this gradient is approximately 10% higher than the transport rate for a comparable pore lacking any affinity gradient, which has a peak transport rate when all nucleoporins have an affinity of 200 µM for Importinβ. Furthermore, this optimal ratio of affinity gradients is representative of the ratio of affinities reported for the yeast nuclear pore complex – suggesting that the affinity gradient seen in vitro is highly optimized. PMID:24282617

Development of high-throughput multi-residue method for non-steroidal anti-inflammatory drugs monitoring in swine muscle by LC-MS/MS.

PubMed

Castilhos, Tamara S; Barreto, Fabiano; Meneghini, Leonardo; Bergold, Ana Maria

2016-07-01

A reliable and simple method for the detection and quantification of residues of 14 non-steroidal anti-inflammatory drugs and a metamizole metabolite in swine muscle was developed using liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-ESI-MS/MS). The samples were extracted with acetonitrile (ACN) in solid-liquid extraction followed by a low-temperature partitioning (LLE-LTP) process at -20 ± 2°C. After evaporation to dryness, the residue was reconstituted with hexane and a mixture of water:acetonitrile (1:1). LC separation was achieved on a reversed-phase (RP18) column with gradient elution using water (phase A) and ACN (phase B) both containing 1 mmol l(-)(1) ammonium acetate (NH4COO) with 0.025% acetic acid. Analysis was carried out on a triple-quadrupole tandem mass spectrometer (LC-MS/MS) in multiple reaction monitoring mode using an electrospray interface in negative and positive mode in a single run. Method validation was performed according to the criteria of Commission Decision No. 2002/657/EC. The matrix effect and linearity were evaluated. Decision limit (CCα), detection capability (CCβ), accuracy and repeatability of the method are also reported. The proposed method proved to be simple, easy and adequate for high-throughput analysis and was applied to routine analysis by the Brazilian Ministry of Agriculture, Livestock and Food Supply.

Small Mammals as Indicators of Climate, Biodiversity, and Ecosystem Change

USGS Publications Warehouse

Hope, Andrew G.; Waltari, Eric; Morse, Nathan R.; Flamme, M.J.; Cook, Joseph A.; Talbot, Sandra L.

2017-01-01

Climate is a driving evolutionary force for biodiversity in high-latitude Alaska. This region is complex and dynamic with high annual variation in temperature and light. Through deeper time, Alaska has experienced major climate extremes over much longer periodicity. For example, the Quaternary Period (the last ~2.5 million years), commonly known as the Ice Age, was punctuated by more than 20 major glacial-interglacial cycles. During glacial phases, water was locked up in ice sheets that covered much of North America, and the resulting lower sea levels exposed a land connection between Alaska and Siberia, a combined region known as Beringia (Figure 1). This isthmus provided vast expanses of land for species to inhabit, provided they could withstand potentially harsh polar conditions. Each extended glacial phase periodically transitioned into a shorter interglacial warm phase. These climate reversals melted continental ice sheets to expose corridors for reinvasion of terrestrial species, particularly those associated with forested habitats further south. Those species that survived at northern latitudes through repeated glacial-interglacial cycles formed the Arctic tundra communities that persist today. At present, Alaska supports diverse communities associated with both tundra and forests (Figure 2). These communities often interact with one another across latitudinal and elevational gradients, with tundra species generally found further north or higher in elevation. Alaska’s climate is continuing to change today, strongly influencing local environments and the distribution and dynamics of wildlife species.

RP-HPLC ANALYSIS OF ACIDIC AND BASIC DRUGS IN SYSTEMS WITH DIETHYLAMINE AS ELUENTS ADDITIVE.

PubMed

Petruczynik, Anna; Wroblewski, Karol; Strozek, Szymon; Waksmundzka-Hajnos, Monika

2016-11-01

The chromatographic behavior of some basic and acidic drugs was studied on Cl 8, Phenyl-Hexyl and Polar RP columns with methanol or acetonitrile as organic modifiers of aqueous mobile phases containing addition of diethylamine. Diethylamine plays a double function of silanol blocker reagent in analysis of basic drugs and ion-pair reagent in analysis of acidic drugs. Most symmetrical peaks and highest system efficiency were obtained on Phenyl-Hexyl and Polar RP columns in tested mobile phase systems compared to results obtained on C18 column. A new rapid, simple, specific and accurate reverse phase liquid chromatographic method was developed for the simultaneous determination of atorvastatin - antihyperlipidemic drug and amlodipine - calcium channel blocker in one pharmaceutical formulation. Atorvastatin is an acidic compounds while amlodipine is a basic substance. The chromatographic separation was carried out on Phenyl-Hexyl column by gradient elution mode with acetonitrile as organic modifier, acetate buffer at pH 3.5 and Q.025 M/L diethylamine. The proposed method was validated for specificity, precision, accuracy, linearity, and robustness. The linearity range of atorvastatin and amlodipine for 5 - 100 μg/mL was obtained with limits of-detection (LOD) 3.2750 gg/mL and 3.2102 μg/mL, respectively. The proposed method made use of DAD as a tool for peak identity and purity confirmation.

A Rapid Novel HPLC Method for Estimation of Eight Related Compounds in Azilsartan Kamedoxomil and Identification of Degradation Compounds by Using LC-MS.

PubMed

Sreenivasulu, J; Venkata Ramana, P; Sampath Kumar Reddy, G; Nagaraju, Ch V S; Thirumalai Rajan, S; Eswaraiah, S

2015-10-01

A novel, rapid, specific and stability-indicating reverse-phase high-performance liquid chromatography method was developed for the quantitative determination of related compounds, obtained from two different synthetic routes and degradation products of Azilsartan kamedoxomil (AZL). The method was developed by using a YMC-Pack pro C18 (150 × 4.6 mm, 3 µm) column with a mobile phase containing a gradient mobile phase combination. The eluted compounds were measured at wavelength 220 nm. The developed method run time was 25 min, within which AZL and its eight impurities were well separated with minimum 3.0 resolution. The drug substance was subjected to stress conditions of hydrolysis (acid, base and water), oxidation, photolysis, sunlight, 75% relative humidity and thermal degradation as per International Conference on Harmonization (ICH) prescribed stress conditions to ascertain the stability-indicating power of the method. Significant degradation was observed during acid, base, peroxide, water hydrolysis and 75% relative humidity studies. The mass balance of AZL was close to 100% in all the stress condition. The developed method was validated as per the ICH guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Mixed-Mode Operation of Hybrid Phase-Change Nanophotonic Circuits.

PubMed

Lu, Yegang; Stegmaier, Matthias; Nukala, Pavan; Giambra, Marco A; Ferrari, Simone; Busacca, Alessandro; Pernice, Wolfram H P; Agarwal, Ritesh

2017-01-11

Phase change materials (PCMs) are highly attractive for nonvolatile electrical and all-optical memory applications because of unique features such as ultrafast and reversible phase transitions, long-term endurance, and high scalability to nanoscale dimensions. Understanding their transient characteristics upon phase transition in both the electrical and the optical domains is essential for using PCMs in future multifunctional optoelectronic circuits. Here, we use a PCM nanowire embedded into a nanophotonic circuit to study switching dynamics in mixed-mode operation. Evanescent coupling between light traveling along waveguides and a phase-change nanowire enables reversible phase transition between amorphous and crystalline states. We perform time-resolved measurements of the transient change in both the optical transmission and resistance of the nanowire and show reversible switching operations in both the optical and the electrical domains. Our results pave the way toward on-chip multifunctional optoelectronic integrated devices, waveguide integrated memories, and hybrid processing applications.

Pure phase encode magnetic field gradient monitor.

PubMed

Han, Hui; MacGregor, Rodney P; Balcom, Bruce J

2009-12-01

Numerous methods have been developed to measure MRI gradient waveforms and k-space trajectories. The most promising new strategy appears to be magnetic field monitoring with RF microprobes. Multiple RF microprobes may record the magnetic field evolution associated with a wide variety of imaging pulse sequences. The method involves exciting one or more test samples and measuring the time evolution of magnetization through the FIDs. Two critical problems remain. The gradient waveform duration is limited by the sample T(2)*, while the k-space maxima are limited by gradient dephasing. The method presented is based on pure phase encode FIDs and solves the above two problems in addition to permitting high strength gradient measurement. A small doped water phantom (1-3 mm droplet, T(1), T(2), T(2)* < 100 micros) within a microprobe is excited by a series of closely spaced broadband RF pulses each followed by FID single point acquisition. Two trial gradient waveforms have been chosen to illustrate the technique, neither of which could be measured by the conventional RF microprobe measurement. The first is an extended duration gradient waveform while the other illustrates the new method's ability to measure gradient waveforms with large net area and/or high amplitude. The new method is a point monitor with simple implementation and low cost hardware requirements.

Remobilizing the Interface of Thermocapillary Driven Bubbles Retarded By the Adsorption of a Surfactant Impurity on the Bubble Surface

NASA Technical Reports Server (NTRS)

Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim (Technical Monitor)

2001-01-01

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow that propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillary to direct the movement of bubbles in space is the fact that surfactant impurities, which are unavoidably present in the continuous phase, can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. (This can also be the case if kinetic desorption of surfactant at the back end of the bubble is much slower than convection.) For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like and bubbles translate as solid particles). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature-induced tension gradient, and can decrease to near zero the bubble's thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have be retarded by the adsorption onto the bubble surface of a surfactant impurity. Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble surface much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition, the rapid kinetic exchange and high bulk concentration maintain a saturated surface with uniform surface concentrations. This prevents retarding surface tension gradients and keeps the thermocapillary velocity high. In our reports over the first 2 years, we presented numerical simulations of the bubble motion and surfactant transport which verified theoretically the concept of remobilization, and the development of an apparatus to track and measure the velocity of rising bubbles in a glycerol/water surfactant solution. This year, we detail experimental observations of remobilization. Two polyethylene oxide surfactants were studied, C12E6 (CH3(CH2)11(OCH2)6OH) and C10E8 (CH3(CH2)4(OCH2CH2)8OH). Measurements of the kinetic exchange for these surfactants show that the one with the longer hydrophobe chain C12E6 has a lower rate of kinetic exchange. In addition, this surfactant is much less soluble in the glycerol/water mixture because of the shorter ethoxylate chain. As a result, we found that C12E6 had only a very limited ability to remobilize rising bubbles because of the limited kinetic exchange and reduced solubility. However, C10E8, with its higher solubility and more rapid exchange was found to dramatically remobilize rising bubbles. We also compared our theoretical calculations to the experimental measurements of velocity for both the non-remobilizing and remobilizing surfactants and found excellent agreement. We further observed that for C10E8 at high concentrations, which exceeded the critical micelle concentrations, additional remobilization was measured. In this case the rapid exchange of monomer between micelle and surfactant provides an additional mechanism for maintaining a uniform surface concentrations.

Development and validation of LC methods for the separation of misoprostol related substances and diastereoisomers.

PubMed

Kahsay, Getu; Song, Huiying; Eerdekens, Fran; Tie, Yaxin; Hendriks, Danny; Van Schepdael, Ann; Cabooter, Deirdre; Adams, Erwin

2015-01-01

Misoprostol is a synthetic prostaglandin E1 analogue which is mainly used for prevention and treatment of gastric ulcers, but also for abortion due to its labour inducing effect. Misoprostol exists as a mixture of diastereoisomers (1:1) and has several related impurities owing to its instability at higher temperatures and moisture. A simple and robust reversed phase liquid chromatographic (RPLC) method is described for the separation of the related substances and a normal phase (NP) LC method for the separation of misoprostol diastereoisomers. The RPLC method was performed using an Ascentis Express C18 (150 mm × 4.6 mm, 5 μm) column kept at 35 °C. The mobile phase was a gradient mixture of mobile phase A (ACN-H2O-MeOH, 28:69:3 v/v/v) and mobile phase B (ACN-H2O-MeOH, 47:50:3 v/v/v) eluted at a flow rate of 1.5 mL/min. UV detection was performed at 200 nm. The NPLC method was undertaken by using an XBridge bare silica (150 mm × 2.1 mm, 3.5 μm) column at 35 °C. The mobile phase contained 1-propanol-heptane-TFA (4:96:0.1%, v/v/v), pumped at a flow rate of 0.5 mL/min. UV detection was performed at 205 nm. This LC method can properly separate the two diastereoisomers (Rs > 2) within an analysis time of less than 20 min. Both methods were validated according to the ICH guidelines. Furthermore, these new LC methods have been successfully applied for purity control and diastereoisomers ratio determination of misoprostol bulk drug, tablets and dispersion. Copyright © 2015 Elsevier B.V. All rights reserved.

On Localized Vapor Pressure Gradients Governing Condensation and Frost Phenomena.

PubMed

Nath, Saurabh; Boreyko, Jonathan B

2016-08-23

Interdroplet vapor pressure gradients are the driving mechanism for several phase-change phenomena such as condensation dry zones, interdroplet ice bridging, dry zones around ice, and frost halos. Despite the fundamental nature of the underlying pressure gradients, the majority of studies on these emerging phenomena have been primarily empirical. Using classical nucleation theory and Becker-Döring embryo formation kinetics, here we calculate the pressure field for all possible modes of condensation and desublimation in order to gain fundamental insight into how pressure gradients govern the behavior of dry zones, condensation frosting, and frost halos. Our findings reveal that in a variety of phase-change systems the thermodynamically favorable mode of nucleation can switch between condensation and desublimation depending upon the temperature and wettability of the surface. The calculated pressure field is used to model the length of a dry zone around liquid or ice droplets over a broad parameter space. The long-standing question of whether the vapor pressure at the interface of growing frost is saturated or supersaturated is resolved by considering the kinetics of interdroplet ice bridging. Finally, on the basis of theoretical calculations, we propose that there exists a new mode of frost halo that is yet to be experimentally observed; a bimodal phase map is developed, demonstrating its dependence on the temperature and wettability of the underlying substrate. We hope that the model and predictions contained herein will assist future efforts to exploit localized vapor pressure gradients for the design of spatially controlled or antifrosting phase-change systems.

A Theoretical Study of Remobilizing Surfactant Retarded Fluid Particle Interfaces

NASA Technical Reports Server (NTRS)

Wang, Yanping; Papageorgiou, Dimitri; Maldarelli, Charles

1996-01-01

Microgravity processes must rely on mechanisms other than bouyancy to move bubbles or droplets from one region to another in a continuous liquid phase. One suggested method is thermocapillary migration in which a temperature gradient is applied to the continuous phase. When a fluid particle contacts this gradient, one pole of the particle becomes warmer than the opposing pole. The interfacial tension between the drop or bubble phase and the continuous phase usually decreases with temperature. Thus the cooler pole is of higher interfacial tension than the warmer pole, and the interface is tugged in the direction of the cooler end. This thermocapillary or thermally induced Marangoni surface stress causes a fluid streaming in the continuous phase from which develops a viscous shear traction and pressure gradient which together propel the particle in the direction of the warmer fluid. In this paper, we provide a theoretical basis for remobilizing surfactant retarded fluid particle interfaces in an effort to make viable the use of thermocapillary migrations for the management of bubbles and drops in microgravity,

A fast referenceless PRFS-based MR thermometry by phase finite difference

NASA Astrophysics Data System (ADS)

Zou, Chao; Shen, Huan; He, Mengyue; Tie, Changjun; Chung, Yiu-Cho; Liu, Xin

2013-08-01

Proton resonance frequency shift-based MR thermometry is a promising temperature monitoring approach for thermotherapy but its accuracy is vulnerable to inter-scan motion. Model-based referenceless thermometry has been proposed to address this problem but phase unwrapping is usually needed before the model fitting process. In this paper, a referenceless MR thermometry method using phase finite difference that avoids the time consuming phase unwrapping procedure is proposed. Unlike the previously proposed phase gradient technique, the use of finite difference in the new method reduces the fitting error resulting from the ringing artifacts associated with phase discontinuity in the calculation of the phase gradient image. The new method takes into account the values at the perimeter of the region of interest because of their direct relevance to the extrapolated baseline phase of the region of interest (where temperature increase takes place). In simulation study, in vivo and ex vivo experiments, the new method has a root-mean-square temperature error of 0.35 °C, 1.02 °C and 1.73 °C compared to 0.83 °C, 2.81 °C, and 3.76 °C from the phase gradient method, respectively. The method also demonstrated a slightly higher, albeit small, temperature accuracy than the original referenceless MR thermometry method. The proposed method is computationally efficient (∼0.1 s per image), making it very suitable for the real time temperature monitoring.

[Management of ascites due to portal hypertension].

PubMed

Godat, S; Antonino, A T; Dehlavi, M-A; Moradpour, D; Doerig, C

2012-09-05

Portal hypertension is regularly encountered by the general practitioner. It is defined by an elevation of the porto-systemic pressure gradient, with complications such as ascites, spontaneous bacterial peritonitis, hepatorenal syndrome, variceal bleeding, hypersplenism, hepatopulmonary syndrome or hepatic encephalopathy occuring when a significant elevation of this gradient is reached. Cirrhosis is the primary cause of portal hypertension in industrialized countries. Symptomatic portal hypertension carries a poor prognosis. Management should be initiated rapidly, including the identification and correction of any reversible underlying condition. Liver transplantation should be considered in advanced cases.