Effects of elevated temperature and mobile phase composition on a novel C18 silica column.

PubMed

Lippert, J Andreas; Johnson, Todd M; Lloyd, Jarem B; Smith, Jared P; Johnson, Bryce T; Furlow, Jason; Proctor, Angela; Marin, Stephanie J

2007-05-01

A novel polydentate C18 silica column was evaluated at an elevated temperature under acidic, basic, and neutral mobile phase conditions using ACN and methanol as the mobile phase organic modifier. The temperature range was 40-200 degrees C. The mobile phase compositions were from 0 to 80% organic-aqueous v/v and the mobile phase pH levels were between 2 and 12. The maximum operating temperature of the column was affected by the amount and type of organic modifier used in the mobile phase. Under neutral conditions, the column showed good column thermal stability at temperatures ranging between 120 and 200 degrees C in methanol-water and ACN-water solvent systems. At pH 2 and 3, the column performed well up to about 160 degrees C at two fixed ACN-buffer compositions. Under basic conditions at elevated temperatures, the column material deteriorated more quickly, but still remained stable up to 100 degrees C at pH 9 and 60 degrees C at pH 10. The results of this study indicate that this novel C18 silica-based column represents a significant advancement in RPLC column technology with enhanced thermal and pH stability when compared to traditional bonded phase silica columns.

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Differential Effects of Low-Molecular-Weight Organic Acids on the Mobilization of Soil-Borne Arsenic and Trace Metals.

PubMed

Nworie, Obinna Elijah; Qin, Junhao; Lin, Chuxia

2017-08-21

A batch experiment was conducted to examine the effects of six low-molecular-weight organic acids on the mobilization of arsenic and trace metals from a range of contaminated soils. The results showed that the organic acids behaved differently when reacting with soil-borne As and trace metals. Oxalic acid and acetic acid had the strongest and weakest capacity to mobilize the investigated elements, respectively. The solubilisation of iron oxides by the organic acids appears to play a critical role in mobilizing other trace metals and As. Apart from acidification and complexation, reductive dissolution played a dominant role in the dissolution of iron oxides in the presence of oxalic acid, while acidification tended to be more important for dissolving iron oxides in the presence of other organic acids. The unique capacity of oxalic acid to solubilize iron oxides tended to affect the mobilization of other elements in different ways. For Cu, Mn, and Zn, acidification-driven mobilization was likely to be dominant while complexation might play a major role in Pb mobilization. The formation of soluble Fe and Pb oxalate complexes could effectively prevent arsenate or arsenite from combining with these metals to form solid phases of Fe or Pb arsenate or arsenite.

Combined effects of mobile phase composition and temperature on the retention of phenolic antioxidants on an octylsilica polydentate column.

PubMed

Jandera, Pavel; Vyňuchalová, Kateřina; Nečilová, Kateřina

2013-11-22

Combined effects of temperature and mobile-phase composition on retention and separation selectivity of phenolic acids and flavonoid compounds were studied in liquid chromatography on a polydentate Blaze C8 silica based column. The temperature effects on the retention can be described by van't Hoff equation. Good linearity of lnk versus 1/T graphs indicates that the retention is controlled by a single mechanism in the mobile phase and temperature range studied. Enthalpic and entropic contributions to the retention were calculated from the regression lines. Generally, enthalpic contributions control the retention at lower temperatures and in mobile phases with lower concentrations of methanol in water. Semi-empirical retention models describe the simultaneous effects of temperature and the volume fraction of the organic solvent in the mobile phase. Using the linear free energy-retention model, selective dipolarity/polarizability, hydrogen-bond donor, hydrogen-bond acceptor and molecular size contributions to retention were estimated at various mobile phase compositions and temperatures. In addition to mobile phase gradients, temperature programming can be used to reduce separation times. Copyright © 2013 Elsevier B.V. All rights reserved.

Application of perfluorinated acids as ion-pairing reagents for reversed-phase chromatography and retention-hydrophobicity relationships studies of selected beta-blockers.

PubMed

Flieger, J

2010-01-22

The addition of the homologous series of perfluorinated acids-trifluoroacetic acid (TFAA), pentafluoropropionic acid (PFPA), heptafluorobutyric acid (HFBA) to mobile phases for reversed-phase high-performance liquid chromatography (RP-HPLC) of beta-blockers was tested. Acidic modifiers were responsible for acidification of mobile phase (pH 3) ensuring the protonation of the beta-blockers and further ion pairs creation. The effect of the type and concentration of mobile phase additives on retention parameters, the efficiency of the peaks, their symmetry and separation selectivity of the beta-blockers mixture were all studied. It appeared that at increasing acid concentration, the retention factor, for all compounds investigated, increased to varying degrees. It should be stressed that the presence of acids more significantly affected the retention of the most hydrophobic beta-blockers. Differences in hydrophobicity of drugs can be maximized through variation of the hydrophobicity of additives. Thus, the relative increase in the retention depends on either concentration and hydrophobicity of the anionic mobile phase additive or hydrophobicity of analytes. According to QSRR (quantitative structure retention relationship) methodology, chromatographic lipophilicity parameters: isocratic log k and log k(w) values (extrapolated retention to pure water) were correlated with the molecular (log P(o/w)) and apparent (log P(app)) octanol-water partition coefficients obtained experimentally by countercurrent chromatography (CCC) or predicted by Pallas software. The obtained, satisfactory retention-hydrophobicity correlations indicate that, in the case of the basic drugs examined in RP-HPLC systems modified with perfluorinated acids, the retention is mainly governed by their hydrophobicity. Copyright 2009 Elsevier B.V. All rights reserved.

[Determination of glycyrrhizinic acid in biotransformation system by reversed-phase high performance liquid chromatography].

PubMed

Li, Hui; Lu, Dingqiang; Liu, Weimin

2004-05-01

A method for determining glycyrrhizinic acid in the biotransformation system by reversed-phase high performance liquid chromatography (RP-HPLC) was developed. The HPLC conditions were as follows: Hypersil C18 column (4.6 mm i.d. x 250 mm, 5 microm) with a mixture of methanol-water-acetic acid (70:30:1, v/v) as the mobile phase; flow rate at 1.0 mL/min; and UV detection at 254 nm. The linear range of glycyrrhizinic acid was 0.2-20 microg. The recoveries were 98%-103% with relative standard deviations between 0.16% and 1.58% (n = 3). The method is simple, rapid and accurate for determining glycyrrhizinic acid.

Reversed-phase high-performance liquid chromatography of unsubstituted aminobenzoic acids

USGS Publications Warehouse

Abidi, S.L.

1989-01-01

High-performance liquid chromatographic (HPLC) characteristics of three position isomers of aminobenzoic acids (potential metabolites of important anesthetic drugs), were delineated with respect to their interactions with various mobile phases and stationary phases. HPLC with five hydrocarbonaceous phase, I?-cyclodextrin silica (CDS), macrophase MP-1 polymer (MP), macroporous polystyrene/divinylbenzene (MPD), octadecylsilica (ODS), and propylphenylsilica (PPS), yielded results explicable in terms of substituent effects derived from the bifunctional amino- and carboxy groups. For cases where mobile phases contained sulfonates or quaternary ammonium salts both having longer chain alkyls, retention of analytes on all but CDS appeared to proceed predominantly via an ion-pairing mechanism. The extent of the corresponding counter-ion effects decreased in the order: MPD > ODS > PPS > MP, while the analyte retention order paralleled thier pH2 values. On the other hand, an inverse relationship between the magnitude of capacity factors (k') and pK1 values of the title compounds was observed in experiments that produced retention data incompatible with ion-pair interaction rationales. The unique HPLC results obtained with the CDS phase are compared with those obtained with other phases.

Retention of ionisable compounds on high-performance liquid chromatography XVII. Estimation of the pH variation of aqueous buffers with the change of the methanol fraction of the mobile phase.

PubMed

Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

2007-01-05

The use of methanol-aqueous buffer mobile phases in HPLC is a common election when performing chromatographic separations of ionisable analytes. The addition of methanol to the aqueous buffer to prepare such a mobile phase changes the buffer capacity and the pH of the solution. In the present work, the variation of these buffer properties is studied for acetic acid-acetate, phosphoric acid-dihydrogenphosphate-hydrogenphosphate, citric acid-dihydrogencitrate-hydrogencitrate-citrate, and ammonium-ammonia buffers. It is well established that the pH change of the buffers depends on the initial concentration and aqueous pH of the buffer, on the percentage of methanol added, and on the particular buffer used. The proposed equations allow the pH estimation of methanol-water buffered mobile phases up to 80% in volume of organic modifier from initial aqueous buffer pH and buffer concentration (before adding methanol) between 0.001 and 0.01 mol L(-1). From both the estimated pH values of the mobile phase and the estimated pKa of the ionisable analytes, it is possible to predict the degree of ionisation of the analytes and therefore, the interpretation of acid-base analytes behaviour in a particular methanol-water buffered mobile phase.

The Use of Ammonium Formate as a Mobile-Phase Modifier for LC-MS/MS Analysis of Tryptic Digests

PubMed Central

Johnson, Darryl; Boyes, Barry; Orlando, Ron

2013-01-01

A major challenge facing current mass spectrometry (MS)-based proteomics research is the large concentration range displayed in biological systems, which far exceeds the dynamic range of commonly available mass spectrometers. One approach to overcome this limitation is to improve online reversed-phase liquid chromatography (RP-LC) separation methodologies. LC mobile-phase modifiers are used to improve peak shape and increase sample load tolerance. Trifluoroacetic acid (TFA) is a commonly used mobile-phase modifier, as it produces peptide separations that are far superior to other additives. However, TFA leads to signal suppression when incorporated with electrospray ionization (ESI), and thus, other modifiers, such as formic acid (FA), are used for LC-MS applications. FA exhibits significantly less signal suppression, but is not as effective of a modifier as TFA. An alternative mobile-phase modifier is the combination of FA and ammonium formate (AF), which has been shown to improve peptide separations. The ESI-MS compatibility of this modifier has not been investigated, particularly for proteomic applications. This work compares the separation metrics of mobile phases modified with FA and FA/AF and explores the use of FA/AF for the LC-MS analysis of tryptic digests. Standard tryptic-digest peptides were used for comparative analysis of peak capacity and sample load tolerance. The compatibility of FA/AF in proteomic applications was examined with the analysis of soluble proteins from canine prostate carcinoma tissue. Overall, the use of FA/AF improved online RP-LC separations and led to significant increases in peptide identifications with improved protein sequence coverage. PMID:24294112

The use of ammonium formate as a mobile-phase modifier for LC-MS/MS analysis of tryptic digests.

PubMed

Johnson, Darryl; Boyes, Barry; Orlando, Ron

2013-12-01

A major challenge facing current mass spectrometry (MS)-based proteomics research is the large concentration range displayed in biological systems, which far exceeds the dynamic range of commonly available mass spectrometers. One approach to overcome this limitation is to improve online reversed-phase liquid chromatography (RP-LC) separation methodologies. LC mobile-phase modifiers are used to improve peak shape and increase sample load tolerance. Trifluoroacetic acid (TFA) is a commonly used mobile-phase modifier, as it produces peptide separations that are far superior to other additives. However, TFA leads to signal suppression when incorporated with electrospray ionization (ESI), and thus, other modifiers, such as formic acid (FA), are used for LC-MS applications. FA exhibits significantly less signal suppression, but is not as effective of a modifier as TFA. An alternative mobile-phase modifier is the combination of FA and ammonium formate (AF), which has been shown to improve peptide separations. The ESI-MS compatibility of this modifier has not been investigated, particularly for proteomic applications. This work compares the separation metrics of mobile phases modified with FA and FA/AF and explores the use of FA/AF for the LC-MS analysis of tryptic digests. Standard tryptic-digest peptides were used for comparative analysis of peak capacity and sample load tolerance. The compatibility of FA/AF in proteomic applications was examined with the analysis of soluble proteins from canine prostate carcinoma tissue. Overall, the use of FA/AF improved online RP-LC separations and led to significant increases in peptide identifications with improved protein sequence coverage.

Post-column mobile phase adjustment: a strategy to eliminate the contradiction between liquid chromatography and mass spectrometry in the determination of flavonoids in rat plasma.

PubMed

Zheng, Shirui; Ma, Zhiyuan; Han, Haixia; Ye, Jianfeng; Wang, Ruwei; Cai, Sheng; Zhou, Hui; Yu, Lushan; Zeng, Su; Jiang, Huidi

2014-07-01

Flavonoids are a group of important naturally occurring polyphenolic compounds with a wide range of biological effects. In this study, a sensitive liquid chromatography tandem mass spectrometry method was developed to simultaneously determine multiple active flavonoids, including quercetin (Que), kaempferol (Kae), apigenin (Api), isorhamnetin (Iso), luteolin (Lut), and naringenin (Nar), in rat plasma. To achieve a satisfied peak shape and LC separation, formic acid with the concentration between 0.05 and 0.2%, or in some case 5%, was generally used to acidify the LC mobile phase in reported studies. Here we found that even 0.05% formic acid could lead to strong mass signal suppression, and the absence of formic acid could reverse the signal suppression but cause serious peak tailing. There is an irreconcilable contradiction between liquid chromatography (LC) and mass spectrometry (MS). In order to simultaneously satisfy LC and MS, LC mobile phase with 0.00075% formic acid and post column mobile phase adjustment with 0.0677% ammonium solution in isopropanol were applied. Compared with the conventional method with mobile phase containing 0.05% formic acid, the mass signal response of Que, Kae, Api, Iso, Lut, Nar, and Oka increased 26.2, 18.6, 13.6, 23.5, 17.5, 15.6 and 15.4 fold, respectively. In addition, the post column mobile phase addition exhibited the better peak shape for the reduction of analytes longitudinal diffusion. The method has been fully validated according to FDA guidelines within the linear range between 0.328 ng mL⁻¹ and 168 ng mL⁻¹, and successfully applied to a pilot pharmacokinetic study of rats after administering 5.43 g kg⁻¹ Pollen of Brassica campestris. Copyright © 2014 Elsevier B.V. All rights reserved.

[[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

PubMed

Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

2014-09-01

Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

Effect of n-octanol in the mobile phase on lipophilicity determination by reversed-phase high-performance liquid chromatography on a modified silica column.

PubMed

Benhaim, Deborah; Grushka, Eli

2008-10-31

In this study, we show that the addition of n-octanol to the mobile phase improves the chromatographic determination of lipophilicity parameters of xenobiotics (neutral solutes, acidic, neutral and basic drugs) on a Phenomenex Gemini C18 column. The Gemini C18 column is a new generation hybrid silica-based column with an extended pH range capability. The wide pH range (2-12) afforded the examination of basic drugs and acidic drugs in their neutral form. Extrapolated retention factor values, [Formula: see text] , obtained on the above column with the n-octanol-modified mobile phase were very well correlated (1:1 correlation) with literature values of logP (logarithm of the partition coefficient in n-octanol/water) of neutral compounds and neutral drugs (69). In addition, we found good linear correlations between measured [Formula: see text] values and calculated values of the logarithm of the distribution coefficient at pH 7.0 (logD(7.0)) for ionized acidic and basic drugs (r(2)=0.95). The Gemini C18 phase was characterized using the linear solvation energy relationship (LSER) model of Abraham. The LSER system constants for the column were compared to the LSER constants of n-octanol/water extraction system using the Tanaka radar plots. The comparison shows that the two methods are nearly equivalent.

[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

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase.

PubMed

Šatínský, Dalibor; Brabcová, Ivana; Maroušková, Alena; Chocholouš, Petr; Solich, Petr

2013-07-01

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A "green" mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04% (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15 × 4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min(-1). The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid-base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, -0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914-0.99997, n = 6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100 ± 5% for all compounds

Environmentally relevant concentrations of aminopolycarboxylate chelating agents mobilize Cd from humic acid.

PubMed

North, Ashley E; Sarpong-Kumankomah, Sophia; Bellavie, Andrew R; White, Wade M; Gailer, Jürgen

2017-07-01

Although Cd is a pollutant of public health relevance, many dietary sources from which it can be absorbed into human tissues remain unknown. While it is well established that the biogeochemical cycle of Cd involves its complexation with environment-derived ligands (e.g., humic acids, HAs) and anthropogenic ones (e.g., chelating agents, CAs), the interaction of Cd with both of these ligands is less well understood. To gain insight, a HA-Cd complex was injected on a size-exclusion chromatography (SEC) column coupled on-line with a flame atomic absorption spectrometer (FAAS) using 10mmol/L Tris buffer (pH8.0) as the mobile phase. This approach allowed us to observe the intact HA-Cd complex and the retention behavior of Cd as a function of 2-20μmol/L concentrations of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) or methylglycinediacetic acid (MGDA) that were added to the mobile phase. An increase of the retention time of Cd was indicative of a partial or complete abstraction of Cd from HA. Our results revealed that all CAs abstracted Cd from the HA-Cd complex at concentrations of 5μmol/L, while MGDA and DTPA were effective at 2μmol/L. The bioavailability of some of the on-column formed CA-Cd complexes explains the previously reported increased accumulation of Cd in periphyton in the ecosystem downstream of wastewater treatment plants. In addition, our results imply that the use of effluents which contain CAs and Cd for the irrigation of food crops can introduce Cd into the food supply and compromise food safety. Copyright © 2017. Published by Elsevier B.V.

Ionic liquid as a mobile phase additive in high-performance liquid chromatography for the simultaneous determination of eleven fluorescent whitening agents in paper materials.

PubMed

Wang, Qing; Chen, Xianbo; Qiu, Bin; Zhou, Liang; Zhang, Hui; Xie, Juan; Luo, Yan; Wang, Bin

2016-04-01

In the present study, 11 4,4'-diaminostilbene-2,2'-disulfonic acid based fluorescent whitening agents with different numbers of sulfonic acid groups were separated by using an ionic liquid as a mobile phase additive in high-performance liquid chromatography with fluorescence detection. The effects of ionic liquid concentration, pH of mobile phase B, and composition of mobile phase A on the separation of fluorescent whitening agents were systematically investigated. The ionic liquid tetrabutylammonium tetrafluoroborate is superior to tetrabutylammomnium bromide for the separation of the fluorescent whitening agents. The optimal separation conditions were an ionic liquid concentration at 8 mM and the pH of mobile phase B at 8.5 with methanol as mobile phase A. The established method exhibited low limits of detection (0.04-0.07 ng/mL) and wide linearity ranges (0.30-20 ng/mL) with high linear correlation coefficients from 0.9994 to 0.9998. The optimized procedure was applied to analyze target analytes in paper samples with satisfactory results. Eleven target analytes were quantified, and the recoveries of spiked paper samples were in the range of 85-105% with the relative standard deviations from 2.1 to 5.1%. The obtained results indicated that the method was efficient for detection of 11 fluorescent whitening agents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

[Determination of geniposidic acid and chlorogenic acid in male flowers and related products of Eucommia ulmoides by reversed-phase high performance liquid chromatography].

PubMed

Dong, Juane; Ma, Xihan

2007-03-01

A simple and rapid high performance liquid chromatographic method has been developed for the determination of geniposidic acid and chlorogenic acid in the male flowers and related products of Eucommia ulmoides. Two components were separated by a Shim-pack VP-ODS column (150 mm x4.6 mm, 5 [microm) with a mobile phase of methanol-water-acetic acid (24 :75: 1, v/v) at a flow rate of 1 mL/min, column temperature of 30 93 and detection wavelength of 240 nm. Under the chromatographic conditions mentioned above, the method performance, such as the number of theoretical plate, resolution, trailing etc have all reached required level. The linear ranges were 0. 025 - 0. 400 g/L for geniposidic acid and 0. 075 - 1. 200 g/L for chlorogenic acid, with the correlation coefficients of 0. 999 7 and 0. 999 9, respectively. The average recoveries were 100. 2% and 100. 5%, and the relative standard deviations (RSDs) were 1. 47% and 1. 49% respectively. The minimum detection limits were 0. 02 microg/L for geniposidic acid, and 0. 06 microg/L for chlorogenic acid. The method developed has demonstrated the characteristics of simple mobile phase composition, short retention, good resolution, high repeatability and precision. It is suitable for the determination of the two compounds in the male flowers of E. ulmoides and related products.

Simulated molecular-scale interaction of supercritical fluid mobile and stationary phases.

PubMed

Siders, Paul D

2017-12-08

In supercritical fluid chromatography, molecules from the mobile phase adsorb on the stationary phase. Stationary-phase alkylsilane-terminated silica surfaces might adsorb molecules at the silica, among the silanes, on a silane layer, or in pore space between surfaces. Mobile phases of carbon dioxide, pure and modified with methanol, and stationary phases were simulated at the molecular scale. Classical atomistic force fields were used in Gibbs-ensemble hybrid Monte Carlo calculations. Excess adsorption of pure carbon dioxide mobile phase peaked at fluid densities of 0.002-0.003Å -3 . Mobile phase adsorption from 7% methanol in carbon dioxide peaked at lower fluid density. Methanol was preferentially adsorbed from the mixed fluid. Surface silanes prevented direct interaction of fluid-phase molecules with silica. Some adsorbed molecules mixed with tails of bonded silanes; some formed layers above the silanes. Much adsorption occurred by filling the space between surfaces in the stationary-phase model. The distribution in the stationary phase of methanol molecules from a modified fluid phase varied with pressure. Copyright © 2017 Elsevier B.V. All rights reserved.

Octanol/water partitioning simulation by RP-HPLC for structurally diverse acidic drugs: comparison of three columns in the presence and absence of n-octanol as the mobile phase additive.

PubMed

Giaginis, Costas; Theocharis, Stamatios; Tsantili-Kakoulidou, Anna

2013-12-01

The advantageous effect of n-octanol as a mobile phase additive for lipophilicity assessment of structurally diverse acidic drugs both in the neutral and ionized form was explored. Two RP C18 columns, ABZ+ and Aquasil, were used for the determination of logkw indices, and the results were compared with those previously reported on a base-deactivated silica column. At pH 2.5, the use of n-octanol-saturated buffer as the mobile phase aqueous component led to high-quality 1:1 correlation between logkw and logP for the ABZ+ column, while inferior statistics were obtained for Aquasil. At physiological pH, the correlations were significantly improved if strongly ionized acidic drugs were treated separately from weakly ionized ones. In the latter case, 1:1 correlations between logD7.4 and logkw(oct) indices were obtained in the presence of 0.25% n-octanol. Concerning strongly ionized compounds, adequate correlations were established under the same conditions; however, slopes were significantly lower than unity, while large negative intercepts were obtained. According to the absolute difference (diff = logD7.4 – logkw) pattern, base-deactivated silica showed a better performance than ABZ+, however, the latter seems more efficient for the lipophilicity assessment of highly lipophilic acidic compounds. Aquasil may be the column of choice if logD7.4<3 with the limitation, however, that very hydrophilic compounds cannot be measured.

Methylammonium formate as a mobile phase modifier for reversed-phase liquid chromatography

PubMed Central

Grossman, Shau; Danielson, Neil D.

2009-01-01

Although alkylammonium ionic liquids such as ethylammonium nitrate and ethylammonium formate have been used as mobile phase “solvents” for liquid chromatography (LC), we have shown that methylammonium formate (MAF), in part because of its lower viscosity, can be an effective replacement for methanol (MeOH) in reversed-phase LC. Plots of log retention factor versus the fraction of MeOH and MAF in the mobile phase indicate quite comparable solvent strength slope values of 2.50 and 2.05, respectively. Using a polar endcapped C18 column, furazolidone and nitrofurantoin using 20% MAF-80% water could be separated in 22 min but no baseline separation was possible using MeOH as the modifier, even down to 10%. Suppression of silanol peak broadening effects by MAF is important permitting a baseline separation of pyridoxine, thiamine, and nicotinamide using 5% MAF-95% water at 0.7 mL/min. Using 5% MeOH-95% water, severe peak broadening for thiamine is evident. The compatibility of MAF as a mobile phase modifer for LC with mass spectrometry detection of water soluble vitamins is also shown. PMID:18849044

Phased Arrays of Ground and Airborne Mobile Terminals for Satellite Communications

NASA Technical Reports Server (NTRS)

Huang, John

1996-01-01

Phased array antenna is beginning to play an important in the arena of mobile/satellite communications. Two examples of mobile terminal phased arrays will be shown. Their technical background, challenges, and cost drivers will be discussed. A possible solution to combat some of the deficiencies of the conventional phased array by exploiting the phased reflectarray technology will be briefly presented.

Deproteinizing methods evaluated for determination of uric acid in serum by reversed-phase liquid chromatography with ultraviolet detection.

PubMed

Sakuma, R; Nishina, T; Kitamura, M

1987-08-01

We evaluated six deproteinizing methods for determination of uric acid in serum by "high-performance" liquid chromatography with ultraviolet detection: those involving zinc hydroxide, sodium tungstate, trichloroacetic acid, perchloric acid, acetonitrile, and centrifugal ultrafiltration (with Amicon MPS-1 devices). We used a Toyosoda ODS-120A reversed-phase column. The mobile phase was sodium phosphate buffer (40 mmol/L, pH 2.2) containing 20 mL of methanol per liter. Absorbance of the eluate was monitored at 284 nm. The precipitation method with perchloric acid gave high recoveries of uric acid and good precision, and results agreed with those by the uricase-catalase method of Kageyama (Clin Chim Acta 1971;31:421-6).

Utilization of deep eutectic solvents as novel mobile phase additives for improving the separation of bioactive quaternary alkaloids.

PubMed

Tan, Ting; Zhang, Mingliang; Wan, Yiqun; Qiu, Hongdeng

2016-01-01

Deep eutectic solvents (DESs) were used as novel mobile phase additives to improve chromatographic separation of four quaternary alkaloids including coptisine chloride, sanguinarine, berberine chloride and chelerythrine on a C18 column. DESs as a new class of ionic liquids are renewably sourced, environmentally benign, low cost and easy to prepare. Seven DESs were obtained by mixing different hydrogen acceptors and hydrogen-bond donors. The effects of organic solvents, the concentration of DESs, the types of DESs and the pH values of the buffer solution on the separation of the analytes were investigated. The composition of acetonitrile and 1.0% deep eutectic solvents aqueous solution (pH 3.3, adjusted with hydrochloric acid) in a 32:68 (v/v) ratio was used as optimized mobile phase, with which four quaternary alkaloids were well separated. When a small amount of DESs was added in the mobile phase for the separation of alkaloids on the C18 column, noticeable improvements were distinctly observed such as decreasing peak tailing and improving resolution. The separation mechanism mediated by DESs as mobile phase additives can be attributed to combined effect of both hydrogen acceptors and hydrogen-bond donors. For example, choline chloride can effectively cover the residual silanols on silica surface and ethylene glycol can reduce the retention time of analytes. The proposed method has been applied to determine BerbC in Lanqin Chinese herbal oral solution and BerbC tablet. Utilization of DESs in mobile phase can efficiently improve separation and selectivity of analytes from complex samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Geographic Mobility of Postsecondary Occupational Education Graduates. Phase II.

ERIC Educational Resources Information Center

Winter, Gene M.; Fadale, LaVerna M.

This report of the second phase of a study of the geographic mobility patterns of postsecondary occupational education graduates in New York State provides a further examination of reasons for the mobility of program completers, verifies the general magnitude of the identified mobility trends, and examines the occupational status of program…

Mobilization of Cr(VI) from chromite ore processing residue through acid treatment.

PubMed

Tinjum, James M; Benson, Craig H; Edil, Tuncer B

2008-02-25

Batch leaching studies on chromite ore processing residue (COPR) were performed using acids to investigate leaching of hexavalent chromium, Cr(VI), with respect to particle size, reaction time, and type of acid (HNO(3) and H(2)SO(4)). Aqueous Cr(VI) is maximized at approximately 0.04 mol Cr(VI) per kg of dry COPR at pH 7.6-8.1. Cr(VI) mobilized more slowly for larger particles, and the pH increased with time and increased more rapidly for smaller particles, suggesting that rate limitations occur in the solid phase. With H(2)SO(4), the pH stabilized at a higher value (8.8 for H(2)SO(4) vs. 8.0 for HNO(3)) and more rapidly (16 h vs. 30 h), and the differences in pH for different particle sizes were smaller. The acid neutralization capacity (ANC) of COPR is very large (8 mol HNO(3) per kg of dry COPR for a stable eluate pH of 7.5). Changes to the elemental and mineralogical composition and distribution in COPR particles after mixing with acid indicate that Cr(VI)-bearing solids dissolved. However, concentrations of Cr(VI) >2800 mg kg(-1) (>50% of the pre-treatment concentration) were still found after mixing with acid, regardless of the particle size, reaction time, or type of acid used. The residual Cr(VI) appears to be partially associated with poorly-ordered Fe and Al oxyhydroxides that precipitated in the interstitial areas of COPR particles. Remediation strategies that use HNO(3) or H(2)SO(4) to neutralize COPR or to maximize Cr(VI) in solution are likely to require extensive amounts of acid, may not mobilize all of the Cr(VI), and may require extended contact time, even under well-mixed conditions.

Procedure for chromatography involving sample solvent with higher elution strength than the mobile phase.

PubMed

Patil, Nitin S; Mendhe, Rakesh B; Sankar, Ajeet A; Iyer, Harish

2008-01-11

In preparative chromatography, often the solubility of the sample in the mobile phase is limited, making the mobile phase unsuitable as a solvent for preparation of load. Generally, solvents that have high solubility for the sample also have higher elution strengths than the mobile phase. Additionally, at high loading volumes, these strong sample solvents are known to adversely affect the band profiles leading to poor chromatographic performance. Here, we show that controlling the mobile phase strength during loading and post-load elution resulted in improved band profiles when the sample solvent was stronger than the mobile phase. Such an approach improves performance in preparative chromatography by allowing either higher sample loading or higher organic content in mobile phase (without loss of yield). Alternately, the approach can be used for improvement in performance by increase in yield or product purity.

A Laterally-Mobile Mixed Polymer/Polyelectrolyte Brush Undergoes a Macroscopic Phase Separation

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Park, Hae-Woong; Tsouris, Vasilios; Choi, Je; Mustafa, Rafid; Lim, Yunho; Meron, Mati; Lin, Binhua; Won, You-Yeon

2013-03-01

We studied mixed PEO and PDMAEMA brushes. The question we attempted to answer was: When the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Two different model mixed PEO/PDMAEMA brush systems were prepared: a mobile mixed brush by spreading a mixture of two diblock copolymers, PEO-PnBA and PDMAEMA-PnBA, onto the air-water interface, and an inseparable mixed brush using a PEO-PnBA-PDMAEMA triblock copolymer having respective brush molecular weights matched to those of the diblock copolymers. These two systems were investigated by surface pressure-area isotherm, X-ray reflectivity and AFM imaging measurements. The results suggest that the mobile mixed brush undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the inseparable system is only microscopically phase separated under comparable brush density conditions. We also conducted an SCF analysis of the phase behavior of the mixed brush system. This analysis further supported the experimental findings. The macroscopic phase separation observed in the mobile system is in contrast to the microphase separation behavior commonly observed in two-dimensional laterally-mobile small molecule mixtures.

Separation of phenolic acids from sugarcane rind by online solid-phase extraction with high-speed counter-current chromatography.

PubMed

Geng, Ping; Fang, Yingtong; Xie, Ronglong; Hu, Weilun; Xi, Xingjun; Chu, Qiao; Dong, Genlai; Shaheen, Nusrat; Wei, Yun

2017-02-01

Sugarcane rind contains some functional phenolic acids. The separation of these compounds from sugarcane rind is able to realize the integrated utilization of the crop and reduce environment pollution. In this paper, a novel protocol based on interfacing online solid-phase extraction with high-speed counter-current chromatography (HSCCC) was established, aiming at improving and simplifying the process of phenolic acids separation from sugarcane rind. The conditions of online solid-phase extraction with HSCCC involving solvent system, flow rate of mobile phase as well as saturated extent of absorption of solid-phase extraction were optimized to improve extraction efficiency and reduce separation time. The separation of phenolic acids was performed with a two-phase solvent system composed of butanol/acetic acid/water at a volume ratio of 4:1:5, and the developed online solid-phase extraction with HSCCC method was validated and successfully applied for sugarcane rind, and three phenolic acids including 6.73 mg of gallic acid, 10.85 mg of p-coumaric acid, and 2.78 mg of ferulic acid with purities of 60.2, 95.4, and 84%, respectively, were obtained from 150 mg sugarcane rind crude extracts. In addition, the three different elution methods of phenolic acids purification including HSCCC, elution-extrusion counter-current chromatography and back-extrusion counter-current chromatography were compared. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast non-aqueous reversed-phase liquid chromatography separation of triacylglycerol regioisomers with isocratic mobile phase. Application to different oils and fats.

PubMed

Tamba Sompila, Arnaud W G; Héron, Sylvie; Hmida, Dorra; Tchapla, Alain

2017-01-15

The distribution of fatty acid species at the sn-1/3 position or the sn-2 position of triacylglycerols (TAGs) in natural fats and oils affects their physical and nutritional properties. In fats and oils, determining the presence of one or two regioisomers and the identification of structure, where they do have one, as well as their separation, became a problem of fundamental importance to solve. A variety of instrumental technics has been proposed, such as MS, chromatography-MS or pure chromatography. A number of studies deal with the optimization of the separation, but very often, they are expensive in time. In the present study, in order to decrease the analysis time while maintaining good chromatographic separation, we tested different monomeric and polymeric stationary phases and different chromatographic conditions (mobile phase composition and analysis temperature) using Non-Aqueous Reversed Phase Liquid Chromatography (NARP-LC). It was demonstrated that mixed polymeric stationary bonded silica with accessible terminal hydroxyl groups leads to very good separation for the pairs of TAGs regioisomers constituted by two saturated and one unsaturated fatty acid (with double bond number: from 1 to 6). A Nucleodur C18 ISIS percolated by isocratic mobile phase (acetonitrile/2-propanol) at 18°C leads to their separations in less than 15min. The difference of retention times between two regioisomers XYX and XXY are large enough to confirm, as application, the presence of POP, SOP, SOS and PLP and no PPO, SPO, SSO and PPL in Theobroma cacao butter. In the same way, this study respectively shows the presence of SOS, SOP and no SSO, PSO in Butyrospermum parkii butter, POP, SOP, SOS and no PPO, PSO and SSO in Carapa oil and finally POP and no PPO in Pistacia Lentiscus oil. Copyright © 2016 Elsevier B.V. All rights reserved.

Use of microfocused X-ray techniques to investigate the mobilization of arsenic by oxalic acid

NASA Astrophysics Data System (ADS)

Wovkulich, Karen; Mailloux, Brian J.; Bostick, Benjamin C.; Dong, Hailiang; Bishop, Michael E.; Chillrud, Steven N.

2012-08-01

Improved linkages between aqueous phase transport and solid-phase reactions are needed to better predict and model transport of contaminants through the subsurface. Here we develop and apply a new method for measuring As mobilization in situ within soil columns that utilizes synchrotron-based X-ray fluorescence. By performing these measurements in situ during column transport experiments, we simultaneously monitor grain-scale solid phase reactions and column-scale transport. Arsenic may be effectively mobilized by oxalic acid but the geochemical and mineralogical factors that influence the rate and extent of mobilization are not well understood. Column experiments (˜4 cm long × 0.635 cm ID) using As contaminated sediments from the Vineland Chemical Company Superfund site were performed on the laboratory bench as well as in the synchrotron beamline. Microfocused synchrotron X-ray fluorescence (μSXRF) maps for As and Fe were collected at the same location in the columns (<1 mm2) before and during treatment with 10 mM oxalic acid. The fraction of As and Fe removed by oxalic acid treatment was calculated from the change in flux-normalized counts for each pixel in the map images, and these data were used to calculate kinetic parameters over the studied area. Between 79% and 83% of the As was removed from the sediments by the oxalic acid treatment based on μSXRF data; these removal percentages agreed well with laboratory data based on column effluent (88-95%). Considerably less Fe was removed by oxalic acid treatment, 14-25% based on μSXRF counts, which is somewhat higher than the 7-9% calculated from laboratory column effluent concentrations. Microfocused X-ray absorption near edge spectroscopy (μXANES) on a subset of points indicates most of the Fe was oxidized and present as a mixture of goethite, hematite, and ferrihydrite on sand grain coatings. Treatment with oxalic acid led to subtle shifts in Fe (III) species following oxalic acid treatment, either removing

Use of Microfocused X-ray Techniques to Investigate the Mobilization of As by Oxalic Acid

PubMed Central

Wovkulich, Karen; Mailloux, Brian J.; Bostick, Benjamin C.; Dong, Hailiang; Bishop, Michael E.; Chillrud, Steven N.

2012-01-01

Improved linkages between aqueous phase transport and solid-phase reactions are needed to better predict and model transport of contaminants through the subsurface. Here we develop and apply a new method for measuring As mobilization in situ within soil columns that utilizes synchrotron-based X-ray fluorescence. By performing these measurements in situ during column transport experiments, we simultaneously monitor grain-scale solid phase reactions and column-scale transport. Arsenic may be effectively mobilized by oxalic acid but the geochemical and mineralogical factors that influence the rate and extent of mobilization are not well understood. Column experiments (~4 cm long × 0.635 cm ID) using As contaminated sediments from the Vineland Chemical Company Superfund site were performed on the laboratory bench as well as in the synchrotron beamline. Microfocused synchrotron X-ray fluorescence (μSXRF) maps for As and Fe were collected at the same location in the columns (<1 mm2) before and during treatment with 10 mM oxalic acid. The fraction of As and Fe removed by oxalic acid treatment was calculated from the change in flux-normalized counts for each pixel in the map images, and these data were used to calculate kinetic parameters over the studied area. Between 79% and 83% of the As was removed from the sediments by the oxalic acid treatment based on μSXRF data; these removal percentages agreed well with laboratory data based on column effluent (88–95%). Considerably less Fe was removed by oxalic acid treatment, 14–25% based on μSXRF counts, which is somewhat higher than the 7–9% calculated from laboratory column effluent concentrations. Microfocused X-ray absorption near edge spectroscopy (μXANES) on a subset of points indicates most of the Fe was oxidized and present as a mixture of goethite, hematite, and ferrihydrite on sand grain coatings. Treatment with oxalic acid led to subtle shifts in Fe (III) species following oxalic acid treatment, either

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

NASA Astrophysics Data System (ADS)

Shi, Wei; Han, Shijiao; Huang, Wei; Yu, Junsheng

2015-01-01

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm2/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role in enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.

Micellar versus hydro-organic mobile phases for retention-hydrophobicity relationship studies with ionizable diuretics and an anionic surfactant.

PubMed

Ruiz-Angel, M J; Carda-Broch, S; García-Alvarez-Coque, M C; Berthod, A

2004-03-19

Logarithm of retention factors (log k) of a group of 14 ionizable diuretics were correlated with the molecular (log P o/w) and apparent (log P(app)) octanol-water partition coefficients. The compounds were chromatographed using aqueous-organic (reversed-phase liquid chromatography, RPLC) and micellar-organic mobile phases (micellar liquid chromatography, MLC) with the anionic surfactant sodium dodecyl sulfate (SDS), in the pH range 3-7, and a conventional octadecylsilane column. Acetonitrile was used as the organic modifier in both modes. The quality of the correlations obtained for log P(app) at varying ionization degree confirms that this correction is required in the aqueous-organic mixtures. The correlation is less improved with SDS micellar media because the acid-base equilibriums are shifted towards higher pH values for acidic compounds. In micellar chromatography, an electrostatic interaction with charged solutes is added to hydrophobic forces; consequently, different correlations should be established for neutral and acidic compounds, and for basic compounds. Correlations between log k and the isocratic descriptors log k(w), log k(wm) (extrapolated retention to pure water in the aqueous-organic and micellar-organic systems, respectively), and psi0 (extrapolated mobile phase composition giving a k = 1 retention factor or twice the dead time), and between these descriptors and log P(app) were also satisfactory, although poorer than those between log k and log P(app) due to the extrapolation. The study shows that, in the particular case of the ionizable diuretics studied, classical RPLC gives better results than MLC with SDS in the retention hydrophobicity correlations.

Mobile, stationary and mixed phase tracers: consequences to sea ice biogeochemistry

NASA Astrophysics Data System (ADS)

Jeffery, N.; Elliott, S.; Hunke, E. C.; Deal, C.; Jin, M.

2016-02-01

Models of brine motion in sea ice have offered mechanisms for transporting biogeochemical compounds vertically within the ice and between the ice-ocean interface. In these models, sea ice microstructure and/or gross physical properties determine the resupply of nitrate, for example, to sympagic algae and that resupply, in large part, constrains sea ice primary production. The assumption of brine transport models is that the transported matter exists in a purely mobile phase within the ice brine channels. As a result, non-reacting, mobile phase tracers evolve like salinity in dynamic sea ice. Field and laboratory observations indicate that this is a good approximation for the primary algal macronutrients - nitrate, silicate and phosphate, but clear deviations are evident for ammonium, micronutrients such as iron, humic substances, algal bi-products such as gels and extracellular polysaccharides, and the algae themselves. This wide range of biogeochemical matter resists brine motion and is present in both the mobile and stationary phases, i.e. these tracers are "mixed" with respect to their transport phases. Although the precise mechanism for this resistance may be due to attachment by frustules, "stickiness" of the material surface, adsorption, or, in the case of microorganisms, active motility, a key common element in all cases is the presence of the ice matrix. In this presentation we investigate the consequences of mixed phase tracers in sea ice on algal concentrations, vertical distributions, and the potential accumulation of biogeochemical matter within the ice. We assume that sea ice growth promotes retention to the stationary phase, while melt and the disintegration of the ice matrix promotes release into the mobile phase. By varying the retention and release timescales of this formulation, we retrieve the purely mobile and maximal accumulation limits.

Mobilization of soil-borne arsenic by three common organic acids: Dosage and time effects.

PubMed

Onireti, Olaronke O; Lin, Chuxia

2016-03-01

A batch experiment was conducted to investigate the mobilization of soil-borne arsenic by three common low-molecular-weight organic acids with a focus on dosage and time effects. The results show that oxalic acid behaved differently from citric acid and malic acid in terms of mobilizing As that was bound to iron compounds. At an equivalent molar concentration, reactions between oxalic acid and soil-borne Fe were kinetically more favourable, as compared to those between either citric acid or malic acid and the soil-borne Fe. It was found that reductive dissolution of soil-borne Fe played a more important role in liberating As, as compared to non-reductive reactions. Prior to the 7th day of the experiment, As mobility increased with increasing dose of oxalic acid while there was no significant difference (P > 0.05) in mobilized As among the treatments with different doses of citric acid or malic acid. The dosage effect on soil-borne As mobilization in the citric acid and malic acid treatments became clear only after the 7th day of the experiment. Soluble Ca present in the soils could cause re-immobilization of As by competing with solution-borne Fe for available organic ligands to form practically insoluble organic compounds of calcium (i.e. calcium oxalate). This resulted in transformation of highly soluble organic complexes of iron (i.e. iron oxalate complexes) into slightly soluble organic compounds of iron (i.e. iron oxalate) or free ferric ion, which then reacted with the solution-borne arsenate ions to form practically insoluble iron arsenates in the latter part of the experiment. Copyright © 2015 Elsevier Ltd. All rights reserved.

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

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

Shi, Wei; Han, Shijiao; Huang, Wei

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm{sup 2}/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role inmore » enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.« less

Effect of Foam on Liquid Phase Mobility in Porous Media

NASA Astrophysics Data System (ADS)

Eftekhari, A. A.; Farajzadeh, R.

2017-03-01

We investigate the validity of the assumption that foam in porous media reduces the mobility of gas phase only and does not impact the liquid-phase mobility. The foam is generated by simultaneous injection of nitrogen gas and a surfactant solution into sandstone cores and its strength is varied by changing surfactant type and concentration. We find, indeed, that the effect of foam on liquid-phase mobility is not pronounced and can be ignored. Our new experimental results and analyses resolve apparent discrepancies in the literature. Previously, some researchers erroneously applied relative permeability relationships measured at small to moderate capillary numbers to foam floods at large capillary number. Our results indicate that the water relative permeability in the absence of surfactant should be measured with the capillary pressure ranging up to values reached during the foam floods. This requires conducting a steady-state gas/water core flood with capillary numbers similar to that of foam floods or measuring the water relative-permeability curve using a centrifuge.

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

Electrophoretic Mobility Shift Assay (EMSA) for Detecting Protein-Nucleic Acid Interactions

PubMed Central

Hellman, Lance M.; Fried, Michael G.

2009-01-01

The gel electrophoresis mobility shift assay (EMSA) is used to detect protein complexes with nucleic acids. It is the core technology underlying a wide range of qualitative and quantitative analyses for the characterization of interacting systems. In the classical assay, solutions of protein and nucleic acid are combined and the resulting mixtures are subjected to electrophoresis under native conditions through polyacrylamide or agarose gel. After electrophoresis, the distribution of species containing nucleic acid is determined, usually by autoradiography of 32P-labeled nucleic acid. In general, protein-nucleic acid complexes migrate more slowly than the corresponding free nucleic acid. In this article, we identify the most important factors that determine the stabilities and electrophoretic mobilities of complexes under assay conditions. A representative protocol is provided and commonly used variants are discussed. Expected outcomes are briefly described. References to extensions of the method and a troubleshooting guide are provided. PMID:17703195

High-performance liquid chromatographic enantioseparation of 2-aminomono- and dihydroxycyclopentanecarboxylic and 2-aminodihydroxycyclohexanecarboxylic acids on macrocyclic glycopeptide-based phases.

PubMed

Berkecz, Róbert; Ilisz, István; Benedek, Gabriella; Fülöp, Ferenc; Armstrong, Daniel W; Péter, Antal

2009-02-06

The direct separation of the enantiomers of four 2-aminomono- or dihydroxycyclopentanecarboxylic acids and four 2-aminodihydroxycyclohexanecarboxylic acids was performed on chiral stationary phases containing macrocyclic glycopeptide antibiotics such as teicoplanin (Astec Chirobiotic T and T2), teicoplanin aglycone (Chirobiotic TAG) or ristocetin A (Chirobiotic R) as chiral selectors. The effects of the nature of organic modifiers, the pH, the mobile phase composition and the structures of the analytes on the separation were investigated. Chirobiotic TAG, and in some cases Chirobiotic T, proved to be the most useful of these columns. The elution sequence was determined in most cases.

Extraterrestrial material analysis: loss of amino acids during liquid-phase acid hydrolysis

NASA Astrophysics Data System (ADS)

Buch, Arnaud; Brault, Amaury; Szopa, Cyril; Freissinet, Caroline

2015-04-01

Searching for building blocks of life in extraterrestrial material is a way to learn more about how life could have appeared on Earth. With this aim, liquid-phase acid hydrolysis has been used, since at least 1970 , in order to extract amino acids and other organic molecules from extraterrestrial materials (e.g. meteorites, lunar fines) or Earth analogues (e.g. Atacama desert soil). This procedure involves drastic conditions such as heating samples in 6N HCl for 24 h, either under inert atmosphere/vacuum, or air. Analysis of the hydrolyzed part of the sample should give its total (free plus bound) amino acid content. The present work deals with the influence of the 6N HCl hydrolysis on amino acid degradation. Our experiments have been performed on a standard solution of 17 amino acids. After liquid-phase acid hydrolysis (6N HCl) under argon atmosphere (24 h at 100°C), the liquid phase was evaporated and the dry residue was derivatized with N-Methyl-N-(t-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF), followed by gas chromatography-mass spectrometry analysis. After comparison with derivatized amino acids from the standard solution, a significant reduction of the chromatographic peak areas was observed for most of the amino acids after liquid-phase acid hydrolysis. Furthermore, the same loss pattern was observed when the amino acids were exposed to cold 6N HCl for a short amount of time. The least affected amino acid, i.e. glycine, was found to be 73,93% percent less abundant compared to the non-hydrolyzed standard, while the most affected, i.e. histidine, was not found in the chromatograms after hydrolysis. Our experiments thereby indicate that liquid-phase acid hydrolysis, even under inert atmosphere, leads to a partial or total loss of all of the 17 amino acids present in the standard solution, and that a quick cold contact with 6N HCl is sufficient to lead to a loss of amino acids. Therefore, in the literature, the reported increase

Use of low volatility mobile phases in electroosmotic thin-layer chromatography.

PubMed

Berezkin, V G; Balushkin, A O; Tyaglov, B V; Litvin, E F

2005-08-19

A variant of electroosmotic thin-layer chromatography is suggested with the use of low volatility compounds as mobile phases aimed at drastically decreasing the evaporation of the mobile phase and improving the reproducibility of the method. The linear movement velocity of zones of separated compounds is experimentally shown to increase 2-12-fold in electroosmotic chromatography (compared to similar values in traditional TLC). The separation efficiency is also considerably increased.

Racemic synthesis and solid phase peptide synthesis application of the chimeric valine/leucine derivative 2-amino-3,3,4-trimethyl-pentanoic acid.

PubMed

Pelà, M; Del Zoppo, L; Allegri, L; Marzola, E; Ruzza, C; Calo, G; Perissutti, E; Frecentese, F; Salvadori, S; Guerrini, R

2014-07-01

The synthesis of non natural amino acid 2-amino-3,3,4-trimethyl-pentanoic acid (Ipv) ready for solid phase peptide synthesis has been developed. Copper (I) chloride Michael addition, followed by a Curtius rearrangement are the key steps for the lpv synthesis. The racemic valine/leucine chimeric amino acid was then successfully inserted in position 5 of neuropeptide S (NPS) and the diastereomeric mixture separated by reverse phase HPLC. The two diastereomeric NPS derivatives were tested for intracellular calcium mobilization using HEK293 cells stably expressing the mouse NPS receptor where they behaved as partial agonist and pure antagonist.

Acid rain effects on aluminum mobilization clarified by inclusion of strong organic acids.

PubMed

Lawrence, G B; Sutherland, J W; Boylen, C W; Nierzwicki-Bauer, S W; Momen, B; Baldigo, B P; Simonin, H A

2007-01-01

Assessments of acidic deposition effects on aquatic ecosystems have often been hindered by complications from naturally occurring organic acidity. Measurements of pH and ANCG, the most commonly used indicators of chemical effects, can be substantially influenced by the presence of organic acids. Relationships between pH and inorganic Al, which is toxic to many forms of aquatic biota, are also altered by organic acids. However, when inorganic Al concentrations are plotted against ANC (the sum of Ca2+, Mg2+, Na+, and K+, minus S042-, N03-, and Cl-), a distinct threshold for Al mobilization becomes apparent. If the concentration of strong organic anions is included as a negative component of ANC, the threshold occurs at an ANC value of approximately zero, the value expected from theoretical charge balance constraints. This adjusted ANC is termed the base-cation surplus. The threshold relationship between the base-cation surplus and Al was shown with data from approximately 200 streams in the Adirondack region of New York, during periods with low and high dissolved organic carbon concentrations, and for an additional stream from the Catskill region of New York. These results indicate that (1) strong organic anions can contribute to the mobilization of inorganic Al in combination with SO42- and N03-, and (2) the presence of inorganic Al in surface waters is an unambiguous indication of acidic deposition effects.

Effect of Foam on Liquid Phase Mobility in Porous Media

PubMed Central

Eftekhari, A. A.; Farajzadeh, R.

2017-01-01

We investigate the validity of the assumption that foam in porous media reduces the mobility of gas phase only and does not impact the liquid-phase mobility. The foam is generated by simultaneous injection of nitrogen gas and a surfactant solution into sandstone cores and its strength is varied by changing surfactant type and concentration. We find, indeed, that the effect of foam on liquid-phase mobility is not pronounced and can be ignored. Our new experimental results and analyses resolve apparent discrepancies in the literature. Previously, some researchers erroneously applied relative permeability relationships measured at small to moderate capillary numbers to foam floods at large capillary number. Our results indicate that the water relative permeability in the absence of surfactant should be measured with the capillary pressure ranging up to values reached during the foam floods. This requires conducting a steady-state gas/water core flood with capillary numbers similar to that of foam floods or measuring the water relative-permeability curve using a centrifuge. PMID:28262795

Features of the adsoprtion of naproxen on the chiral stationary phase (S,S)-Whelk-O1 under reversed-phase conditions

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

Asnin, Leonid; Gritti, Fabrice; Kaczmarski, Krzysztof

Using elution chromatography, we studied the adsorption mechanism of the Naproxen enantiomers on the chiral stationary phase (S,S)-Whelk-O1, from buffered methanol-water solutions. We propose an adsorption mechanism that assumes monolayer adsorption of the more retained enantiomer and the associative adsorption of the less retained one. The effects of the mobile phase composition on the adsorption of Naproxen are discussed. The combination of an elevated column temperature and of the use of an acidic mobile phase led to the degradation of the column and caused a major loss of its separation ability. The use of a moderately acidic mobile phase atmore » temperature slightly above ambient did not produce rapid severe damages but, nevertheless, hampered the experiments and caused a slow gradual deterioration of the column.« less

High-performance liquid chromatographic enantioseparation of monoterpene-based 2-amino carboxylic acids on macrocyclic glycopeptide-based phases.

PubMed

Sipos, László; Ilisz, István; Pataj, Zoltán; Szakonyi, Zsolt; Fülöp, Ferenc; Armstrong, Daniel W; Péter, Antal

2010-10-29

The enantiomers of five monoterpene-based 2-amino carboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics such as teicoplanin (Astec Chirobiotic T and T2) and teicoplanin aglycone (Chirobiotic TAG) as chiral selectors. The effects of pH, the mobile phase composition, the structure of the analyte and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 10-40°C to study the effects of temperature and thermodynamic parameters on separations. Apparent thermodynamic parameters and T(iso) values were calculated from plots of ln k or ln α versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantioseparations were in most cases enthalpy driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2010 Elsevier B.V. All rights reserved.

Acid rain effects on aluminum mobilization clarified by inclusion of strong organic acids

USGS Publications Warehouse

Lawrence, G.B.; Sutherland, J.W.; Boylen, C.W.; Nierzwicki-Bauer, S. W.; Momen, B.; Baldigo, Barry P.; Simonin, H.A.

2007-01-01

Assessments of acidic deposition effects on aquatic ecosystems have often been hindered by complications from naturally occurring organic acidity. Measurements of pH and ANCG, the most commonly used indicators of chemical effects, can be substantially influenced by the presence of organic acids. Relationships between pH and inorganic Al, which is toxic to many forms of aquatic biota, are also altered by organic acids. However, when inorganic Al concentrations are plotted against ANC (the sum of Ca2+, Mg 2+, Na+, and K+, minus SO42-, NO3-, and Cl-), a distinct threshold for Al mobilization becomes apparent. If the concentration of strong organic anions is included as a negative component of ANC, the threshold occurs at an ANC value of approximately zero, the value expected from theoretical charge balance constraints. This adjusted ANC is termed the base-cation surplus. The threshold relationship between the base-cation surplus and Al was shown with data from approximately 200 streams in the Adirondack region of New York, during periods with low and high dissolved organic carbon concentrations, and for an additional stream from the Catskill region of New York. These results indicate that (1) strong organic anions can contribute to the mobilization of inorganic Al in combination with SO42- and NO 3-, and (2) the presence of inorganic Al in surface waters is an unambiguous indication of acidic deposition effects. ?? 2007 American Chemical Society.

The influence of addition of ion-pairing acid and organic modifier of the mobile phase on retention and migration of peptides in pressurized planar electrochromatography system with octadecyl silica-based adsorbent.

PubMed

Gwarda, Radosław Ł; Dzido, Tadeusz H

2018-07-13

In our previous papers we have investigated the influence of the mobile phase composition on mechanism of retention, selectivity and efficiency of peptide separation in various high-performance thin-layer chromatography (HPTLC) systems with commercially available silica-based adsorbents. We have also investigated the influence of pH of the mobile phase buffer on migration and separation of peptides in pressurized planar electrochromatography (PPEC). Here we investigate the influence of concentration of ion-pairing additive, and concentration and type of organic modifier of the mobile phase on migration of peptides in PPEC system with octadecyl silica-based adsorbent, and with the same set of the solutes as before. We compare our current results with the results obtained before for similar HPTLC and PPEC systems, and discuss the influence of particular variables on retention, electrophoretic mobility of solutes and electroosmotic flow of the mobile phase. We show, that the final selectivity of peptide separation results from co-influence of all the three factors mentioned. Concentration of organic modifier of the mobile phase, as well as concentration of ion-pairing additive, affect the retention, the electrophoretic mobility, and the electroosmotic flow simultaneously. This makes independent optimization of these factors rather difficult. Anyway PPEC offers much faster separation of peptides with quite different selectivity, in comparison to HPTLC, with similar adsorbents and similar mobile phase composition. However, we also present and discuss the issue of extensive tailing of peptide zones in the PPEC in comparison to similar HPTLC systems. Copyright © 2018 Elsevier B.V. All rights reserved.

30 CFR 77.900 - Low- and medium-voltage circuits serving portable or mobile three-phase alternating current...

Code of Federal Regulations, 2011 CFR

2011-07-01

... portable or mobile three-phase alternating current equipment; circuit breakers. 77.900 Section 77.900... mobile three-phase alternating current equipment; circuit breakers. Low- and medium-voltage circuits supplying power to portable or mobile three-phase alternating current equipment shall be protected by...

Effect of the ionic strength of a mobile phase on the chromatographic retention and thermodynamic characteristics of the adsorption of enantiomers of α-phenylcarboxylic acids on a chiral adsorbent with grafted antibiotic eremomycin

NASA Astrophysics Data System (ADS)

Reshetova, E. N.

2017-01-01

The effect the ionic strength of an aqueous ethanol mobile phase containing buffer salt has the on retention and thermodynamics of adsorption of optical isomers of some α-phenylcarboxylic acids on chiral adsorbent Nautilus-E with grafted antibiotic eremomycin is investigated. It is shown that ion exchange processes participate in the adsorption of enantiomers of α-phenylcarboxylic acids. It is established that electrostatic interactions contribute to the retention of enantiomers of α-phenylcarboxylic acids and affect selectivity only slightly. The dependences of retention characteristics, selectivity, and thermodynamic parameters on the concentration of the buffer salt in the eluent are determined. A statistical analysis of enthalpy-entropy compensation is performed, and the compensation effect is shown to be true. It is found that the points corresponding to the investigated adsorbates are distributed over the compensation dependence according to the spatial structural characteristics of molecules.

78 FR 45071 - Annual Report for Mobility Fund Phase I Support and Record Retention

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-26

... for Mobility Fund Phase I Support and Record Retention AGENCY: Federal Communications Commission... information collection associated with the Commission's Annual Report for Mobility Fund Phase I Support and... or sponsor a collection of information unless it displays a current, valid OMB Control Number. No...

Linking molecular models with ion mobility experiments. Illustration with a rigid nucleic acid structure

PubMed Central

D'Atri, Valentina; Porrini, Massimiliano; Rosu, Frédéric; Gabelica, Valérie

2015-01-01

Ion mobility spectrometry experiments allow the mass spectrometrist to determine an ion's rotationally averaged collision cross section ΩEXP. Molecular modelling is used to visualize what ion three-dimensional structure(s) is(are) compatible with the experiment. The collision cross sections of candidate molecular models have to be calculated, and the resulting ΩCALC are compared with the experimental data. Researchers who want to apply this strategy to a new type of molecule face many questions: (1) What experimental error is associated with ΩEXP determination, and how to estimate it (in particular when using a calibration for traveling wave ion guides)? (2) How to generate plausible 3D models in the gas phase? (3) Different collision cross section calculation models exist, which have been developed for other analytes than mine. Which one(s) can I apply to my systems? To apply ion mobility spectrometry to nucleic acid structural characterization, we explored each of these questions using a rigid structure which we know is preserved in the gas phase: the tetramolecular G-quadruplex [dTGGGGT]4, and we will present these detailed investigation in this tutorial. © 2015 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26259654

Rapid Determination of Bile Acids in Bile from Various Mammals by Reversed-Phase Ultra-Fast Liquid Chromatography.

PubMed

Si, Gu Leng Ri; Yao, Peng; Shi, Luwen

2015-08-01

A valid and efficient reversed-phase ultra-fast liquid chromatography method was developed for the simultaneous determination of 13 bile acids in the bile of three mammal species, including rat, pig and human gallstone patients. Chromatographic separation was performed with a Shim-pack XR-ODS column, and the mobile phase consisted of acetonitrile and potassium phosphate buffer (pH 2.6) at a flow rate of 0.5 mL min(-1). The linear detection range of most bile acids ranged from 2 to 600 ng µL(-1) with a good correlation coefficient (>0.9995). The precision of each bile acid was <1.8% for intraday and <4.8% for interday. All bile acids were separated in 15 min with satisfactory resolution, and the total analysis time was 18 min, including equilibration. The method was successfully applied in rapid screening of bile samples from the three mammals. Significant metabolic frameworks of bile acids among various species were observed, whereas considerable quantitative variations in both inter- and intraspecies were also observed, especially for gallstone patients. Our results suggest that detecting the change of bile acid profiles could be applied for the diagnosis of gallstone disease. © Crown copyright 2014.

High-performance liquid chromatographic enantioseparation of unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids on macrocyclic glycopeptide-based chiral stationary phases.

PubMed

Sipos, László; Ilisz, István; Nonn, Melinda; Fülöp, Ferenc; Pataj, Zoltán; Armstrong, Daniel W; Péter, Antal

2012-04-06

The enantiomers of four unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics teicoplanin (Astec Chirobiotic T and T2), teicoplanin aglycone (Chirobiotic TAG), vancomycin (Chirobiotic V) and vancomycin aglycone (Chirobiotic VAG) as chiral selectors. The effects of the mobile phase composition, the structure of the analytes and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 5-45 °C to study the effects of temperature, and thermodynamic parameters were calculated from plots of lnk or lnα versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantiomeric separations were in most cases enthalpy-driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2011 Elsevier B.V. All rights reserved.

Cobalt ferrite nanoparticles with improved aqueous colloidal stability and electrophoretic mobility

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

Munjal, Sandeep, E-mail: drsandeepmunjal@gmail.com; Khare, Neeraj, E-mail: nkhare@physics.iitd.ernet.in

We have synthesized CoFe{sub 2}O{sub 4} (CFO) nanoparticles of size ∼ 12.2 nm by hydrothermal synthesis method. To control the size of these CFO nanoparticles, oleic acid was used as a surfactant. The inverse spinel phase of the synthesized nanoparticles was confirmed by X-ray diffraction method. As synthesized oleic acid coated CFO (OA@CFO) nanoparticles has very less electrophoretic mobility in the water and are not water dispersible. These OA@CFO nanoparticles were successfully turned into water soluble phase with a better colloidal aqueous stability, through a chemical treatment using citric acid. The modified citric acid coated CFO (CA@CFO) nanoparticles were dispersible inmore » water and form a stable aqueous solution with high electrophoretic mobility.« less

Charge carrier mobility in a two-phase disordered organic system in the low-carrier concentration regime

NASA Astrophysics Data System (ADS)

Woellner, Cristiano F.; Li, Zi; Freire, José A.; Lu, Gang; Nguyen, Thuc-Quyen

2013-09-01

In this paper we use a three-dimensional Pauli master equation to investigate the charge carrier mobility of a two-phase system which can mimic donor-acceptor and amorphous-crystalline bulk heterojunctions. By taking the energetic disorder of each phase, their energy offset, and domain morphology into consideration, we show that the carrier mobility can have a completely different behavior when compared to a one-phase system. When the energy offset is equal to zero, the mobility is controlled by the more disordered phase. When the energy offset is nonzero, we show that the mobility electric field dependence switches from negative to positive at a threshold field proportional to the energy offset. Additionally, the influence of morphology, through the domain size and volume ratio parameters, on the transport is investigated and an approximate analytical expression for the zero field mobility is provided.

Safety and mobility impacts of winter weather : phase I.

DOT National Transportation Integrated Search

2011-08-01

Highway agencies spend millions of dollars to ensure safe and efficient winter travel. However, the effectiveness of winter weather maintenance practices on safety and mobility are somewhat difficult to quantify. : Phase I of this project investigate...

Selectivity in reversed-phase separations: general influence of solvent type and mobile phase pH.

PubMed

Neue, Uwe D; Méndez, Alberto

2007-05-01

The influence of the mobile phase on retention is studied in this paper for a group of over 70 compounds with a broad range of multiple functional groups. We varied the pH of the mobile phase (pH 3, 7, and 10) and the organic modifier (methanol, acetonitrile (ACN), and tetrahydrofuran (THF)), using 15 different stationary phases. In this paper, we describe the overall retention and selectivity changes observed with these variables. We focus on the primary effects of solvent choice and pH. For example, transfer rules for solvent composition resulting in equivalent retention depend on the packing as well as on the type of analyte. Based on the retention patterns, one can calculate selectivity difference values for different variables. The selectivity difference is a measure of the importance of the different variables involved in method development. Selectivity changes specific to the type of analyte are described. The largest selectivity differences are obtained with pH changes.

Project inspection using mobile technology - phase II : assessing the impacts of mobile technology on project inspection.

DOT National Transportation Integrated Search

2015-01-01

As mobile technology becomes widely available and affordable, transportation agencies can use this : technology to streamline operations involved within project inspection. This research, conducted in two : phases, identified opportunities for proces...

Spontaneous Growth and Mobilization of a Gas Phase in the Presence of Dense Non- Aqueous Phase Liquid (DNAPL)

NASA Astrophysics Data System (ADS)

Roy, J. W.; Smith, J. E.

2006-12-01

A number of mechanisms can lead to the presence of disconnected bubbles or ganglia of gas phase in groundwater. When associated with or near a DNAPL phase, the disconnected gas phase experiences mass transfer of dissolved gases including the volatile components of the DNAPL. The properties of the gas phase interface, such as interfacial tension and contact angle, can also be affected. This work addresses the behavior of spontaneous continual growth of initially trapped seed gas bubbles within DNAPL source zones. Three different experiments were performed in a 2-dimensional transparent flow cell 15 cm by 20 cm by 1.5 cm. In each case, a DNAPL pool was created within larger glass beads over smaller glass beads that served as a capillary barrier. The DNAPL consisted of either a 1:2 (v/v) tetrachloroethene (PCE) to benzene mixture, single component PCE, or single component TCE. The experiments effectively demonstrate spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone. A cycle of gas phase growth and mobilization was facilitated by the presence of secondary seed bubbles left behind due to snap-off during vertical bubble (ganglion) mobilization. This gas phase growth process was relatively slow but continuous and could be expected to continue until the NAPL is completely dissolved. Some implications of the demonstrated behavior for water flow and mass transfer within and near the DNAPL source zone are highlighted.

Reversed phase liquid chromatography with UV absorbance and flame ionization detection using a water mobile phase and a cyano propyl stationary phase Analysis of alcohols and chlorinated hydrocarbons.

PubMed

Quigley, W W; Ecker, S T; Vahey, P G; Synovec, R E

1999-10-01

The development of liquid chromatography with a commercially available cyano propyl stationary phase and a 100% water mobile phase is reported. Separations were performed at ambient temperature, simplifying instrumental requirements. Excellent separation efficiency using a water mobile phase was achieved, for example N=18 800, or 75 200 m(-1), was obtained for resorcinol, at a retention factor of k'=4.88 (retention time of 9.55 min at 1 ml min(-1) for a 25 cmx4.6 mm i.d. column, packed with 5 mum diameter particles with the cyano propyl stationary phase). A separation via reversed phase liquid chromatography (RP-LC) with a 100% water mobile phase of six phenols and related compounds was compared to a separation of the same compounds by traditional RP-LC, using octadecylsilane (ODS), i.e. C18, bound to silica and an aqueous mobile phase modified with acetonitrile. Nearly identical analysis time was achieved for the separation of six phenols and related compounds using the cyano propyl stationary phase with a 100% water mobile phase, as compared to traditional RP-LC requiring a relatively large fraction of organic solvent modifier in the mobile phase (25% acetonitrile:75% water). Additional understanding of the retention mechanism with the 100% water mobile phase was obtained by relating measured retention factors of aliphatic alcohols, phenols and related compounds, and chlorinated hydrocarbons to their octanol:water partition coefficients. The retention mechanism is found to be consistent with a RP-LC mechanism coupled with an additional retention effect due to residual hydroxyl groups on the cyano propyl stationary phase. Advantages due to a 100% water mobile phase for the chemical analysis of alcohol mixtures and chlorinated hydrocarbons are reported. By placing an absorbance detector in-series and preceding a novel drop interface to a flame ionization detector (FID), selective detection of a separated mixture of phenols and related compounds and aliphatic

Chromatographic retention prediction and octanol-water partition coefficient determination of monobasic weak acidic compounds in ion-suppression reversed-phase liquid chromatography using acids as ion-suppressors.

PubMed

Ming, Xin; Han, Shu-ying; Qi, Zheng-chun; Sheng, Dong; Lian, Hong-zhen

2009-08-15

Although simple acids, replacing buffers, have been widely applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography (RPLC), none of the previously reported works focused on the systematic studies about the retention behavior of the acidic solutes in this ion-suppression RPLC mode. The subject of this paper was therefore to investigate the retention behavior of monobasic weak acidic compounds using acetic, perchloric and phosphoric acids as the ion-suppressors. The apparent octanol-water partition coefficient (K" ow) was proposed to calibrate the octanol-water partition coefficient (K(ow)) of these weak acidic compounds, which resulted in a better linear correlation with log k(w), the logarithm of the hypothetical retention factor corresponding to neat aqueous fraction of hydroorganic mobile phase. This log K" ow-log k w linear correlation was successfully validated by the results of monocarboxylic acids and monohydrating phenols, and moreover by the results under diverse experimental conditions for the same solutes. This straightforward relationship not only can be used to effectively predict the retention values of weak acidic solutes combined with Snyder-Soczewinski equation, but also can offer a promising medium for directly measuring K(ow) data of these compounds via Collander equation. In addition, the influence of the different ion-suppressors on the retention of weak acidic compounds was also compared in this RPLC mode.

Molecular Mobility in Phase Segregated Bottlebrush Block Copolymer Melts

NASA Astrophysics Data System (ADS)

Yavitt, Benjamin; Gai, Yue; Song, Dongpo; Winter, H. Henning; Watkins, James

We investigate the linear viscoelastic behavior of poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) brush block copolymer (BBCP) materials over a range of vol. fractions and with side chain lengths below the entanglement molecular weights. The high chain mobility of the brush architecture results in rapid micro-phase segregation of the brush copolymer segments, which occurs during thermal annealing at mild temperatures. Master curves of the dynamic moduli were obtained by time-temperature superposition. The reduced degree of chain entanglements leads to a unique liquid-like rheology similar to that of bottlebrush homopolymers, even in the phase segregated state. We also explore the alignment of phase segregated domains at exceptionally low strain amplitudes (γ = 0.01) and mild processing temperatures using small angle X-ray scattering (SAXS). Domain orientation occurred readily at strains within the linear viscoelastic regime without noticeable effect on the moduli. This interplay of high molecular mobility and rapid phase segregation that are exhibited simultaneously in BBCPs is in contrast to the behavior of conventional linear block copolymer (LBCP) analogs and opens up new possibilities for processing BBCP materials for a wide range of nanotechnology applications. NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-1025020).

[Separation of p-aminobenzenearsonic acid and its oxide by ion-pair reversed-phase high performance liquid chromatography].

PubMed

Kang, J; Ma, X; Meng, L; Ma, D

1999-05-01

To study the separation of p-aminobenzenearsonic acid (PABAA) and its oxide, p-aminophenylarsine oxide (PAPAO), both the absorption spectra were scanned at the wavelengths from 200 nm to 380 nm. PABAA had absorption maximum at 254 nm and PAPAO 258 nm. The effects of salt concentration, column temperature, methanol and ion-pair agent concentrations on the capacity factor were investigated. Compounds of high polarity showed almost no retention on reversed-phase column; as the volume fraction of the methanol decreased from 90% to 10%, the retention time of PABAA gradually increased with broad peak, and partially eluted when methanol volume fraction being below 20%. With temperature rising, the retention time of PABAA was decreased. But PABAA capacity factor can be increased by selecting an appropriate salt concentration for the mobile phase. The cetyltrimethyl and tetrabutyl ammonium ions were separately added as ion-pair agents to the mobile phase containing methanol in phosphate buffer of 10 mmol/L, the changes of retention time were observed. The mechanism of retention based on reversed phase ion-pair model is proposed. Besides, the retention behaviour is also influenced by size exclusion in stationary phase as well as polar interactions with residual silanol group on the silica surface.

Method for the isolation of citric acid and malic acid in Japanese apricot liqueur for carbon stable isotope analysis.

PubMed

Akamatsu, Fumikazu; Hashiguchi, Tomokazu; Hisatsune, Yuri; Oe, Takaaki; Kawao, Takafumi; Fujii, Tsutomu

2017-02-15

A method for detecting the undeclared addition of acidic ingredients is required to control the authenticity of Japanese apricot liqueur. We developed an analytical procedure that minimizes carbon isotope discrimination for measurement of the δ(13)C values of citric and malic acid isolated from Japanese apricot liqueur. Our results demonstrated that freeze-drying is preferable to nitrogen spray-drying, because it does not significantly affect the δ(13)C values of citric acid and results in smaller isotope discrimination for malic acid. Both 0.1% formic acid and 0.2% phosphoric acid are acceptable HPLC mobile phases for the isolation of citric and malic acid, although the δ(13)C values of malic acid exhibited relatively large variation compared with citric acid following isolation using either mobile phase. The developed procedure allows precise δ(13)C measurements of citric and malic acid isolated from Japanese apricot liqueur. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

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

Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxylmore » groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley

Optimising reversed-phase liquid chromatographic separation of an acidic mixture on a monolithic stationary phase with the aid of response surface methodology and experimental design.

PubMed

Wang, Y; Harrison, M; Clark, B J

2006-02-10

An optimization strategy for the separation of an acidic mixture by employing a monolithic stationary phase is presented, with the aid of experimental design and response surface methodology (RSM). An orthogonal array design (OAD) OA(16) (2(15)) was used to choose the significant parameters for the optimization. The significant factors were optimized by using a central composite design (CCD) and the quadratic models between the dependent and the independent parameters were built. The mathematical models were tested on a number of simulated data set and had a coefficient of R(2) > 0.97 (n = 16). On applying the optimization strategy, the factor effects were visualized as three-dimensional (3D) response surfaces and contour plots. The optimal condition was achieved in less than 40 min by using the monolithic packing with the mobile phase of methanol/20 mM phosphate buffer pH 2.7 (25.5/74.5, v/v). The method showed good agreement between the experimental data and predictive value throughout the studied parameter space and were suitable for optimization studies on the monolithic stationary phase for acidic compounds.

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.

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on a terguride-based stationary phase.

PubMed

Dondi, M; Flieger, M; Olsovska, J; Polcaro, C M; Sinibaldi, M

1999-10-29

The direct enantioseparation of chrysanthemic acid [2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid] and its halogen-substituted analogues was systematically studied by HPLC using a terguride-based chiral stationary phase in combination with a UV diode array and chiroptical detectors. Isomers with (1R) configuration always eluted before those with (IS) configuration. The elution sequence of cis- and trans-isomers was strongly affected by mobile phase pH, whereas the enantioselectivity remained the same. Conditions for the separation of all the enantiomers were also examined. This method was used for monitor the hydrolytic degradation products of Cyfluthrin (Baythroid) in soil under laboratory conditions.

77 FR 32092 - Mobility Fund Phase I Auction Scheduled for September 27, 2012; Notice and Filing Requirements...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-31

... Mobility Fund Phase I support they seek, including any agreements relating to post-auction market structure... FEDERAL COMMUNICATIONS COMMISSION [AU Docket No. 12-25; DA 12-641 and DA 12-721] Mobility Fund... million in one-time Mobility Fund Phase I support scheduled to commence on September 27, 2012. The Bureaus...

High-performance liquid chromatographic determination of ursodeoxycholic acid after solid phase extraction of blood serum and detection-oriented derivatization.

PubMed

Nobilis, M; Pour, M; Kunes, J; Kopecký, J; Kvĕtina, J; Svoboda, Z; Sládková, K; Vortel, J

2001-03-01

Ursodeoxycholic acid (3 alpha,7 beta-dihydroxy-5 beta-cholanoic acid, UDCA) is a therapeutically applicable bile acid widely used for the dissolution of cholesterol-rich gallstones and in the treatment of chronic liver diseases associated with cholestasis. UDCA is more hydrophilic and less toxic than another therapeutically valuable bile acid, chenodeoxycholic acid (CDCA), the 7 alpha-epimer of UDCA. Procedures for sample preparation and HPLC determination of UDCA in blood serum were developed and validated. A higher homologue of UDCA containing an additional methylene group in the side chain was synthetized and used as an internal standard (IS). Serum samples with IS were diluted with a buffer (pH=7). The bile acids and IS were captured using solid phase extraction (C18 cartridges). The carboxylic group of the analytes was derivatized using 2-bromo-2'-acetonaphthone (a detection-oriented derivatization), and reaction mixtures were analyzed (HPLC with UV 245 nm detection; a 125--4 mm column containing Lichrospher 100 C18, 5 microm; mobile phase: acetonitrile--water, 6:4 (v/v)). Following validation, this method was used for pharmacokinetic studies of UDCA in humans.

Use of vancomycin silica stationary phase in packed capillary electrochromatography: III. enantiomeric separation of basic compounds with the polar organic mobile phase.

PubMed

Fanali, Salvatore; Catarcini, Paolo; Quaglia, Maria Giovanna

2002-02-01

The separation of basic compounds into their enantiomers was achieved using capillary electrochromatography in 50 or 75 microm inner diameter (ID) fused-silica capillaries packed with silica a stationary phase derivatized with vancomycin and mobile phases composed of mixtures of polar organic solvents containing 13 mM ammonium acetate. Enantiomer resolution, electroosmotic flow, and the number of theoretical plates were strongly influenced by the type and concentration of the organic solvent. Mobile phases composed of 13 mM ammonium acetate dissolved in mixtures of acetonitrile/methanol, ethanol, n-propanol, or isopropanol were tested and the highest enantioresolutions were achieved using the first mobile phase, allowing the separation of almost all investigated enantiomers (9 from 11 basic compounds). The use of capillaries with different ID (50 and 75 microm ID) packed with the same chiral stationary phase revealed that a higher number of theoretical plates and higher enantioresolution was achieved with the tube with lowest ID.

A new acetonitrile-free mobile phase method for LC-ELSD quantification of fructooligosaccharides in onion (Allium cepa L.).

PubMed

Downes, Katherine; Terry, Leon A

2010-06-30

Onion soluble non-structural carbohydrates consist of fructose, glucose and sucrose plus fructooligosaccharides (FOS) with degrees of polymerisation (DP) in the range of 3-19. In onion, sugars and FOS are typically separated using liquid chromatography (LC) with acetonitrile (ACN) as a mobile phase. In recent times, however, the production of ACN has diminished due, in part, to the current worldwide economic recession. A study was therefore undertaken, to find an alternative LC method to quantify sugars and FOS from onion without the need for ACN. Two mobile phases were compared; the first taken from a paper by Vågen and Slimestad (2008) using ACN mobile phase, the second, a newly reported method using ethanol (EtOH). The EtOH mobile phase eluted similar concentrations of all FOS compared to the ACN mobile phase. In addition, limit of detection, limit of quantification and relative standard deviation values were sufficiently and consistently lower for all FOS using the EtOH mobile phase. The drawback of the EtOH mobile phase was mainly the inability to separate all individual sugar peaks, yet FOS could be successfully separated. However, using the same onion extract, a previously established LC method based on an isocratic water mobile phase could be used in a second run to separate sugars. Although the ACN mobile phase method is more convenient, in the current economic climate a method based on inexpensive and plentiful ethanol is a valid alternative and could potentially be applied to other fresh produce types. In addition to the mobile phase solvent, the effect of extraction solvents on sugar and FOS concentration was also investigated. EtOH is still widely used to extract sugars from onion although previous literature has concluded that MeOH is a superior solvent. For this reason, an EtOH-based extraction method was compared with a MeOH-based method to extract both sugars and FOS. The MeOH-based extraction method was more efficacious at extracting sugars and

Characterization of charged polymer self-assemblies by multidetector thermal field-flow fractionation in aqueous mobile phases.

PubMed

Greyling, Guilaume; Pasch, Harald

2018-01-12

Charged block copolymer self-assemblies, such as charged micelles, have attracted much attention as versatile drug delivery systems due to their readily tunable characteristics such as size and surface charge. However, current column-based analytical techniques are not suitable to fractionate and comprehensively characterize charged micelles in terms of size, molar mass, chemical composition and morphology. Multidetector thermal field-flow fractionation (ThFFF) is shown to be a unique characterization platform that can be used to characterize charged micelles in terms of size, molar mass, chemical composition and morphology in aqueous mobile phases with various ionic strengths and pH. This is demonstrated by the characterization of poly(methacrylic acid)-b-poly(methyl methacrylate) self-assemblies in high pH buffers as well as the characterization of cationic poly(2-vinyl pyridine)-b-polystyrene and poly(4-vinyl pyridine)-b-polystyrene self-assemblies in low pH buffers. Moreover, it is shown that ThFFF is capable of separating charged micelles according to the corona composition. These investigations prove convincingly that ThFFF is broadly applicable to the comprehensive characterization of amphiphilic self-assemblies even when aqueous mobile phases are used. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid-phase extraction of acidic herbicides.

PubMed

Wells, M J; Yu, L Z

2000-07-14

A discussion of solid-phase extraction method development for acidic herbicides is presented that reviews sample matrix modification, extraction sorbent selection, derivatization procedures for gas chromatographic analysis, and clean-up procedures for high-performance liquid chromatographic analysis. Acidic herbicides are families of compounds that include derivatives of phenol (dinoseb, dinoterb and pentachlorophenol), benzoic acid (acifluorfen, chloramben, dicamba, 3,5-dichlorobenzoic acid and dacthal--a dibenzoic acid derivative), acetic acid [2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], propanoic acid [dichlorprop, fluazifop, haloxyfop, 2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP) and silvex], butanoic acid [4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB) and 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB)], and other miscellaneous acids such as pyridinecarboxylic acid (picloram) and thiadiazine dioxide (bentazon).

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

1995-01-01

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

Simultaneous determination of ascorbic acid and caffeine in commercial soft drinks using reversed-phase ultraperformance liquid chromatography.

PubMed

Turak, Fatma; Güzel, Remziye; Dinç, Erdal

2017-04-01

A new reversed-phase ultraperformance liquid chromatography method with a photodiode array detector was developed for the quantification of ascorbic acid (AA) and caffeine (CAF) in 11 different commercial drinks consisting of one energy drink and 10 ice tea drinks. Separation of the analyzed AA and CAF with an internal standard, caffeic acid, was performed on a Waters BEH C 18 column (100 mm × 2.1 mm, 1.7 μm i.d.), using a mobile phase consisting of acetonitrile and 0.2M H 3 PO 4 (11:89, v/v) with a flow rate of 0.25 mL/min and an injection volume of 1.0 μL. Calibration graphs for AA and CAF were computed from the peak area ratio of AA/internal standard and CAF/internal standard detected at 244.0 nm and 273.6 nm, respectively. The developed reversed-phase ultraperformance liquid chromatography method was validated by analyzing standard addition samples. The proposed reversed-phase ultraperformance liquid chromatography method gave us successful results for the quantitative analysis of commercial drinks containing AA and CAF substances. Copyright © 2016. Published by Elsevier B.V.

Mobilization of aluminum by the acid percolates within unsaturated zone of sandstones.

PubMed

Navrátil, Tomáš; Vařilová, Zuzana; Rohovec, Jan

2013-09-01

The area of the Black Triangle has been exposed to extreme levels of acid deposition in the twentieth century. The chemical weathering of sandstones found within the Black Triangle became well-known phenomenon. Infiltration of acid rain solutions into the sandstone represents the main input of salt components into the sandstone. The infiltrated solutions--sandstone percolates--react with sandstone matrix and previously deposited materials such as salt efflorescence. Acidic sandstone percolates pH 3.2-4.8 found at ten sites within the National Park Bohemian Switzerland contained high Al-tot (0.8-10 mg L(-1)) concentrations and high concentrations of anions SO4 (5-66 mg L(-1)) and NO3 (2-42 mg L(-1)). A high proportion (50-98 %) of Al-tot concentration in acid percolates was represented by toxic reactive Al(n+). Chemical equilibrium modeling indicated as the most abundant Al species Al(3+), AlSO4 (+), and AlF(2+). The remaining 2-50 % of Al-tot concentration was present in the form of complexes with dissolved organic matter Al-org. Mobilization and transport of Al from the upper zones of sandstone causes chemical weathering and sandstone structure deterioration. The most acidic percolates contained the highest concentrations of dissolved organic material (estimated up to 42 mg L(-1)) suggesting the contribution of vegetation on sandstone weathering processes. Very low concentrations of Al-tot in springs at BSNP suggest that Al mobilized in unsaturated zone is transported deeper into the sandstone. This process of mobilization could represent a threat for the water quality small-perched aquifers.

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.

Multiphase mean curvature flows with high mobility contrasts: A phase-field approach, with applications to nanowires

NASA Astrophysics Data System (ADS)

Bretin, Elie; Danescu, Alexandre; Penuelas, José; Masnou, Simon

2018-07-01

The structure of many multiphase systems is governed by an energy that penalizes the area of interfaces between phases weighted by surface tension coefficients. However, interface evolution laws depend also on interface mobility coefficients. Having in mind some applications where highly contrasted or even degenerate mobilities are involved, for which classical phase field models are inapplicable, we propose a new effective phase field approach to approximate multiphase mean curvature flows with mobilities. The key aspect of our model is to incorporate the mobilities not in the phase field energy (which is conventionally the case) but in the metric which determines the gradient flow. We show the consistency of such an approach by a formal analysis of the sharp interface limit. We also propose an efficient numerical scheme which allows us to illustrate the advantages of the model on various examples, as the wetting of droplets on solid surfaces or the simulation of nanowires growth generated by the so-called vapor-liquid-solid method.

Combined effects of low-molecular-weight organic acids on mobilization of arsenic and lead from multi-contaminated soils.

PubMed

Onireti, Olaronke O; Lin, Chuxia; Qin, Junhao

2017-03-01

A batch experiment was conducted to examine the combined effects of three common low-molecular-weight organic acids (LMWOAs) on the mobilization of arsenic and lead in different types of multi-contaminated soils. The capacity of individual LMWOAs (at a same molar concentration) to mobilize soil-borne As and Pb varied significantly. The combination of the organic acids did not make a marked "additive" effect on the mobilization of the investigated three elements. An "antagonistic" effect on element mobilization was clear in the treatments involving oxalic acid for some soils. The acid strength of a LMWOA did not play an important role in controlling the mobilization of elements. While the mobilization of As and Pb was closely associated with the dissolution of soil-borne Fe, soil properties such as original soil pH, organic matter contents and the total amount of the element relative to the total Fe markedly complicated the mobility of that element. Aging led to continual consumption of proton introduced from addition of LMWOAs and consequently caused dramatic changes in solution-borne Fe, which in turn resulted in change in As and Pb in the soil solution though different elements behaved differently. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal mobilization from metallurgical wastes by soil organic acids.

PubMed

Potysz, Anna; Grybos, Malgorzata; Kierczak, Jakub; Guibaud, Gilles; Fondaneche, Patrice; Lens, Piet N L; van Hullebusch, Eric D

2017-07-01

Three types of Cu-slags differing in chemical and mineralogical composition (historical, shaft furnace, and granulated slags) and a matte from a lead recovery process were studied with respect to their susceptibility to release Cu, Zn and Pb upon exposure to organic acids commonly encountered in soil environments. Leaching experiments (24-960 h) were conducted with: i) humic acid (20 mg/L) at pH t 0  = 4.4, ii) fulvic acid (20 mg/L) at pH t 0  = 4.4, iii) an artificial root exudates (ARE) (17.4 g/L) solution at pH t 0  = 4.4, iv) ARE solution at pH t 0  = 2.9 and v) ultrapure water (pH t 0  = 5.6). The results demonstrated that the ARE contribute the most to the mobilization of metals from all the wastes analyzed, regardless of the initial pH of the solution. For example, up to 14%, 30%, 24% and 5% of Cu is released within 960 h from historical, shaft furnace, granulated slags and lead matte, respectively, when exposed to the artificial root exudates solution (pH 2.9). Humic and fulvic acids were found to have a higher impact on granulated and shaft furnace slags as compared to the ultrapure water control and increased the release of metals by a factor up to 37.5 (Pb) and 20.5 (Cu) for granulated and shaft furnace slags, respectively. Humic and fulvic acids amplified the mobilization of metals by a maximal factor of 13.6 (Pb) and 12.1 (Pb) for historical slag and lead matte, respectively. The studied organic compounds contributed to different release rates of metallic contaminants from individual metallurgical wastes under the conditions tested. Copyright © 2017 Elsevier Ltd. All rights reserved.

Aqueous-phase source of formic acid in clouds

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1983-01-01

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Computed phase diagrams for the system: Sodium hydroxide-uric acid-hydrochloric acid-water

NASA Astrophysics Data System (ADS)

Brown, W. E.; Gregory, T. M.; Füredi-Milhofer, H.

1987-07-01

Renal stone formation is made complex by the variety of solid phases that are formed, by the number of components in the aqueous phase, and by the multiplicity of ionic dissociation and association processes that are involved. In the present work we apply phase diagrams calculated by the use of equilibrium constants from the ternary system sodium hydroxide-uric acid-water to simplify and make more rigorous the understanding of the factors governing dissolution and precipitation of uric acid (anhydrous and dihydrate) and sodium urate monohydrate. The system is then examined in terms of four components. Finally, procedures are described for fluids containing more than four components. The isotherms, singular points, and fields of supersaturation and undersaturation are shown in various forms of phase diagrams. This system has two notable features: (1) in the coordinates -log[H 2U] versus -log[NaOH], the solubility isotherms for anhydrous uric acid and uric acid dihydrate approximate straight lines with slopes equal to +1 over a wide range of concentrations. As a result, substantial quantities of sodium acid urate monohydrate can precipitate from solution or dissolve without changing the degree of saturation of uric acid significantly. (2) The solubility isotherm for NaHU·H 2O has a deltoid shape with the low-pH branch having a slope of infinity. As a result of the vertical slope of this isotherm, substantial quantities of uric acid can dissolve or precipitate without changing the degree of saturation of sodium acid urate monohydrate significantly. The H 2U-NaOH singular point has a pH of 6.87 at 310 K in the ternary system.

[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.

Multiplicative effects model with internal standard in mobile phase for quantitative liquid chromatography-mass spectrometry.

PubMed

Song, Mi; Chen, Zeng-Ping; Chen, Yao; Jin, Jing-Wen

2014-07-01

Liquid chromatography-mass spectrometry assays suffer from signal instability caused by the gradual fouling of the ion source, vacuum instability, aging of the ion multiplier, etc. To address this issue, in this contribution, an internal standard was added into the mobile phase. The internal standard was therefore ionized and detected together with the analytes of interest by the mass spectrometer to ensure that variations in measurement conditions and/or instrument have similar effects on the signal contributions of both the analytes of interest and the internal standard. Subsequently, based on the unique strategy of adding internal standard in mobile phase, a multiplicative effects model was developed for quantitative LC-MS assays and tested on a proof of concept model system: the determination of amino acids in water by LC-MS. The experimental results demonstrated that the proposed method could efficiently mitigate the detrimental effects of continuous signal variation, and achieved quantitative results with average relative predictive error values in the range of 8.0-15.0%, which were much more accurate than the corresponding results of conventional internal standard method based on the peak height ratio and partial least squares method (their average relative predictive error values were as high as 66.3% and 64.8%, respectively). Therefore, it is expected that the proposed method can be developed and extended in quantitative LC-MS analysis of more complex systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Separation of chlorogenic acid and concentration of trace caffeic acid from natural products by pH-zone-refining countercurrent chromatography.

PubMed

Lu, Yuanyuan; Dong, Genlai; Gu, Yanxiang; Ito, Yoichiro; Wei, Yun

2013-07-01

Chlorogenic acid and caffeic acid were selected as test samples for separation by the pH-zone-refining countercurrent chromatography (CCC). The separation of these test samples was performed with a two-phase solvent system composed of methyl-tert-butyl-ether/acetonitrile/water at a volume ratio of 4:1:5 v/v/v where trifluoroacetic acid (TFA; 8 mM) was added to the organic stationary phase as a retainer and NH4 OH (10 mM) to the aqueous mobile phase as an eluter. Chlorogenic acid was successfully separated from Flaveria bidentis (L.) Kuntze (F. bidentis) and Lonicerae Flos by pH-zone-refining CCC, a slightly polar two-phase solvent system composed of methyl-tert-butyl-ether/acetonitrile/n-butanol/water at a volume ratio of 4:1:1:5 v/v/v/v was selected where TFA (3 mM) was added to the organic stationary phase as a retainer and NH4 OH (3 mM) to the aqueous mobile phase as an eluter. A 16.2 mg amount of chlorogenic acid with the purity of 92% from 1.4 g of F. bidentis, and 134 mg of chlorogenic acid at the purity of 99% from 1.3 g of crude extract of Lonicerae Flos have been obtained. These results suggest that pH-zone-refining CCC is suitable for the isolation of the chlorogenic acid from the crude extracts of F. bidentis and Lonicerae Flos. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Genealogical Tree of Ethanol: Gas-phase Formation of Glycolaldehyde, Acetic Acid, and Formic Acid

NASA Astrophysics Data System (ADS)

Skouteris, Dimitrios; Balucani, Nadia; Ceccarelli, Cecilia; Vazart, Fanny; Puzzarini, Cristina; Barone, Vincenzo; Codella, Claudio; Lefloch, Bertrand

2018-02-01

Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star-forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesized is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this paper, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid, and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid, and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of 10, which might imply a yet incomplete reaction network.

Boundary of Phase Co-existence in Docosahexaenoic Acid System

NASA Astrophysics Data System (ADS)

Lor, Chai; Hirst, Linda S.

2011-11-01

Docosahexaenoic acid (DHA) is a highly polyunsaturated fatty acid (PUFA) that exhibits six double bonds in the hydrocarbon tail. It induces phase separation of the membrane into liquid order and liquid disorder in mixtures containing other lipids with more saturation and cholesterol. With the utilization of atomic force microscopy, phase co-existence is observed in lipid mixtures containing DHA on a single supported lipid bilayer. The boundary of phase co-existence with decreasing DHA concentration is explored. The elastic force, thickness, and roughness of the different phases are investigated.

Cyclodextrins as a chiral mobile phase additive in nano-liquid chromatography: comparison of reversed-phase silica monolithic and particulate capillary columns.

PubMed

Rocco, Anna; Maruška, Audrius; Fanali, Salvatore

2012-03-01

Enantioseparations of racemic nonsteroidal anti-inflammatory drugs (naproxen, ibuprofen, ketoprofen, flurbiprofen, suprofen, indoprofen, cicloprofen, and carprofen) were performed by nano-liquid chromatography, employing achiral capillary columns and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD) or hydroxylpropyl-β-cyclodextrin (HP-β-CD) as a chiral mobile phase additive (CMPA). Working under the same experimental conditions (in terms of mobile phase and linear velocity), the performance of a RP-C18 monolithic column was compared with that of a RP-C18 packed column of the same dimensions (100 μm i.d. × 10 cm). Utilizing a mobile phase composed of 30% ACN (v/v) buffered with 50 mM sodium acetate at pH 3, and containing 30 mM TM-β-CD, the monolithic column provided faster analysis but lower resolution than the packed column. This behavior was ascribed to the high permeability of the monolithic column, as well as to its minor selectivity. HP-β-CD was chosen as an alternative to TM-β-CD. Employing the monolithic column, the effects of different parameters such as HP-β-CD concentration, mobile phase composition, and pH on the retention factor and the chiral resolution of the analytes were studied. For the most of the analytes, enantioresolution (which ranged from R(s) = 1.80 for naproxen to R(s) = 0.86 for flurbiprofen) was obtained with a mobile phase consisting of sodium acetate buffer (25 mM, pH 3), 10% MeOH, and 15 mM HP-β-CD. When the same experimental conditions were used with the packed column, no compound eluted within 1 h. Upon increasing the percentage of organic modifier to favor analyte elution, only suprofen eluted within 30 min, with an R(s) value of 1.14 (20% MeOH). Replacing MeOH with ACN resulted in a loss of enantioresolution, except for naproxen (R(s) = 0.89).

Determination of branched chain amino acids, methionine, phenylalanine, tyrosine and alpha-keto acids in plasma and dried blood samples using HPLC with fluorescence detection.

PubMed

Kand'ár, Roman; Záková, Pavla; Jirosová, Jana; Sladká, Michaela

2009-01-01

The determination of branched chain amino acids [BCAA; valine (Val), leucine (Leu), isoleucine (Ile)], alpha-keto acids derived from BCAA [BCKA; alpha-ketoisovaleric acid (KIV), alpha-ketoisocaproic acid (KIC), alpha-ketomethylvaleric acid (KMV)], methionine (Met), phenylalanine (Phe) and tyrosine (Tyr) is currently the most reliable approach for the diagnosis of maple syrup urine disease (MSUD), hypermethioninemia, phenylketonuria (PKU) and tyrosinemia. The aim of this study was to develop rapid and simple HPLC methods for measurement of BCAA, Met, Phe, Tyr and BCKA in plasma and dried blood samples. Samples of peripheral venous blood with EDTA as anticoagulant were obtained from a group of healthy blood donors (n=70, 35 females, 27-41 years of age and 35 males, 28-43 years of age). Blood-spot samples from a group of newborns (n=80, 40 girls and 40 boys 3-5 days of age) were collected onto #903 Specimen Collection Paper and allowed to dry for at least 24 h before analysis. Prior to separation, the amino acids (AA) were derivatized with o-phthaldialdehyde (OPA) and BCKA with o-phenylenediamine (OPD). Reverse phase column chromatography (LiChroCart 125-4 Purospher RP-18e, 5 microm) was used for separation and fluorescence detection used to monitoring of effluent. For AA analysis, 25 mmol/L sodium hydrogenphosphate-methanol (90:10, v/v), pH 6.5+/-0.1 was used as mobile phase A and 100% methanol was used as mobile phase B. Measurement of BCKA used a mixture of methanol and deionized water (55:45, v/v) as mobile phase A and mobile phase B consisted of 100% methanol. Analytical performance of these methods was satisfactory for the determination of all AA and BCKA. The intra-assay and inter-assay coefficients of variation were below 10% and recovery ranged from 90%-110%. We have developed simple, rapid and selective HPLC methods with fluorescence detection for the determination of BCAA, Met, Phe, Tyr and BCKA in plasma and dried blood samples.

Chemical speciation and mobilization of copper and zinc in naturally contaminated mine soils with citric and tartaric acids.

PubMed

Pérez-Esteban, Javier; Escolástico, Consuelo; Moliner, Ana; Masaguer, Alberto

2013-01-01

A one-step extraction procedure and a leaching column experiment were performed to assess the effects of citric and tartaric acids on Cu and Zn mobilization in naturally contaminated mine soils to facilitate assisted phytoextraction. A speciation modeling of the soil solution and the metal fractionation of soils were performed to elucidate the chemical processes that affected metal desorption by organic acids. Different extracting solutions were prepared, all of which contained 0.01 M KNO(3) and different concentrations of organic acids: control without organic acids, 0.5 mM citric, 0.5 mM tartaric, 10 mM citric, 10 mM tartaric, and 5 mM citric +5 mM tartaric. The results of the extraction procedure showed that higher concentrations of organic acids increased metal desorption, and citric acid was more effective at facilitating metal desorption than tartaric acid. Metal desorption was mainly influenced by the decreasing pH and the dissolution of Fe and Mn oxides, not by the formation of soluble metal-organic complexes as was predicted by the speciation modeling. The results of the column study reported that low concentrations of organic acids did not significantly increase metal mobilization and that higher doses were also not able to mobilize Zn. However, 5-10 mM citric acid significantly promoted Cu mobilization (from 1 mg kg(-1) in the control to 42 mg kg(-1) with 10 mM citric acid) and reduced the exchangeable (from 21 to 3 mg kg(-1)) and the Fe and Mn oxides (from 443 to 277 mg kg(-1)) fractions. Citric acid could efficiently facilitate assisted phytoextraction techniques. Copyright © 2012 Elsevier Ltd. All rights reserved.

Validation of a multi-analyte HPLC-DAD method for determination of uric acid, creatinine, homovanillic acid, niacinamide, hippuric acid, indole-3-acetic acid and 2-methylhippuric acid in human urine.

PubMed

Remane, Daniela; Grunwald, Soeren; Hoeke, Henrike; Mueller, Andrea; Roeder, Stefan; von Bergen, Martin; Wissenbach, Dirk K

2015-08-15

During the last decades exposure sciences and epidemiological studies attracts more attention to unravel the mechanisms for the development of chronic diseases. According to this an existing HPLC-DAD method for determination of creatinine in urine samples was expended for seven analytes and validated. Creatinine, uric acid, homovanillic acid, niacinamide, hippuric acid, indole-3-acetic acid, and 2-methylhippuric acid were separated by gradient elution (formate buffer/methanol) using an Eclipse Plus C18 Rapid Resolution column (4.6mm×100mm). No interfering signals were detected in mobile phase. After injection of blank urine samples signals for the endogenous compounds but no interferences were detected. All analytes were linear in the selected calibration range and a non weighted calibration model was chosen. Bias, intra-day and inter-day precision for all analytes were below 20% for quality control (QC) low and below 10% for QC medium and high. The limits of quantification in mobile phase were in line with reported reference values but had to be adjusted in urine for homovanillic acid (45mg/L), niacinamide 58.5(mg/L), and indole-3-acetic acid (63mg/L). Comparison of creatinine data obtained by the existing method with those of the developed method showing differences from -120mg/L to +110mg/L with a mean of differences of 29.0mg/L for 50 authentic urine samples. Analyzing 50 authentic urine samples, uric acid, creatinine, hippuric acid, and 2-methylhippuric acid were detected in (nearly) all samples. However, homovanillic acid was detected in 40%, niacinamide in 4% and indole-3-acetic acid was never detected within the selected samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Mated Drosophila melanogaster females consume more amino acids during the dark phase

PubMed Central

Uchizono, Shun; Tabuki, Yumi; Kawaguchi, Natsumi; Tanimura, Teiichi; Itoh, Taichi Q.

2017-01-01

To maintain homeostasis, animals must ingest appropriate quantities, determined by their internal nutritional state, of suitable nutrients. In the fruit fly Drosophila melanogaster, an amino acid deficit induces a specific appetite for amino acids and thus results in their increased consumption. Although multiple processes of physiology, metabolism, and behavior are under circadian control in many organisms, it is unclear whether the circadian clock also modulates such motivated behavior driven by an internal need. Differences in levels of amino acid consumption by flies between the light and dark phases of the day:night cycle were examined using a capillary feeder assay following amino acid deprivation. Female flies exhibited increased consumption of amino acids during the dark phase compared with the light phase. Investigation of mutants lacking a functional period gene (per0), a well-characterized clock gene in Drosophila, found no difference between the light and dark phases in amino acid consumption by per0 flies. Furthermore, increased consumption of amino acids during the dark phase was observed in mated but not in virgin females, which strongly suggested that mating is involved in the rhythmic modulation of amino acid intake. Egg production, which is induced by mating, did not affect the rhythmic change in amino acid consumption, although egg-laying behavior showed a per0-dependent change in rhythm. Elevated consumption of amino acids during the dark phase was partly induced by the action of a seminal protein, sex peptide (SP), on the sex peptide receptor (SPR) in females. Moreover, we showed that the increased consumption of amino acids during the dark phase is induced in mated females independently of their internal level of amino acids. These results suggest that a post-mating SP/SPR signal elevates amino acid consumption during the dark phase via the circadian clock. PMID:28241073

Mated Drosophila melanogaster females consume more amino acids during the dark phase.

PubMed

Uchizono, Shun; Tabuki, Yumi; Kawaguchi, Natsumi; Tanimura, Teiichi; Itoh, Taichi Q

2017-01-01

To maintain homeostasis, animals must ingest appropriate quantities, determined by their internal nutritional state, of suitable nutrients. In the fruit fly Drosophila melanogaster, an amino acid deficit induces a specific appetite for amino acids and thus results in their increased consumption. Although multiple processes of physiology, metabolism, and behavior are under circadian control in many organisms, it is unclear whether the circadian clock also modulates such motivated behavior driven by an internal need. Differences in levels of amino acid consumption by flies between the light and dark phases of the day:night cycle were examined using a capillary feeder assay following amino acid deprivation. Female flies exhibited increased consumption of amino acids during the dark phase compared with the light phase. Investigation of mutants lacking a functional period gene (per0), a well-characterized clock gene in Drosophila, found no difference between the light and dark phases in amino acid consumption by per0 flies. Furthermore, increased consumption of amino acids during the dark phase was observed in mated but not in virgin females, which strongly suggested that mating is involved in the rhythmic modulation of amino acid intake. Egg production, which is induced by mating, did not affect the rhythmic change in amino acid consumption, although egg-laying behavior showed a per0-dependent change in rhythm. Elevated consumption of amino acids during the dark phase was partly induced by the action of a seminal protein, sex peptide (SP), on the sex peptide receptor (SPR) in females. Moreover, we showed that the increased consumption of amino acids during the dark phase is induced in mated females independently of their internal level of amino acids. These results suggest that a post-mating SP/SPR signal elevates amino acid consumption during the dark phase via the circadian clock.

Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

PubMed

Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

2016-10-07

Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of simulated acid rain on fluorine mobility and the bacterial community of phosphogypsum.

PubMed

Wang, Mei; Tang, Ya; Anderson, Christopher W N; Jeyakumar, Paramsothy; Yang, Jinyan

2018-06-01

Contamination of soil and water with fluorine (F) leached from phosphogypsum (PG) stacks is a global environmental issue. Millions of tons of PG is produced each year as a by-product of fertilizer manufacture, and in China, weathering is exacerbated by acid rain. In this work, column leaching experiments using simulated acid rain were run to evaluate the mobility of F and the impact of weathering on native bacterial community composition in PG. After a simulated summer rainfall, 2.42-3.05 wt% of the total F content of PG was leached and the F concentration in leachate was above the quality standard for surface water and groundwater in China. Acid rain had no significant effect on the movement of F in PG. A higher concentration of F was observed at the bottom than the top section of PG columns suggesting mobility and reprecipitation of F. Throughout the simulation, the PG was environmentally safe according the TCLP testing. The dominant bacteria in PG were from the Enterococcus and Bacillus genus. Bacterial community composition in PG leached by simulated acid rain (pH 3.03) was more abundant than at pH 6.88. Information on F mobility and bacterial community in PG under conditions of simulated rain is relevant to management of environmental risk in stockpiled PG waste.

Considerations of digital phase modulation for narrowband satellite mobile communication

NASA Technical Reports Server (NTRS)

Grythe, Knut

1990-01-01

The Inmarsat-M system for mobile satellite communication is specified as a frequency division multiple access (FDMA) system, applying Offset Quadrature Phase Shift Keying (QPSK) for transmitting 8 kbit/sec in 10 kHz user channel bandwidth. We consider Digital Phase Modulation (DPM) as an alternative modulation format for INMARSAT-M. DPM is similar to Continuous Phase Modulation (CPM) except that DPM has a finite memory in the premodular filter with a continuous varying modulation index. It is shown that DPM with 64 states in the VA obtains a lower bit error rate (BER). Results for a 5 kHz system, with the same 8 kbit/sec transmitted bitstream, is also presented.

Validation of a 2 percent lactic acid antimicrobial rinse for mobile poultry slaughter operations.

PubMed

Killinger, Karen M; Kannan, Aditi; Bary, Andy I; Cogger, Craig G

2010-11-01

Poultry processing antimicrobial interventions are critical for pathogen control, and organic, mobile operations in Washington seek alternatives to chlorine. Laboratory and field studies (three replications each) evaluated lactic acid efficacy as a chlorine alternative. For the laboratory study, retail-purchased, conventionally processed chicken wings inoculated with Salmonella were randomly assigned to the following treatments: Salmonella inoculation followed by no treatment (10 wings) or by 3-min rinses of water, 50 to 100 ppm of chlorine, or 2% lactic acid (20 wings for each rinse treatment). Wings were sampled for Salmonella enumeration on xylose lysine desoxycholate agar. During pastured poultry processing at mobile slaughter units for each field study replication, 20 chicken carcasses were randomly assigned to each treatment: untreated control or 3-min immersion in lactic acid or chlorine. Whole-carcass rinses were examined for aerobic plate count (APC) on tryptic soy agar and coliforms on violet red bile agar. Untreated controls were also examined for Salmonella. In the laboratory study, lactic acid produced a significant (P < 0.01) Salmonella reduction compared with the inoculated no-rinse, water, and chlorine treatments, which were statistically similar to each other. In the field study, no Salmonella was detected on untreated controls. Lactic acid produced significant >2-log (P < 0.01) reductions in APC and coliforms, whereas chlorine resulted in slight, but significant 0.4-log reductions (P < 0.01) and 0.21-log reductions (P < 0.05) in APC and coliforms compared with untreated controls. Considering laboratory and field studies, lactic acid produced greater reductions in Salmonella, APC, and coliforms, validating its effectiveness as a chlorine alternative in mobile poultry slaughter operations.

Project inspection using mobile technology - phase I : an investigation into existing business processes and areas for improvement using mobile technology.

DOT National Transportation Integrated Search

2013-08-01

As mobile technology becomes widely available and affordable, transportation agencies can use this technology to : streamline operations involved within project inspection. This research, conducted in two phases, identified : opportunities for proces...

Prediction of peak shape in hydro-organic and micellar-organic liquid chromatography as a function of mobile phase composition.

PubMed

Baeza-Baeza, J J; Ruiz-Angel, M J; García-Alvarez-Coque, M C

2007-09-07

A simple model is proposed that relates the parameters describing the peak width with the retention time, which can be easily predicted as a function of mobile phase composition. This allows the further prediction of peak shape with global errors below 5%, using a modified Gaussian model with a parabolic variance. The model is useful in the optimisation of chromatographic resolution to assess an eventual overlapping of close peaks. The dependence of peak shape with mobile phase composition was studied for mobile phases containing acetonitrile in the presence and absence of micellised surfactant (micellar-organic and hydro-organic reversed-phase liquid chromatography, RPLC). In micellar RPLC, both modifiers (surfactant and acetonitrile) were observed to decrease or improve the efficiencies in the same percentage, at least in the studied concentration ranges. The study also revealed that the problem of achieving smaller efficiencies in this chromatographic mode, compared to hydro-organic RPLC, is not only related to the presence of surfactant covering the stationary phase, but also to the smaller concentration of organic solvent in the mobile phase.

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.

77 FR 57085 - Mobility Fund Phase I Auction; Release of Files with Recalculated Road Miles for Auction 901...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-17

... FEDERAL COMMUNICATIONS COMMISSION [AU Docket No. 12-25; DA 12-1446] Mobility Fund Phase I Auction... Mobility Fund Phase I support to be offered in Auction 901, which is to be held on September 27, 2012, and the change of the mock auction date from September 25, 2012 to September 21, 2012. DATES: The mock...

Metallomesogenic stationary phase for open-tubular capillary electrochromatography.

PubMed

Chen, Jian-Lian

2006-02-01

A synthetic coppermesogenic polymer is prepared and then covalently bonded to the siloxane-based deactivated column as the stationary phases of open-tubular CEC with essentially high phase ratio. The EOF generated from the modified phase is surveyed through conventional aqueous buffers and hydroorganic mobile phases. Zeta potentials, which are computed from the EOF data and the ratio of dielectric constant to viscosity, are plotted as a function of pH, ionic molarity, and compositional range. These plots responsible for the electroosmotic characteristic of the bonded phases are found to be like those of bare fused-silica or deactivated columns through decreasing or increasing the ACN content in the mobile phase, respectively. This two-phase characteristic is basically derived from the polymeric configuration with carboxylato ligands attached onto the polysiloxane backbone. Phthalates and amino acids are suitable probes to examine the two phenomena, more-polar and less-polar mediums, respectively, and to judge whether the chromatographic retention is the major source of separation mechanism. With the mixing modes of Lewis acid-base interaction, dispersive force, and shape discrimination, the chromatographic partition adequately accomplishes the uneasily resolved separations by only CZE mode, although the electrophoretic migration is truly somewhat involved.

Signal enhancement for peptide analysis in liquid chromatography-electrospray ionization mass spectrometry with trifluoroacetic acid containing mobile phase by postcolumn electrophoretic mobility control.

PubMed

Wang, Nan-Hsuan; Lee, Wan-Li; Her, Guor-Rong

2011-08-15

A strategy based on postcolumn electrophoretic mobility control (EMC) was developed to alleviate the adverse effect of trifluoroacetic acid (TFA) on the liquid chromatography-mass spectrometry (LC-MS) analysis of peptides. The device created to achieve this goal consisted of a poly(dimethylsiloxane) (PDMS)-based junction reservoir, a short connecting capillary, and an electrospray ionization (ESI) sprayer connected to the outlet of the high-performance liquid chromatography (HPLC) column. By apply different voltages to the junction reservoir and the ESI emitter, an electric field was created across the connecting capillary. Due to the electric field, positively charged peptides migrated toward the ESI sprayer, whereas TFA anions remained in the junction reservoir and were removed from the ionization process. Because TFA did not enter the ESI source, ion suppression from TFA was alleviated. Operation of the postcolumn device was optimized using a peptide standard mixture. Under optimized conditions, signals for the peptides were enhanced 9-35-fold without a compromise in separation efficiency. The optimized conditions were also applied to the LC-MS analysis of a tryptic digest of bovine serum albumin.

Simultaneous determination of all-trans and 13-cis retinoic acids and their 4-oxo metabolites by adsorption liquid chromatography after solid-phase extraction.

PubMed

Lefebvre, P; Agadir, A; Cornic, M; Gourmel, B; Hue, B; Dreux, C; Degos, L; Chomienne, C

1995-04-07

All-trans retinoic acid (all-trans RA), the active metabolite of vitamin A, has been demonstrated to be an efficient alternative to chemotherapy in the treatment of acute promyelocytic leukemia (APL), the AML3 subtype of the FAB cytological classification. Complete remission is obtained by inducing terminal granulocytic differentiation of the leukemic cells. To study all-trans RA pharmacokinetics in patients with APL, a rapid, precise and selective high-performance liquid chromatographic (HPLC) assay was developed. This method is easy and shows good repeatability (C.V. = 8.41-12.44%), reproducibility (C.V. = 9.19-14.73%), accuracy (C.V. = 3.5-11%) and sensitivity with a detection limit of 5 pmol/ml. The analysis is performed using normal-phase HPLC in an isocratic mode with UV detection after solid-phase extraction on octadecyl (C18) columns. The mobile phase is hexane-dichloromethane-dioxane (78:18:4, v/v) containing 1% acetic acid.

Simultaneous determination of ochratoxin A and cyclopiazonic, mycophenolic, and tenuazonic acids in cornflakes by solid-phase microextraction coupled to high-performance liquid chromatography.

PubMed

Aresta, Antonella; Cioffi, Nicola; Palmisano, Francesco; Zambonin, Carlo G

2003-08-27

A solid-phase microextraction (SPME) method, coupled to liquid chromatography with diode array UV detection (LC-UV/DAD), for the simultaneous determination of cyclopiazonic acid, mycophenolic acid, tenuazonic acid, and ochratoxin A is described. Chromatographic separation was achieved on a propylamino-bonded silica gel stationary phase using acetonitrile/methanol/ammonium acetate buffer mixture (78:2:20, v/v/v) as mobile phase. SPME adsorption and desorption conditions were optimized using a silica fiber coated with a 60 microm thick polydimethylsiloxane/divinylbenzene film. Estimated limits of detection and limits of quantitation ranged from 3 to 12 ng/mL and from 7 to 29 ng/mL, respectively. The method has been applied to cornflake samples. Samples were subjected to a preliminary short sonication in MeOH/2% KHCO(3) (70:30, v/v); the mixture was evaporated to near dryness and reconstituted in 1.5 mL of 5 mM phosphate buffer (pH 3) for SPME followed by LC-UV/DAD. The overall procedure had recoveries (evaluated on samples spiked at 200 ng/g level) ranging from 74 +/- 4 to 103 +/- 9%. Samples naturally contaminated with cyclopiazonic and tenuazonic acids were found; estimated concentrations were 72 +/- 9 and 25 +/- 6 ng/g, respectively.

Determination of phenolic acids and flavonoids in raw propolis by silica-supported ionic liquid-based matrix solid phase dispersion extraction high performance liquid chromatography-diode array detection.

PubMed

Wang, Zhibing; Sun, Rui; Wang, Yuanpeng; Li, Na; Lei, Lei; Yang, Xiao; Yu, Aimin; Qiu, Fangping; Zhang, Hanqi

2014-10-15

The silica-supported ionic liquid (S-SIL) was prepared by impregnation and used as the dispersion adsorbent of matrix solid phase dispersion (MSPD) for the simultaneous extraction of eight phenolic acids and flavonoids, including caffeic acid, ferulic acid, morin, luteolin, quercetin, apigenin, chrysin, and kaempferide in raw propolis. High performance liquid chromatography with a Zorbax SB-C18 column (150mm×4.6mm, 3.5μm) was used for separation of the analytes. The mobile phase consisted of 0.2% phosphoric acid aqueous solution and acetonitrile and the flow rate of the mobile phase was 0.5mL/min. The experimental conditions for silica-supported ionic liquid-based matrix solid phase dispersion (S-SIL-based MSPD) were optimized. S-SIL containing 10% [C6MIM]Cl was used as dispersant, 20mL of n-hexane as washing solvent and 15mL of methanol as elution solvent. The ratio of S-SIL to sample was selected to be 4:1. The standard curves showed good linear relationship (r>0.9995). The limits of detection and quantification were in the range of 5.8-22.2ngmL(-1) and 19.2-74.0ngmL(-1), respectively. The relative standard deviations (RSDs) of intra-day and inter-day determination were lower than 8.80% and 11.19%, respectively. The recoveries were between 65.51% and 92.32% with RSDs lower than 8.95%. Compared with ultrasound-assisted extraction (UAE) and soxhlet extraction, the present method consumed less sample, organic solvent, and extraction time, although the extraction yields obtained by S-SIL-based MSPD are slightly lower than those obtained by UAE. Copyright © 2014 Elsevier B.V. All rights reserved.

Combining Structural Probes in the Gas Phase - Ion Mobility- Resolved Action-FRET

NASA Astrophysics Data System (ADS)

Daly, Steven; MacAleese, Luke; Dugourd, Philippe; Chirot, Fabien

2018-01-01

In the context of native mass spectrometry, the development of gas-phase structural probes sensitive to the different levels of structuration of biomolecular assemblies is necessary to push forward conformational studies. In this paper, we provide the first example of the combination of ion mobility (IM) and Förster resonance energy transfer (FRET) measurements within the same experimental setup. The possibility to obtain mass- and mobility-resolved FRET measurements is demonstrated on a model peptide and applied to monitor the collision-induced unfolding of ubiquitin. [Figure not available: see fulltext.

Solid/liquid phase diagram of the ammonium sulfate/glutaric acid/water system.

PubMed

Beyer, Keith D; Pearson, Christian S; Henningfield, Drew S

2013-05-02

We have studied the low temperature phase diagram and water activities of the ammonium sulfate/glutaric acid/water system using differential scanning calorimetry, infrared spectroscopy of thin films, and a new technique: differential scanning calorimetry-video microscopy. Using these techniques, we have determined that there is a temperature-dependent kinetic effect to the dissolution of glutaric acid in aqueous solution. We have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/glutaric acid phase boundary as well as the ternary eutectic composition and temperature. We have also modified our glutaric acid/water binary phase diagram previously published based on these new results. We compare our results for the ternary system to the predictions of the Extended AIM Aerosol Thermodynamics Model (E-AIM), and find good agreement for the ice melting points in the ice primary phase field of this system; however, significant differences were found with respect to phase boundaries, concentration and temperature of the ternary eutectic, and glutaric acid dissolution.

Rapid determination of thiamine, riboflavin, niacinamide, pantothenic acid, pyridoxine, folic acid and ascorbic acid in Vitamins with Minerals Tablets by high-performance liquid chromatography with diode array detector.

PubMed

Jin, Pengfei; Xia, Lufeng; Li, Zheng; Che, Ning; Zou, Ding; Hu, Xin

2012-11-01

A simple, isocratic, and stability-indicating high-performance liquid chromatography (HPLC) method has been developed for the rapid determination of thiamine (VB(1)), niacinamide (VB(3)), pyridoxine (VB(6)), ascorbic acid (VC), pantothenic acid (VB(5)), riboflavin (VB(2)) and folic acid (VB(9)) in Vitamins with Minerals Tablets (VMT). An Alltima C(18) column (250 mm × 4.6 mm i.d., 5 μm) was used for the separation at ambient temperature, with 50mM ammonium dihydrogen phosphate (adjusting with phosphoric acid to pH 3.0) and acetonitrile as the mobile phase at the flow rate of 0.5 ml min(-1). VB(1), VB(3), VB(6), VC and VB(5) were extracted with a solution containing 0.05% phosphoric acid (v/v) and 0.3% sodium thiosulfate (w/v), and were then simultaneously analyzed by using the mobile phase of phosphate buffer-acetonitrile (95:5, v/v), while VB(2) and VB(9) were extracted with a solution containing 0.5% ammonium hydroxide solution (v/v), and were then simultaneously analyzed by using the mobile phase of phosphate buffer-acetonitrile (85:15, v/v). The detection wavelengths were 275 nm for VB(1), VB(3), VB(6), VC, 210 nm for VB(5), and 282 nm for VB(2) and VB(9). The method showed good system suitability, sensitivity, linearity, specificity, precision, stability and accuracy. All the seven water-soluble vitamins were well separated from other ingredients and degradation products. Method comparison indicated good concordance between the developed method and the USP method. The developed method was reliable and convenient for the rapid determination of VB(1), VB(3), VB(6), VC, VB(5), VB(2) and VB(9) in VMT. Copyright © 2012 Elsevier B.V. All rights reserved.

Evaluation of mobile phase characteristics on three zwitterionic columns in hydrophilic interaction liquid chromatography mode for liquid chromatography-high resolution mass spectrometry based untargeted metabolite profiling of Leishmania parasites.

PubMed

Zhang, Rong; Watson, David G; Wang, Lijie; Westrop, Gareth D; Coombs, Graham H; Zhang, Tong

2014-10-03

It has been reported that HILIC column chemistry has a great effect on the number of detected metabolites in LC-HRMS-based untargeted metabolite profiling studies. However, no systematic investigation has been carried out with regard to the optimisation of mobile phase characteristics. In this study using 223 metabolite standards, we explored the retention mechanisms on three zwitterionic columns with varied mobile phase composition, demonstrated the interference from poor chromatographic peak shapes on the output of data extraction, and assessed the quality of chromatographic signals and the separation of isomers under each LC condition. As expected, on the ZIC-cHILIC column the acidic metabolites showed improved chromatographic performance at low pH which can be attributed to the opposite arrangement of the permanently charged groups on this column in comparison with the ZIC-HILIC column. Using extracts from the protozoan parasite Leishmania, we compared the numbers of repeatedly detected LC-HRMS features under different LC conditions with putative identification of metabolites not amongst the standards being based on accurate mass (±3ppm). Besides column chemistry, the pH of the mobile phase plays a key role in not only determining the retention mechanisms of solutes but also the output of the LC-HRMS data processing. Fast evaporation of ammonium carbonate produced less ion suppression in ESI source and consequently improved the detectability of the metabolites in low abundance in comparison with other ammonium salts. Our results show that the combination of a ZIC-pHILIC column with an ammonium carbonate mobile phase, pH 9.2, at 20mM in the aqueous phase or 10mM in both aqueous and organic mobile phase components, provided the most suitable LC conditions for LC-HRMS-based untargeted metabolite profiling of Leishmania parasite extracts. The signal reliability of the mass spectrometer used in this study (Exactive Orbitrap) was also investigated. Copyright © 2014

Trying to detect gas-phase ions? Understanding Ion Mobility Spectrometry

PubMed Central

Cumeras, R.; Figueras, E.; Davis, C.E.; Baumbach, J.I.; Gràcia, I.

2014-01-01

Ion Mobility Spectrometry (IMS) is a widely used and ‘well-known’ technique of ion separation in gaseous phase based on the differences of ion mobilities under an electric field. This technique has received increased interest over the last several decades as evidenced by the pace and advances of new IMS devices available. In this review we explore the hyphenated techniques that are used with IMS, especially mass spectrometry as identification approach and multi-capillary column as pre-separation approach. Also, we will pay special attention to the key figures of merit of the ion mobility spectrum and how data is treated, and the influences of the experimental parameters in both a conventional drift time IMS (DTIMS) and a miniaturized IMS also known as high Field Asymmetric IMS (FAIMS) in the planar configuration. The current review article is preceded by a companion review article which details the current instrumentation and to the sections that configures both a conventional DTIMS and FAIMS devices. Those reviews will give the reader an insightful view of the main characteristics and aspects of the IMS technique. PMID:25465248

A weak cation-exchange monolith as stationary phase for the separation of peptide diastereomers by CEC.

PubMed

Ludewig, Ronny; Nietzsche, Sandor; Scriba, Gerhard K E

2011-01-01

A CEC weak cation-exchange monolith has been prepared by in situ polymerization of acrylamide, methylenebisacrylamide and 4-acrylamidobutyric acid in a decanol-dimethylsulfoxide mixture as porogen. The columns were evaluated by SEM and characterized with regard to the separation of diastereomers and α/β-isomers of aspartyl peptides. Column preparation was reproducible as evidenced by comparison of the analyte retention times of several columns prepared simultaneously. Analyte separation was achieved using mobile phases consisting of acidic phosphate buffer and ACN. Under these conditions the peptides migrated due to their electrophoretic mobility but the EOF also contributed as driving force as a function of the pH of the mobile phase due to increasing dissociation of the carboxyl groups of the polymer. Raising the pH of the mobile phase also resulted in deprotonation of the peptides reducing analyte mobility. Due to these mechanisms each pair of diastereomeric peptides displayed the highest resolution at a different pH of the buffer component of the mobile phase. Comparing the weak-cation exchange monolith to an RP monolith and a strong cation-exchange monolith different elution order of some peptide diastereomers was observed, clearly illustrating that interactions with the stationary phase contribute to the CEC separations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interactive Computer-Assisted Instruction in Acid-Base Physiology for Mobile Computer Platforms

ERIC Educational Resources Information Center

Longmuir, Kenneth J.

2014-01-01

In this project, the traditional lecture hall presentation of acid-base physiology in the first-year medical school curriculum was replaced by interactive, computer-assisted instruction designed primarily for the iPad and other mobile computer platforms. Three learning modules were developed, each with ~20 screens of information, on the subjects…

Electron mobility enhancement in ZnO thin films via surface modification by carboxylic acids

NASA Astrophysics Data System (ADS)

Spalenka, Josef W.; Gopalan, Padma; Katz, Howard E.; Evans, Paul G.

2013-01-01

Modifying the surface of polycrystalline ZnO films using a monolayer of organic molecules with carboxylic acid attachment groups increases the field-effect electron mobility and zero-bias conductivity, resulting in improved transistors and transparent conductors. The improvement is consistent with the passivation of defects via covalent bonding of the carboxylic acid and is reversible by exposure to a UV-ozone lamp. The properties of the solvent used for the attachment are crucial because solvents with high acid dissociation constants (Ka) for carboxylic acids lead to high proton activities and etching of the nanometers-thick ZnO films, masking the electronic effect.

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.

Analysis of iodinated haloacetic acids in drinking water by reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry with large volume direct aqueous injection.

PubMed

Li, Yongtao; Whitaker, Joshua S; McCarty, Christina L

2012-07-06

A large volume direct aqueous injection method was developed for the analysis of iodinated haloacetic acids in drinking water by using reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry in the negative ion mode. Both the external and internal standard calibration methods were studied for the analysis of monoiodoacetic acid, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid in drinking water. The use of a divert valve technique for the mobile phase solvent delay, along with isotopically labeled analogs used as internal standards, effectively reduced and compensated for the ionization suppression typically caused by coexisting common inorganic anions. Under the optimized method conditions, the mean absolute and relative recoveries resulting from the replicate fortified deionized water and chlorinated drinking water analyses were 83-107% with a relative standard deviation of 0.7-11.7% and 84-111% with a relative standard deviation of 0.8-12.1%, respectively. The method detection limits resulting from the external and internal standard calibrations, based on seven fortified deionized water replicates, were 0.7-2.3 ng/L and 0.5-1.9 ng/L, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

High-performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide-based chiral columns and polar organic mobile phases.

PubMed

Matarashvili, Iza; Shvangiradze, Iamze; Chankvetadze, Lali; Sidamonidze, Shota; Takaishvili, Nino; Farkas, Tivadar; Chankvetadze, Bezhan

2015-12-01

The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide-based chiral columns in high-performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Determination of ferulic acid in chuanxiong and in animal serum and cerebrospinal fluid by reversed-phase high performance liquid chromatography].

PubMed

Lü, K; Ding, M Y; Li, H X; Liu, D L

2000-11-01

An easy, rapid and sensitive method for the determination of ferulic acid(FA) in Chuanxiong extracts, animal (mouse) serum and cerebrospinal fluid by RP-HPLC has been developed. The FA was separated on an ODS column, Nova-Pak C18(3.9 mm i.d. x 150 mm) and detected at the wavelength of 320 nm. The mobile phase was methanol-water-acetic acid (35:65:0.5, V/V), with a flow rate of 0.8 mL/min. The detection limit of FA was 1.7 micrograms/L(S/N = 3) and the calibration curve was linear within the range of 0.85 mg/L-4.00 mg/L(r = 0.99904, n = 6). The mean recovery from animal serum and cerebrospinal was 95%-102%.

An innovative monolithic zwitterionic stationary phase for the separation of phenolic acids in coffee bean extracts by capillary electrochromatography.

PubMed

Murauer, Adele; Bakry, Rania; Schottenberger, Herwig; Huck, Christian; Ganzera, Markus

2017-04-22

A methacrylate based monolith, containing the innovative zwitterionic monomer (3-allyl-1-imidazol)propane sulfonate, was prepared in 100 μm I.D. silica capillaries by UV initiated photo-polymerization. Composition of the porogen, i.e. a mixture of 1-propanol, 1,4 butanediol and water, was of great importance to obtain a homogeneous monolith with satisfactory permeability and good electrochromatographic performance. Morphology of the stationary phase was studied in Scanning Electron Microscopy and IR experiments, which revealed a good attachment to the capillary wall, flowthrough-pores in the range of 0.5-2 μm, and a continuous monolithic structure. The developed material was well suited for the analysis of six common phenolic acids (salicylic, cinnamic, syringic, rosmarinic, caffeic and chlorogenic acid) by CEC. Their separation was possible in less than 8 min with a mobile phase comprising a 12 mM aqueous ammonium acetate solution with pH 8.5 and acetonitrile, at an applied voltage of - 20 kV. The developed method was validated (R 2  ≥ 0.995; LOD ≤ 3.9 μg mL -1 , except for salicylic acid; recovery rates from 94 to 104%) and successfully used for the determination of phenolic acids in Coffea arabica samples. All of them contained cinnamic, syringic and caffeic acid, however only in unroasted coffee beans chlorogenic acid (0.06%) was found. The quantitative results were in good agreement to reported literature data. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Packed-column capillary electrochromatography and capillary electrochromatography-mass spectrometry using a lithocholic acid stationary phase

PubMed Central

Norton, Dean; Shamsi, Shahab A.

2009-01-01

The preparation and characterization of a novel lithocholic acid (LCA)-based liquid crystalline (LC) stationary phase (SP) suitable for application in packed-column CEC and CEC coupled to MS is described. The extent of bonding reactions of LCA-SP was assessed using 1H-NMR, 13C-NMR and elemental analysis. This characterization is followed by application of the LCA-SP for separation of β-blockers, phenylethylamines (PEAs), polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Using the optimum mobile phase operating conditions (pH 3.0-4.5, 10 mM ammonium acetate, 85% v/v ACN), a comparison of the chromatographic ability of the aminopropyl silica phase vs. the LCA-bonded phase was conducted. The results showed improved selectivity for all test analytes using the latter phase. For example, the CEC-MS of β-blockers demonstrated that the LCA-bonded phase provides separation of six out of seven β-blockers, whereas the amino silica phase provides four peaks of several co-eluting β-blockers. For the CEC-MS analysis of PEAs, the LCA-bonded phase showed improved resolution and different selectivity as compared to the aminopropyl phase. An evaluation of the retention trends for PEAs on both phases suggested that the PEAs were retained based on varying degree of hydroxyl substitution on the aromatic ring. In addition, the MS characterization shows several PEAs fragment in the electrospray either by loss of an alkyl group and/or by loss of H2O. Finally, the LCA-bonded phase displayed significantly higher separation selectivity for PAHs and PCBs as compared to the amino silica phase. PMID:18425746

[Determination of chlorogenic acid, caffeic acid and linarin in Flos Chrysanthemi Indici from different places by RP-hPLC].

PubMed

Guo, Qiaosheng; Fang, Hailing; Shen, Haijin

2010-05-01

To evaluate the quality of Flos Chrysanthemi Indici which produced in twenty-two different producing places. Chlorogenic acid and caffeic acid were analyzed on a Shim-pack C8 colunm (4.6 mm x 250 mm, 5 microm) eluted with the mobile phase consisted of acetonitrile-0.5% phosphoric acid( 19:81). The detection wavelength was set at 326 nm. Linarin were eluted with the mobile phase consisted of methanol-water-acetic acid(26: 23: 1). The detection wavelength was set at 334 nm. The column temperature was 25 degrees C. The flow rate was 1.0 mL x min . The linear response ranged within 2.5-50 microg for chlorogenic acid (r = 0.998), 2.5-25 microg for caffeic acid (r = 0.998) and 4.97-41.47 microg for linarin (r = 0.999), respectively. Recoveries were 100.8% with RSD 2.1% for chlorogenic acid, 96.2% with RSD 2.3% for caffeic acid and 103.7% with RSD 1.8% for linarin. There was a significant difference in the content of chlorogenic acid, caffeic acid, linarin among the samples. The content of chlorogenic in the sample from Fengdou Chongqing city was the highest in those from other places. The content of caffeic acid in the all samples is very low. The content of linarin in the samples from Jiangsu province and Anhui province almost reached the national standard in pharmacopoeia.

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.

Silica-Based, Hyper-Crosslinked Acid Stable Stationary Phases for High Performance Liquid Chromatography

PubMed Central

Zhang, Yu; Luo, Hao; Carr, Peter W.

2011-01-01

A new family of Hyper-Crosslinked (HC) phases has been recently introduced for use under very aggressive acid conditions including those encountered in ultra-fast, high temperature Two-Dimensional Liquid Chromatography (2DLC). This type of stationary phase showed significantly enhanced acid and thermal stability compared to the most acid stable, commercial RPLC phases. In addition, the use of “orthogonal” chemistry to make surface-confined polymer networks ensures good reproducibility and high efficiency. One of the most interesting features of the HC phases is the ability to derivatize the surface aromatic groups with various functional groups. This led to the development of a family of hyper-crosslinked phases possessing a wide variety of chromatographic selectivities by attaching hydrophobic (e.g. –C8), ionizable (e.g. -COOH, -SO3H), aromatic (e.g. –toluene) or polar (e.g. -OH) species to the aromatic polymer network. HC reversed phases with various degrees of hydrophobicity and mixed-mode HC phases with added strong and weak cation exchange sites have been synthesized, characterized and applied. These silica-based acid-stable HC phases, with their attractive chromatographic properties, should be very useful in the separations of bases or biological analytes in acidic media, especially at elevated temperatures. This work reviews the prior research on HC phases and introduces a novel HC phase made by alternative chemistry. PMID:21906745

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.

Enhanced detection of amino acids in hydrophilic interaction chromatography electrospray tandem mass spectrometry with carboxylic acids as mobile phase additives.

PubMed

Yin, Dengyang; Hu, Xunxiu; Liu, Dantong; Du, Wencheng; Wang, Haibo; Guo, Mengzhe; Tang, Daoquan

2017-06-01

Liquid chromatography coupled with mass spectrometry technique has been widely used in the analysis of biological targets such as amino acids, peptides, and proteins. In this work, eight common single carboxylic acids or diacids, which contain different pKa have been investigated as the additives to the analysis of amino acids. As the results, carboxylic acid additive can improve the signal intensity of acidity amino acids such as Asp and Glu and the chromatographic separation of basic amino acids such as Arg, His, and Lys. In particular, the diacids have better performance than single acids. The proposed mechanism is that the diacid has hydrogen bond interaction with amino acids to reduce their polarity/amphiprotic characteristics. Besides, oxalic acid has been found having better enhancement than phthalic acid by overall consideration. Therefore, we successfully quantified the 15 amino acids in Sepia bulk pharmaceutical chemical by using oxalic acid as the additive.

Simultaneous determination of phenolic acids and flavonoids in rice using solid-phase extraction and RP-HPLC with photodiode array detection.

PubMed

Irakli, Maria N; Samanidou, Victoria F; Biliaderis, Costas G; Papadoyannis, Ioannis N

2012-07-01

An analytical method based on an optimized solid-phase extraction procedure and followed by high-performance liquid chromatography (HPLC) separation with diode array detection was developed and validated for the simultaneous determination of phenolic acids (gallic, protocatechuic, 4-hydroxy-benzoic, vanillic, caffeic, syringic, p-coumaric, ferulic, sinapic, and cinnamic acids), flavanols (catechin and epicatechin), flavonols (myricetin, quercetin, kaempferol, quercetin-3-O-glucoside, hyperoside, and rutin), flavones (luteolin and apigenin) and flavanones (naringenin and hesperidin) in rice flour (Oryza sativa L.). Chromatographic separation was carried out on a PerfectSil Target ODS-3 (250 mm × 4.6 mm, 3 μm) column at temperature 25°C using a mobile phase, consisting of 0.5% (v/v) acetic acid in water, methanol, and acetonitrile at a flow rate 1 mL min(-1) , under gradient elution conditions. Application of optimum extraction conditions, elaborated on both Lichrolut C(18) and Oasis HLB cartridges, have led to extraction of phenolic acids and flavonoids from rice flour with mean recoveries 84.3-113.0%. The developed method was validated in terms of linearity, accuracy, precision, stability, and sensitivity. Repeatability (n = 5) and inter-day precision (n = 4) revealed relative standard deviation (RSD) <13%. The optimized method was successfully applied to the analysis of phenolic acids and flavonoids in pigmented (red and black rice) and non-pigmented rice (brown rice) samples. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two Phase Admission Control for QoS Mobile Ad Hoc Networks

NASA Astrophysics Data System (ADS)

Chen, Chien-Sheng; Su, Yi-Wen; Liu, Wen-Hsiung; Chi, Ching-Lung

In this paper a novel and effective two phase admission control (TPAC) for QoS mobile ad hoc networks is proposed that satisfies the real-time traffic requirements in mobile ad hoc networks. With a limited amount of extra overhead, TPAC can avoid network congestions by a simple and precise admission control which blocks most of the overloading flow-requests in the route discovery process. When compared with previous QoS routing schemes such as QoS-aware routing protocol and CACP protocols, it is shown from system simulations that the proposed scheme can increase the system throughput and reduce both the dropping rate and the end-to-end delay. Therefore, TPAC is surely an effective QoS-guarantee protocol to provide for real-time traffic.

Model-based identification of optimal operating conditions for amino acid simulated moving bed enantioseparation using a macrocyclic glycopeptide stationary phase.

PubMed

Fuereder, Markus; Majeed, Imthiyas N; Panke, Sven; Bechtold, Matthias

2014-06-13

Teicoplanin aglycone columns allow efficient separation of amino acid enantiomers in aqueous mobile phases and enable robust and predictable simulated moving bed (SMB) separation of racemic methionine despite a dependency of the adsorption behavior on the column history (memory effect). In this work we systematically investigated the influence of the mobile phase (methanol content) and temperature on SMB performance using a model-based optimization approach that accounts for methionine solubility, adsorption behavior and back pressure. Adsorption isotherms became more favorable with increasing methanol content but methionine solubility was decreased and back pressure increased. Numerical optimization suggested a moderate methanol content (25-35%) for most efficient operation. Higher temperature had a positive effect on specific productivity and desorbent requirement due to higher methionine solubility, lower back pressure and virtually invariant selectivity at high loadings of racemic methionine. However, process robustness (defined as a difference in flow rate ratios) decreased strongly with increasing temperature to the extent that any significant increase in temperature over 32°C will likely result in operating points that cannot be realized technically even with the lab-scale piston pump SMB system employed in this study. Copyright © 2014. Published by Elsevier B.V.

Determination of the Acid Dissociation Constant of a Phenolic Acid by High Performance Liquid Chromatography: An Experiment for the Upper Level Analytical Chemistry Laboratory

ERIC Educational Resources Information Center

Raboh, Ghada

2018-01-01

A high performance liquid chromatography (HPLC) experiment for the upper level analytical chemistry laboratory is described. The students consider the effect of mobile-phase composition and pH on the retention times of ionizable compounds in order to determine the acid dissociation constant, K[subscript a], of a phenolic acid. Results are analyzed…

77 FR 14012 - Eligible Telecommunications Carrier Designation for Participation in Mobility Fund Phase I

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-08

...; DA 12-271] Eligible Telecommunications Carrier Designation for Participation in Mobility Fund Phase I... Wireless Telecommunications and Wireline Competition Bureaus describe the process and requirements for applicants seeking Eligible Telecommunications Carrier (ETC) Designation from the Commission for...

A High Omega-3 Fatty Acid Multinutrient Supplement Benefits Cognition and Mobility in Older Women: A Randomized, Double-blind, Placebo-controlled Pilot Study.

PubMed

Strike, Siobhán C; Carlisle, Alison; Gibson, E Leigh; Dyall, Simon C

2016-02-01

Mobility is a key determinant of frailty in older persons, and a variety of dietary factors, such as the omega-3 fatty acid docosahexaenoic acid (DHA), are positively associated with decreased frailty and improved mobility and cognition in older persons. The effects of a multinutrient supplement on mobility and cognition were assessed in postmenopausal women (60-84 years). Participants received either Efalex Active 50+ (1g DHA, 160 mg eicosapentaenoic acid, 240 mg Ginkgo biloba, 60 mg phosphatidylserine, 20mg d-α tocopherol, 1mg folic acid, and 20 µg vitamin B12 per day; N = 15) or placebo (N = 12) for 6 months. Mobility was assessed by VICON 9 motion capture camera system synchronized with Kistler force plates, cognitive performance by computerized cognitive function tests, and blood fatty acid levels by pin-prick analysis. Significant effects of treatment were seen in two of the four cognitive tests, with shorter mean latencies in a motor screening task (p < .05) and more words remembered (p < .03), and one of the three primary mobility measures with improved habitual walking speed (p < .05). Compared with the placebo group, supplementation also resulted in significantly higher blood DHA levels (p < .02). In this pilot study, multinutrient supplementation improved cognition and mobility in able older females at clinically relevant levels, suggesting a potential role in reducing the decline to frailty. © The Author 2015. Published by Oxford University Press on behalf of The Gerontological Society of America.

77 FR 38803 - Mobility Fund Phase I Auction Updated Data For Auction 901

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-29

... FEDERAL COMMUNICATIONS COMMISSION [AU Docket No. 12-25; DA 12-990] Mobility Fund Phase I Auction Updated Data For Auction 901 AGENCY: Federal Communications Commission. ACTION: Notice. SUMMARY: In this... blocks. The map is a visual representation of data from the Attachment A files, which contain more...

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.

Relationship between Acute Phase Proteins and Serum Fatty Acid Composition in Morbidly Obese Patients

PubMed Central

Fernandes, Ricardo; Beserra, Bruna Teles Soares; Cunha, Raphael Salles Granato; Hillesheim, Elaine; Camargo, Carolina de Quadros; Pequito, Danielle Cristina Tonello; de Castro, Isabela Coelho; Fernandes, Luiz Cláudio; Nunes, Everson Araújo; Trindade, Erasmo Benício Santos de Moraes

2013-01-01

Background. Obesity is considered a low-grade inflammatory state and has been associated with increased acute phase proteins as well as changes in serum fatty acids. Few studies have assessed associations between acute phase proteins and serum fatty acids in morbidly obese patients. Objective. To investigate the relationship between acute phase proteins (C-Reactive Protein, Orosomucoid, and Albumin) and serum fatty acids in morbidly obese patients. Methods. Twenty-two morbidly obese patients were enrolled in this study. Biochemical and clinical data were obtained before bariatric surgery, and fatty acids measured in preoperative serum. Results. Orosomucoid was negatively correlated with lauric acid (P = 0.027) and eicosapentaenoic acid (EPA) (P = 0.037) and positively with arachidonic acid (AA) (P = 0.035), AA/EPA ratio (P = 0.005), and n-6/n-3 polyunsaturated fatty acids ratio (P = 0.035). C-Reactive Protein (CRP) was negatively correlated with lauric acid (P = 0.048), and both CRP and CRP/Albumin ratio were negatively correlated with margaric acid (P = 0.010, P = 0.008, resp.). Albumin was positively correlated with EPA (P = 0.027) and margaric acid (P = 0.008). Other correlations were not statistically significant. Conclusion. Our findings suggest that serum fatty acids are linked to acute phase proteins in morbidly obese patients. PMID:24167354

Gradient enhanced-fluidity liquid hydrophilic interaction chromatography of ribonucleic acid nucleosides and nucleotides: A "green" technique.

PubMed

Beilke, Michael C; Beres, Martin J; Olesik, Susan V

2016-03-04

A "green" hydrophilic interaction liquid chromatography (HILIC) technique for separating the components of mixtures with a broad range of polarities is illustrated using enhanced-fluidity liquid mobile phases. Enhanced-fluidity liquid chromatography (EFLC) involves the addition of liquid CO2 to conventional liquid mobile phases. Decreased mobile phase viscosity and increased analyte diffusivity results when a liquefied gas is dissolved in common liquid mobile phases. The impact of CO2 addition to a methanol:water (MeOH:H2O) mobile phase was studied to optimize HILIC gradient conditions. For the first time a fast separation of 16 ribonucleic acid (RNA) nucleosides/nucleotides was achieved (16min) with greater than 1.3 resolution for all analyte pairs. By using a gradient, the analysis time was reduced by over 100% compared to similar separations conducted under isocratic conditions. The optimal separation using MeOH:H2O:CO2 mobile phases was compared to MeOH:H2O and acetonitrile:water (ACN:H2O) mobile phases. Based on chromatographic performance parameters (efficiency, resolution and speed of analysis) and an assessment of the environmental impact of the mobile phase mixtures, MeOH:H2O:CO2 mixtures are preferred over ACN:H2O or MeOH:H2O mobile phases for the separation of mixtures of RNA nucleosides and nucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Diffusivity of dicarboxylic acids molecules to secondary organic material governed by particle phase state

NASA Astrophysics Data System (ADS)

Han, Y.; Gong, Z.; Liu, P.; de Sá, S. S.; McKinney, K. A.; Martin, S. T.

2017-12-01

Atmospheric secondary organic material (SOM) from oxidation of volatile organic compounds can exist in amorphous solid, semisolid, and liquid states depending on a range of factors such as relative humidity (RH), temperature, and reaction history. The phase state of SOM affects the dynamic exchange and reactivity between particles and gas-phase molecules. Dicarboxylic acids are ubiquitous in ambient atmosphere and the uptake of which may lead to substantial changes in hygroscopicity, absorption property, and light scattering of aerosol particles. This study investigates the diffusivity of dicarboxylic acids to the matrix of SOM particles. SOM was generated from dark ozonolysis of a-pinene in Harvard Environmental Chamber. The produced SOM particles were passed through an ozone scrubber to remove gas-phase chemistry before being led into a flask reactor, where gas-phase dicarboxylic acid was injected continuously and RH was varied from 5% to 85%. The probe dicarboxylic acids molecules including malonic acid and a-ketoglutaric acid have been investigated for the uptake to SOM particles. Organic composition in the outflow of the flask was measured with a high-resolution time-of-flight aerosol mass spectrometer. The mass fractions of tracer ions in total organic mass for both malonic acid and a-ketoglutaric acid increased substantially with the increase of RH values. The tracer ions of malonic acid were also more abundant in a-pinene SOM particles with increased gas-phase concentrations. These results suggest that the diffusion of the studied dicarboxylic acids molecules to a-pinene SOM particles was enhanced at increased RH values, which is possibly due to the phase transition of a-pinene SOM particles from non-liquid to liquid states. Therefore, particle phase state may be an important factor governing the diffusivity of dicarboxylic acids molecules to a-pinene SOM. Further dicarboxylic acids with various functional groups will be investigated to understand the

Observations of a high-pressure phase creation in oleic acid

NASA Astrophysics Data System (ADS)

Kościesza, R.; Kulisiewicz, L.; Delgado, A.

2010-03-01

Oleic acid is one of the unsaturated fatty acids which frequently appears in food products such as edible fats and oils. A molecule of oleic acid possesses a double carbon bond, C=C, which is responsible for a transition to a new phase when pressure is applied. This work presents the results of optical observations of such a transition. The observations were made in two cases, the first being static p-T conditions under 60 MPa at 20°C and the other the dynamic application of the pressure up to 350 MPa. The obtained visualization reveals differences in the creation of the phase and in its further appearance. Some crystal forms may be recognized. These results tend to be of interest for food engineers due to increasing interest in high-pressure food preservation among nutritionists and medical scientists concerned with fatty acids.

Preparation, characterization and application of a reversed phase liquid chromatography/hydrophilic interaction chromatography mixed-mode C18-DTT stationary phase.

PubMed

Wang, Qing; Long, Yao; Yao, Lin; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2016-01-01

A mixed-mode chromatographic stationary phase, C18-DTT (dithiothreitol) silica (SiO2) was prepared through "thiol-ene" click chemistry. The obtained material was characterized by fourier transform infrared spectroscope, nitrogen adsorption analysis and contact angle analysis. Chromatographic performance of the C18-DTT was systemically evaluated by studying the effect of acetonitrile content, pH, buffer concentration of the mobile phase and column temperature. It was demonstrated that the novel stationary phase possessed reversed phase liquid chromatography (RPLC)/hydrophilic interaction liquid chromatography (HILIC) mixed-mode property. The stop-flow test revealed that C18-DTT exhibited excellent compatibility with 100% aqueous mobile phase. Additionally, the stability and column-to-column reproducibility of the C18-DTT material were satisfactory, with relative standard deviations of retention factor of the tested analytes (verapamil, fenbufen, guanine, tetrandrine and nicotinic acid) in the range of 1.82-3.72% and 0.85-1.93%, respectively. Finally, the application of C18-DTT column was demonstrated in the separation of non-steroidal anti-inflammatory drugs, aromatic carboxylic acids, alkaloids, nucleo-analytes and polycyclic aromatic hydrocarbons. It had great resolving power in the analysis of various compounds in HILIC and RPLC chromatographic conditions and was a promising RPLC/HILIC mixed-mode stationary phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

PubMed

Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

2011-12-28

We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE PAGES

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary; ...

2017-09-21

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

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

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 3. Relating Solution-Phase to Gas-Phase Structures.

PubMed

Kondalaji, Samaneh Ghassabi; Khakinejad, Mahdiar; Valentine, Stephen J

2018-06-01

Molecular dynamics (MD) simulations have been utilized to study peptide ion conformer establishment during the electrospray process. An explicit water model is used for nanodroplets containing a model peptide and hydronium ions. Simulations are conducted at 300 K for two different peptide ion charge configurations and for droplets containing varying numbers of hydronium ions. For all conditions, modeling has been performed until production of the gas-phase ions and the resultant conformers have been compared to proposed gas-phase structures. The latter species were obtained from previous studies in which in silico candidate structures were filtered according to ion mobility and hydrogen-deuterium exchange (HDX) reactivity matches. Results from the present study present three key findings namely (1) the evidence from ion production modeling supports previous structure refinement studies based on mobility and HDX reactivity matching, (2) the modeling of the electrospray process is significantly improved by utilizing initial droplets existing below but close to the calculated Rayleigh limit, and (3) peptide ions in the nanodroplets sample significantly different conformers than those in the bulk solution due to altered physicochemical properties of the solvent. Graphical Abstract ᅟ.

Computational findings of metastable ferroelectric phases of squaric acid

NASA Astrophysics Data System (ADS)

Ishibashi, Shoji; Horiuchi, Sachio; Kumai, Reiji

2018-05-01

Antiferroelectric-to-ferroelectric transitions in squaric acid are simulated by computationally applying a static electric field. Depending on the direction of the electric field, two different metastable ferroelectric (and piezoelectric) phases have been found. One of them corresponds to the experimentally confirmed phase, whereas the other is an optimally polarized phase. The structural details of these phases have been determined as a function of the electric field. The spontaneous polarization values of the phases are 14.5 and 20.5 μ C /cm2, respectively, and are relatively high among those of the existing organic ferroelectrics.

Quantitation of antihistamines in pharmaceutical preparations by liquid chromatography with a micellar mobile phase of sodium dodecyl sulfate and pentanol.

PubMed

Gil-Agustí, M; Monferrer-Pons, L; Esteve-Romero, J; García-Alvarez-Coque, M C

2001-01-01

A reversed-phase liquid chromatographic procedure with a micellar mobile phase of sodium dodecyl sulfate (SDS), containing a small amount of pentanol, was developed for the control of 7 antihistamines of diverse action in pharmaceutical preparations (tablets, capsules, powders, solutions, and syrups): azatadine, carbinoxamine, cyclizine, cyproheptadine, diphenhydramine, doxylamine, and tripelennamine. The retention times of the drugs were <9 min with a mobile phase of 0.15M SDS-6% (v/v) pentanol. The recoveries with respect to the declared compositions were in the range of 93-110%, and the intra- and interday repeatabilities and interday reproducibility were <1.2%. The results were similar to those obtained with a conventional 60 + 40 (v/v) methanol-water mixture, with the advantage of reduced toxicity, flammability, environmental impact, and cost of the micellar-pentanol solutions. The lower risk of evaporation of the organic solvent dissolved in the micellar solutions also increased the stability of the mobile phase.

Cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase for the enantioseparation of drugs in supercritical fluid chromatography: comparison with HPLC.

PubMed

Kalíková, Květa; Martínková, Monika; Schmid, Martin G; Tesařová, Eva

2018-03-01

A cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase was studied as a tool for the enantioselective separation of 21 selected analytes with different pharmaceutical and physicochemical properties. The enantioseparations were performed using supercritical fluid chromatography. The effect of the mobile phase composition was studied. Four different additives (diethylamine, triethylamine, isopropylamine, and trifluoroacetic acid) and isopropylamine combined with trifluoroacetic acid were tested and their influence on enantioseparation was compared. The influence of two different mobile phase co-solvents (methanol and propan-2-ol) combined with all the additives was also evaluated. The best mobile phase compositions for the separation of the majority of enantiomers were CO 2 /methanol/isopropylamine 80:20:0.1 v/v/v or CO 2 /propan-2-ol/isopropylamine/trifluoroacetic acid 80:20:0.05:0.05 v/v/v/v. The best results were obtained from the group of basic β-blockers. A high-performance liquid chromatography separation system composed of the same stationary phase and mobile phase of similar properties prepared as a mixture of hexane/propan-2-ol/additive 80:20:0.1 v/v/v was considered for comparison. Supercritical fluid chromatography was found to yield better results, i.e. better enantioresolution for shorter analysis times than high-performance liquid chromatography. However, examples of enantiomers better resolved under the optimized conditions in high-performance liquid chromatography were also found. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of growth phase on the fatty acid compositions of four species of marine diatoms

NASA Astrophysics Data System (ADS)

Liang, Ying; Mai, Kangsen

2005-04-01

The fatty acid compositions of four species of marine diatoms ( Chaetoceros gracilis MACC/B13, Cylindrotheca fusiformis MACC/B211, Phaeodactylum tricornutum MACC/B221 and Nitzschia closterium MACC/B222), cultivated at 22°C±1°C with the salinity of 28 in f/2 medium and harvested in the exponential growth phase, the early stationary phase and the late stationary phase, were determined. The results showed that growth phase has significant effect on most fatty acid contents in the four species of marine diatoms. The proportions of 16:0 and 16:1n-7 fatty acids increased while those of 16:3n-4 and eicosapentaenoic acid (EPA) decreased with increasing culture age in all species studied. The subtotal of saturated fatty acids (SFA) increased with the increasing culture age in all species with the exception of B13. The subtotal of monounsaturated fatty acids (MUFA) increased while that of polyunsaturated fatty acids (PUFA) decreased with culture age in the four species of marine diatoms. MUFA reached their lowest value in the exponential growth phase, whereas PUFA reached their highest value in the same phase.

STTR Phase 1 Final Technical Report for Project Entitled "Developing a Mobile Torrefaction Machine"

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

James, Joseph J.

The goal of this project, sponsored by Agri-Tech Producers, LLC (ATP), the small business grantee, was to determine if the torrefaction technology, developed by North Carolina State University (NCSU), which ATP has licensed, could be feasibly deployed in a mobile unit. The study adds to the area investigated, by having ATP’s STTR Phase I team give thoughtful consideration to how to use NCSU’s technology in a mobile unit. The findings by ATP’s team were that NCSU’s technology would best perform in units 30’ by 80’ (See Spec Sheet for the Torre-Tech 5.0 Unit in the Appendix) and the technical effectivenessmore » and economic feasibility investigation suggested that such units were not easily, efficiently or safely utilized in a forest or farm setting. (Note rendering of possible mobile system in the Appendix) Therefore, the findings by ATP’s team were that NCSU’s technology could not feasibly be deployed as a mobile unit.« less

Molecular Dynamics Simulations on Gas-Phase Proteins with Mobile Protons: Inclusion of All-Atom Charge Solvation.

PubMed

Konermann, Lars

2017-08-31

Molecular dynamics (MD) simulations have become a key tool for examining the properties of electrosprayed protein ions. Traditional force fields employ static charges on titratable sites, whereas in reality, protons are highly mobile in gas-phase proteins. Earlier studies tackled this problem by adjusting charge patterns during MD runs. Within those algorithms, proton redistribution was subject to energy minimization, taking into account electrostatic and proton affinity contributions. However, those earlier approaches described (de)protonated moieties as point charges, neglecting charge solvation, which is highly prevalent in the gas phase. Here, we describe a mobile proton algorithm that considers the electrostatic contributions from all atoms, such that charge solvation is explicitly included. MD runs were broken down into 50 ps fixed-charge segments. After each segment, the electrostatics was reanalyzed and protons were redistributed. Challenges associated with computational cost were overcome by devising a streamlined method for electrostatic calculations. Avidin (a 504-residue protein complex) maintained a nativelike fold over 200 ns. Proton transfer and side chain rearrangements produced extensive salt bridge networks at the protein surface. The mobile proton technique introduced here should pave the way toward future studies on protein folding, unfolding, collapse, and subunit dissociation in the gas phase.

Polydopamine-coated magnetic molecularly imprinted polymer for the selective solid-phase extraction of cinnamic acid, ferulic acid and caffeic acid from radix scrophulariae sample.

PubMed

Yin, Yuli; Yan, Liang; Zhang, Zhaohui; Wang, Jing; Luo, Ningjing

2016-04-01

We describe novel cinnamic acid polydopamine-coated magnetic imprinted polymers for the simultaneous selective extraction of cinnamic acid, ferulic acid and caffeic acid from radix scrophulariae sample. The novel magnetic imprinted polymers were synthesized by surface imprinting polymerization using magnetic multi-walled carbon nanotubes as the support material, cinnamic acid as the template and dopamine as the functional monomer. The magnetic imprinted polymers were characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometry. The results revealed that the magnetic imprinted polymers had outstanding magnetic properties, high adsorption capacity, selectivity and fast kinetic binding toward cinnamic acid, ferulic acid and caffeic acid. Coupled with high-performance liquid chromatography, the extraction conditions of the magnetic imprinted polymers as a magnetic solid-phase extraction sorbent were investigated in detail. The proposed imprinted magnetic solid phase extraction procedure has been used for the purification and enrichment of cinnamic acid, ferulic acid and caffeic acid successfully from radix scrophulariae extraction sample with recoveries of 92.4-115.0% for cinnamic acid, 89.4-103.0% for ferulic acid and 86.6-96.0% for caffeic acid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application and comparison of high-speed countercurrent chromatography and high performance liquid chromatography in preparative enantioseparation of α-substitution mandelic acids

PubMed Central

Tong, Shengqiang; Zhang, Hu; Shen, Mangmang; Ito, Yoichiro; Yan, Jizhong

2014-01-01

Preparative enantioseparations of α-cyclopentylmandelic acid and α-methylmandelic acid by high-speed countercurrent chromatography (HSCCC) and high performance liquid chromatography (HPLC) were compared using hydroxypropy-β-cyclodextrin (HP-β-CD) and sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as the chiral mobile phase additives. In preparative HPLC the enantioseparation was achieved on the ODS C18 reverse phase column with the mobile phase composed of a mixture of acetonitrile and 0.10 mol L−1 phosphate buffer at pH 2.68 containing 20 mmol L−1 HP-β-CD for α-cyclopentylmandelic acid and 20 mmol L−1 SBE-β-CD for α-methylmandelic acid. The maximum sample size for α-cyclopentylmandelic acid and α-methylmandelic acid was only about 10 mg and 5 mg, respectively. In preparative HSCCC the enantioseparations of these two racemates were performed with the two-phase solvent system composed of n-hexane-methyl tert.-butyl ether-0.1 molL−1 phosphate buffer solution at pH 2.67 containing 0.1 mol L−1 HP-β-CD for α-cyclopentylmandelic acid (8.5:1.5:10, v/v/v) and 0.1 mol L−1 SBE-β-CD for α-methylmandelic acid (3:7:10, v/v/v). Under the optimum separation conditions, total 250 mg of racemic α-cyclopentylmandelic acid could be completely enantioseparated by HSCCC with HP-β-CD as a chiral mobile phase additive in a single run, yielding 105-110 mg of enantiomers with 95-98% purity and 85-90% recovery. But, no complete enantioseparation of α-methylmandelic acid was achieved by preparative HSCCC with either of the chiral selectors due to their limited enantioselectivity. In this paper preparative enantioseparation by HSCCC and HPLC was compared from various aspects. PMID:25983356

Application and comparison of high-speed countercurrent chromatography and high performance liquid chromatography in preparative enantioseparation of α-substitution mandelic acids.

PubMed

Tong, Shengqiang; Zhang, Hu; Shen, Mangmang; Ito, Yoichiro; Yan, Jizhong

2015-04-01

Preparative enantioseparations of α-cyclopentylmandelic acid and α-methylmandelic acid by high-speed countercurrent chromatography (HSCCC) and high performance liquid chromatography (HPLC) were compared using hydroxypropy-β-cyclodextrin (HP-β-CD) and sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as the chiral mobile phase additives. In preparative HPLC the enantioseparation was achieved on the ODS C 18 reverse phase column with the mobile phase composed of a mixture of acetonitrile and 0.10 mol L -1 phosphate buffer at pH 2.68 containing 20 mmol L -1 HP-β-CD for α-cyclopentylmandelic acid and 20 mmol L -1 SBE-β-CD for α-methylmandelic acid. The maximum sample size for α-cyclopentylmandelic acid and α-methylmandelic acid was only about 10 mg and 5 mg, respectively. In preparative HSCCC the enantioseparations of these two racemates were performed with the two-phase solvent system composed of n -hexane-methyl tert. -butyl ether-0.1 molL -1 phosphate buffer solution at pH 2.67 containing 0.1 mol L -1 HP-β-CD for α-cyclopentylmandelic acid (8.5:1.5:10, v/v/v) and 0.1 mol L -1 SBE-β-CD for α-methylmandelic acid (3:7:10, v/v/v). Under the optimum separation conditions, total 250 mg of racemic α-cyclopentylmandelic acid could be completely enantioseparated by HSCCC with HP-β-CD as a chiral mobile phase additive in a single run, yielding 105-110 mg of enantiomers with 95-98% purity and 85-90% recovery. But, no complete enantioseparation of α-methylmandelic acid was achieved by preparative HSCCC with either of the chiral selectors due to their limited enantioselectivity. In this paper preparative enantioseparation by HSCCC and HPLC was compared from various aspects.

Influence of lactic acid on the two-phase anaerobic digestion of kitchen wastes.

PubMed

Zhang, Bo; Cai, Wei-min; He, Pin-jing

2007-01-01

To evaluate the influence of lactic acid on the methanogenesis, anaerobic digestion of kitchen wastes was firstly conducted in a two-phase anaerobic digestion process, and performance of two digesters fed with lactic acid and glucose was subsequently compared. The results showed that the lactic acid was the main fermentation products of hydrolysis-acidification stage in the two-phase anaerobic digestion process for kitchen wastes. The lactic acid concentration constituted approximately 50% of the chemical oxygen demand (COD) concentration in the hydrolysis-acidification liquid. The maximum organic loading rate was lower in the digester fed with lactic acid than that fed with glucose. Volatile fatty acids (VFAs) and COD removal were deteriorated in the methanogenic reactor fed with lactic acid compared to that fed with glucose. The specific methanogenic activity (SMA) declined to 0.343 g COD/(gVSSxd) when the COD loading were designated as 18.8 g/(Lxd) in the digester fed with lactic acid. The propionic acid accumulation occurred due to the high concentration of lactic acid fed. It could be concluded that avoiding the presence of the lactic acid is necessary in the hydrolysis-acidification process for the improvement of the two-phase anaerobic digestion process of kitchen wastes.

Diffusion of tricarboxylic acid cycle enzymes in the mitochondrial matrix in vivo. Evidence for restricted mobility of a multienzyme complex.

PubMed

Haggie, Peter M; Verkman, A S

2002-10-25

It has been proposed that enzymes in many metabolic pathways, including the tricarboxylic acid cycle in the mitochondrial matrix, are physically associated to facilitate substrate channeling and overcome diffusive barriers. We have used fluorescence recovery after photobleaching to measure the diffusional mobilities of chimeras consisting of green fluorescent protein (GFP) fused to the C terminus of four tricarboxylic acid cycle enzymes: malate dehydrogenase, citrate synthase, isocitrate dehydrogenase, and succinyl-CoA synthetase. The GFP-enzyme chimeras were localized selectively in the mitochondrial matrix in transfected Chinese hamster ovary (CHO) and COS7 cells. Laser photobleaching using a 0.7-microm diameter spot demonstrated restricted diffusion of the GFP-enzyme chimeras. Interestingly, all four chimeras had similar diffusional characteristics, approximately 45% of each chimera was mobile and had a diffusion coefficient of 4 x 10(-8) cm(2)/s. In contrast, unconjugated GFP in the mitochondrial matrix (targeted using COX8 leader sequence) diffused freely (nearly 100% mobility) with a greater diffusion coefficient of 20 x 10(-8) cm(2)/s. The mobility of the GFP-enzyme chimeras was insensitive to substrate source, ATP depletion, or inhibition of the adenine nucleotide translocase. These results indicate similar mobility characteristics of unrelated tricarboxylic acid cycle enzymes having different sizes and physical properties, providing biophysical evidence for a diffusible multienzyme complex in the mitochondrial matrix.

Hydrophilic interaction liquid chromatography-mass spectrometry of (lyso)phosphatidic acids, (lyso)phosphatidylserines and other lipid classes.

PubMed

Cífková, Eva; Hájek, Roman; Lísa, Miroslav; HolĿapek, Michal

2016-03-25

The goal of this work is a systematic optimization of hydrophilic interaction liquid chromatography (HILIC) separation of acidic lipid classes (namely phosphatidic acids-PA, lysophosphatidic acids-LPA, phosphatidylserines-PS and lysophosphatidylserines-LPS) and other lipid classes under mass spectrometry (MS) compatible conditions. The main parameters included in this optimization are the type of stationary phases used in HILIC, pH of the mobile phase, the type and concentration of mobile phase additives. Nine HILIC columns with different chemistries (unmodified silica, modified silica using diol, 2-picolylamine, diethylamine and 1-aminoanthracene and hydride silica) are compared with the emphasis on peak shapes of acidic lipid classes. The optimization of pH is correlated with the theoretical calculation of acidobasic equilibria of studied lipid classes. The final method using the hydride column, pH 4 adjusted by formic acid and the gradient of acetonitrile and 40 mmol/L of aqueous ammonium formate provides good peak shapes for all analyzed lipid classes including acidic lipids. This method is applied for the identification of lipids in real samples of porcine brain and kidney extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

Tandem differential mobility analysis-mass spectrometry reveals partial gas-phase collapse of the GroEL complex.

PubMed

Hogan, Christopher J; Ruotolo, Brandon T; Robinson, Carol V; Fernandez de la Mora, Juan

2011-04-07

A parallel-plate differential mobility analyzer and a time-of-flight mass spectrometer (DMA-MS) are used in series to measure true mobility in dry atmospheric pressure air for mass-resolved electrosprayed GroEL tetradecamers (14-mers; ~800 kDa). Narrow mobility peaks are found (2.6-2.9% fwhm); hence, precise mobilities can be obtained for these ions without collisional activation, just following their generation by electrospray ionization. In contrast to previous studies, two conformers are found with mobilities (Z) differing by ~5% at charge state z ~ 79. By extrapolating to small z, a common mobility/charge ratio Z(0)/z = 0.0117 cm(2) V(-1) s(-1) is found for both conformers. When interpreted as if the GroEL ion surface were smooth and the gas molecule-protein collisions were perfectly elastic and specular, this mobility yields an experimental collision cross section, Ω, 11% smaller than in an earlier measurement, and close to the cross section, A(C,crystal), expected for the crystal structure (determined by a geometric approximation). However, the similarity between Ω and A(C,crystal) does not imply a coincidence between the native and gas-phase structures. The nonideal nature of protein-gas molecule collisions introduces a drag enhancement factor, ξ = 1.36, with which the true cross section A(C) is related to Ω via A(C) = Ω/ξ. Therefore, A(C) for GroEL 14-mer ions determined by DMA measurements is 0.69A(C,crystal). The factor 1.36 used here is based on the experimental Stokes-Millikan equation, as well as on prior and new numerical modeling accounting for multiple scattering events via exact hard-sphere scattering calculations. Therefore, we conclude that the gas-phase structure of the GroEL complex as electrosprayed is substantially more compact than the corresponding X-ray crystal structure.

Use of itaconic acid-based polymers for solid-phase extraction of deoxynivalenol and application to pasta analysis.

PubMed

Pascale, Michelangelo; De Girolamo, Annalisa; Visconti, Angelo; Magan, Naresh; Chianella, Iva; Piletska, Elena V; Piletsky, Sergey A

2008-02-25

Molecular modelling and computational design were used to identify itaconic acid (IA) as a functional monomer with high affinity towards deoxynivalenol (DON), a Fusarium-toxin frequently occurring in cereals. IA-based polymers were photochemically synthesised in dimethyl formamide (porogen) using ethylenglycol dimethacrylate as cross-linker and 1,1'-azo-bis(cyclohexane carbonitrile) as initiator, and the relevant binding interactions with DON in solvents with different polarity were investigated. The performances of the non-imprinted IA-based polymer (blank polymer, BP) and the corresponding molecularly imprinted polymer (MIP) were compared using DON as a template. Both BP and MIP were able to bind about 90% DON either in toluene, water or water containing 5% polyethylene glycol. Non-imprinted polymers with different molar ratios of IA to cross-linker were evaluated as adsorbents for solid-phase extraction (SPE) clean-up and pre-concentration of DON from wheat and pasta samples prior to HPLC analysis. Samples were extracted with PBS/0.1M EDTA solution and cleaned up through a cartridge containing blank IA-based polymer. The column was washed with PBS (pH 9.2) and the toxin was eluted with methanol and quantified by reversed-phase HPLC with UV detector (lambda=220nm), using methanol:water:acetic acid (15:85:0.1, v/v/v) as the mobile phase. Effective removal of matrix interferences was observed only for pasta with DON recoveries higher than 70% (RSD<7%, n=3) at levels close to or higher than EU regulatory limit.

Gas-phase hydration of glyoxylic acid: Kinetics and atmospheric implications.

PubMed

Liu, Ling; Zhang, Xiuhui; Li, Zesheng; Zhang, Yunhong; Ge, Maofa

2017-11-01

Oxocarboxylic acids are one of the most important organic species found in secondary organic aerosols and can be detected in diverse environments. But the hydration of oxocarboxylic acids in the atmosphere has still not been fully understood. Neglecting the hydration of oxocarboxylic acids in atmospheric models may be one of the most important reasons for the significant discrepancies between field measurements and abundance predictions of atmospheric models for oxocarboxylic acids. In the present paper, glyoxylic acid, as the most abundant oxocarboxylic acids in the atmosphere, has been selected as an example to study whether the hydration process can occur in the atmosphere and what the kinetic process of hydration is. The gas-phase hydration of glyoxylic acid to form the corresponding geminal diol and those catalyzed by atmospheric common substances (water, sulfuric acid and ammonia) have been investigated at the CCSD(T)-F12/cc-pVDZ-F12//M06-2X/6-311++G(3df,3pd) level of theory. The contour map of electron density difference of transition states have been further analyzed. It is indicated that these atmospheric common substances can all catalyze on the hydration to some extent and sulfuric acid is the most effective reducing the Gibbs free energy of activation to 9.48 kcal/mol. The effective rate constants combining the overall rate constants and concentrations of the corresponding catalysts have shown that water and sulfuric acid are both important catalysts and the catalysis of sulfuric acid is the most effective for the gas-phase hydration of glyoxylic acid. This catalyzed processes are potentially effective in coastal regions and polluted regions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of three low-molecular-weight organic acids (LMWOAs) and pH on the mobilization of arsenic and heavy metals (Cu, Pb, and Zn) from mine tailings.

PubMed

Wang, Suiling; Mulligan, Catherine N

2013-02-01

Natural organic acids may play an important role in influencing the mobility of toxic contaminants in the environment. The mobilization of arsenic (As) and heavy metals from an oxidized Pb-Zn mine tailings sample in the presence of three low-molecular-weight organic acids, aspartic acid, cysteine, and succinic acid, was investigated at a mass ratio of 10 mg organic additive/g mine tailings in this study. The effect of pH was also evaluated. The mine tailings sample, containing elevated levels of As (2,180 mg/kg), copper (Cu, 1,100 mg/kg), lead (Pb, 12,860 mg/kg), and zinc (Zn, 5,075 mg/kg), was collected from Bathurst, New Brunswick, Canada. It was found that the organic additives inhibited As and heavy metal mobilization under acidic conditions (at pH 3 or 5), but enhanced it under neutral to alkaline conditions (at pH above 7) through forming aqueous organic complexes. At pH 11, As, Cu, Pb, and Zn were mobilized mostly by the organic additives, 45, 46, 1,660, and 128 mg/kg by aspartic acid, 31, 28, 1,040, and 112 mg/kg by succinic acid, and 53, 38, 2,020, and 150 mg/kg by cysteine, respectively, whereas those by distilled water were 6, 16, 260, and 52 mg/kg, respectively. It was also found that the mobilization of As and the heavy metals was closely correlated, and both were closely correlated to Fe mobilization. Arsenic mobilization by the three LMWOAs was found to be consistent with the order of the stability of Fe-, Cu-, Pb-, and Zn-organic ligand complexes. The organic acids might be used potentially in the natural attenuation and remediation of As and heavy metal-contaminated sites.

Selectivity differences of water-soluble vitamins separated on hydrophilic interaction stationary phases.

PubMed

Yang, Yuanzhong; Boysen, Reinhard I; Hearn, Milton T W

2013-06-01

In this study, the retention behavior and selectivity differences of water-soluble vitamins were evaluated with three types of polar stationary phases (i.e. an underivatized silica phase, an amide phase, and an amino phase) operated in the hydrophilic interaction chromatographic mode with ESI mass spectrometric detection. The effects of mobile phase composition, including buffer pH and concentration, on the retention and selectivity of the vitamins were investigated. In all stationary phases, the neutral or weakly charged vitamins exhibited very weak retention under each of the pH conditions, while the acidic and more basic vitamins showed diverse retention behaviors. With the underivatized silica phase, increasing the salt concentration of the mobile phase resulted in enhanced retention of the acidic vitamins, but decreased retention of the basic vitamins. These observations thus signify the involvement of secondary mechanisms, such as electrostatic interaction in the retention of these analytes. Under optimized conditions, a baseline separation of all vitamins was achieved with excellent peak efficiency. In addition, the effects of water content in the sample on retention and peak efficiency were examined, with sample stacking effects observed when the injected sample contained a high amount of water. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First steps towards a gas-phase acidity ladder for derivatized fullerene dications

NASA Astrophysics Data System (ADS)

Petrie, Simon; Javahery, Gholamreza; Bohme, Diethard K.

1993-03-01

C2+60 can be derivatized by gas-phase ion/molecule reactions with polar hydrogen-bearing molecules. The adduct dications so produced may then undergo proton transfer to neutrals. The occurrence or absence of proton transfer as a secondary process gives information on the gas-phase acidity of the dicationic species C60·(XH)2+in. We have performed studies using a selected-ion flow tube at 294 ± 2 K and 0.35 ± 0.01 Torr, and have used observed reactivity of such dicationic fullerene adducts to determine upper or lower limits to their apparent and absolute gas-phase acidities. We present also a rationale for assessing the proton-transfer reactivity of dications via the apparent gas-phase acidity of these species, rather than the traditional use of gas-phase basicities or proton affinities. We propose that further studies of proton transfer from polycharged fullerene adducts may provide considerable useful information to model the reactivity of polyprotonated proteins and other large molecular polycatiions which can now be produced by techniques such as electrospray ionization.

CEC with new monolithic stationary phase based on a fluorinated monomer, trifluoroethyl methacrylate.

PubMed

Yurtsever, Arda; Saraçoğlu, Berna; Tuncel, Ali

2009-02-01

A new, fluorinated monolithic stationary phase for CEC was first synthesized by a single-stage, thermally initiated copolymerization of a fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEM) and ethylene dimethacrylate (EDMA) in the presence of a porogen mixture. In this preparation, 2-acrylamido-2-methyl-1-propanesulfonic acid was used as the charge-bearing monomer. The porogen mixture was prepared by mixing isoamylalcohol and 1,4-butanediol. A clear increase in the electroosmotic mobility was observed with increasing pH. The electroosmotic mobility decreased with increasing ACN concentration. Poly(TFEM-co-EDMA) monolith prepared under optimized polymerization conditions was successfully used in the separation of alkylbenzenes and phenols by CEC. The best chromatographic separation for alkylbenzenes was performed with lower ACN concentrations (i.e. 60% v/v) with respect to the common acrylic-based CEC monoliths. The theoretical plate numbers up to 220 000 plates/m were achieved in the reversed phase separation of phenols. Poly(TFEM-co-EDMA) monolith also allowed the simultaneous separation of aniline and benzoic acid derivatives by a single run and by using a lower ACN concentration in the mobile phase with respect to the similar electrochromatographic separations. A stable retention behaviour in reversed phase separation of alkylbenzenes was obtained with the poly(TFEM-co-EDMA) monolith.

Evaluation of ODS-AQ stationary phase for use in capillary electrochromatography.

PubMed

Djordjevic, N M; Fitzpatrick, F; Houdiere, F

2001-04-01

The aim of this study was to evaluate the applicability of ODS-AQ packing material as a stationary phase in capillary electrochromatography (CEC). The electroosmotic flow created on an ODS-AQ stationary phase was measured at different mobile phase compositions and at different column temperatures. It was observed that the electroosmotic flow generated in the column increased by 50% when the temperature of the system was raised from 20 degrees C to 60 degrees C, while all other conditions were kept constant. The electroosmotic flow produced by the ODS-AQ stationary phase was found to be comparable to the flow generated in a column packed with Nucleosil bare-silica material. In addition, a set of polar compounds (D-lysergic acid diethylamide derivatives) was utilized to determine the influence of temperature and mobile phase composition on their chromatographic behavior on an ODS-AQ stationary phase in a CEC mode. A linear relationship between the solute retention factor and column temperatures was seen over the temperature range studied (20 degrees C to 60 degrees C). A quadratic function was used to describe the changes in the solute retention factors with variation of acetonitrile concentration in the mobile phase.

Magnetic self-orientation of lyotropic hexagonal phases based on long chain alkanoic (fatty) acids.

PubMed

Douliez, Jean-Paul

2010-07-06

It is presently shown that long chain (C14, C16, and C18) alkanoic (saturated fatty) acids can form magnetically oriented hexagonal phases in aqueous concentrated solutions in mixtures with tetrabutylammonium (TBAOH) as the counterion. The hexagonal phase occurred for a molar ratio, alkanoic acid/TBAOH, higher than 1, i.e., for an excess of fatty acid. The hexagonal phase melted to an isotropic phase (micelles) upon heating at a given temperature depending on the alkyl chain length. The self-orientation of the hexagonal phase occurred upon cooling from the "high-temperature" isotropic phase within the magnetic field. The long axis of the hexagonal phase was shown to self-orient parallel to the magnetic field as evidenced by deuterium solid-state NMR. This finding is expected to be of interest in the field of structural biology and materials chemistry for the synthesis of oriented materials.

Mobile Clinical Decision Support System for Acid-base Balance Diagnosis and Treatment Recommendation.

PubMed

Mandzuka, Mensur; Begic, Edin; Boskovic, Dusanka; Begic, Zijo; Masic, Izet

2017-06-01

This paper presents mobile application implementing a decision support system for acid-base disorder diagnosis and treatment recommendation. The application was developed using the official integrated development environment for the Android platform (to maximize availability and minimize investments in specialized hardware) called Android Studio. The application identifies disorder, based on the blood gas analysis, evaluates whether the disorder has been compensated, and based on additional input related to electrolyte imbalance, provides recommendations for treatment. The application is a tool in the hands of the user, which provides assistance during acid-base disorders treatment. The application will assist the physician in clinical practice and is focused on the treatment in intensive care.

Semi-Preparative Isolation and Purification of Three Tauro-Conjugated Cholic Acids from Pulvis Fellis Suis by HSCCC Coupled with ELSD Detection.

PubMed

He, Jiao; Zhang, Yongmin; Ito, Yoichiro; Sun, Wenji

2011-01-01

Coupled with evaporative light scattering detection, a high-speed counter-current chromatography (HSCCC) method was applied to the separation and purification of three tauro-conjugated cholic acids of taurochenodeoxycholic acid (TCDCA), taurohyodeoxycholic acid (THDCA) and taurohyocholic acid (THCA) from Pulvis Fellis Suis (Pig gallbladder bile) for the first time. The two-phase solvent system composed of chloroform-methanol-water-acetic acid (4:4:2:0.3, v/v/v/v) was selected for the one-step separation where the lower phase was used as the mobile phase in the head to tail elution mode. The revolution speed of the separation column, flow rate of the mobile phase and separation temperature were 800 rpm, 1.5 ml/min and 25°C respectively. From 100 mg of the crude extract, 10.2 mg of TCDCA, 11.8 mg of THDCA and 5.3 mg of THCA were obtained with the purity of 94.6%, 96.5% and 95.4%, respectively. in one step separation The HSCCC fractions were analyzed by high-performance liquid chromatography (HPLC) and the structures of the three tauro-conjugated cholic acids were identified by ESI-MS, (1)H NMR and (13)C NMR.

[Simultaneous isolation and purification of gallic acid and brevifolincarboxylic acid from Polygonum capitatum by high-speed counter-current chromatography].

PubMed

Chen, Xinxia; Zhang, Liyan; Wan, Jinzhi; Liang, Bin; Xie, Yu

2010-08-01

To isolate and purify gallic acid and brevifolincarboxylic acid simultaneously by high-speed counter-current chromatography (HSCCC) from a crude extract of Polygonum capitatum. The biphasic solvent system composed of ethyl acetate-n-butanol-0.44% acetic acid (3:1:5) was used at a flow rate of 2.0 mL x min(-1), while the aqueous phase was selected as the mobile phase and the apparatus was rotated at 860 r x min(-1). The effluent was detected at 272 nm. 51.5 mg of gallic acid and 5.9 mg of brevifolincarboxylic acid were separated from 1.07 g of the crude extract with the purities of 99.7% and 97.5%, respectively, while brevifolincarboxylic acid was obtained firstly from the genus Polygonum. The structures of the compounds were identified by ultraviolet spectrometry (UV), infra-red spectrometry (IR), liquid chromatography/mass spectrometry (LC/MS), time-of-flight mass spectrometry( TOF-MS), 1H-nuclear magnetic resonance (NMR) and 13C-NMR. This method is feasible and rapid for isolation and purification of gallice acid and brevifolincarboxylil acid.

Phase Behavior of Complex Superprotonic Solid Acids

NASA Astrophysics Data System (ADS)

Panithipongwut, Chatr

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2

Quantitative high-performance liquid chromatographic determination of retinoids in human serum using on-line solid-phase extraction and column switching. Determination of 9-cis-retinoic acid, 13-cis-retinoic acid, all-trans-retinoic acid, 4-oxo-all-trans-retinoicacid and 4-oxo-13-cis-retinoic acid.

PubMed

Gundersen, T E; Lundanes, E; Blomhoff, R

1997-03-28

A fully automated isocratic high-performance liquid chromatographic method for the determination of 9-cis-retinoic acid, 13-cis-retinoic acid, all-trans-retinoic acid, 4-oxo-13-cis-retinoic acid and 4-oxo-all-trans-retinoic acid, has been developed using on-line solid-phase extraction and a column switching technique allowing clean-up and pre-concentration in a single step. A 500-microliter sample of serum was diluted with 750 microliters of a solution containing 20% acetonitrile and the internal standard 9,10-dimethylanthracene. About 1000 microliters of this mixture was injected on a 20 x 4.6 mm I.D. poly ether ether ketone (PEEK) pre-column with titanium frits packed with Bondapak C18, 37-53 microns, 300 A particles. Proteins and very polar compounds were washed out to waste, from the pre-column, with 0.05% trifluoroacetic acid (TFA)-acetonitrile (8.5:1.5, v/v). More than 200 aliquots of diluted serum could be injected on this pre-column before elevated back-pressure enforces replacement. Components retained on the pre-column were backflushed to the analytical column for separation and detection at 360 nm. Baseline separation was achieved using a single 250 x 4.6 mm I.D. Suplex pKb-100 column and a mobile phase containing 69:10:2:16:3 (v/v) of acetonitrile-methanol-n-butanol-2% ammonium acetate-glacial acetic acid. A total time of analysis of less than 30 min, including sample preparation, was achieved. Recoveries were in the range of 79-86%. The limit of detection was 1-7 ng/ml serum and the precision, in the concentration range 20-1000 ng/ml, was between 1.3 and 4.5% for all five compounds. The method was applied for the analysis of human serum after oral administration of 60 mg Roaccutan. The method is well suited for pharmacological studies, while the endogenous levels of some retinoic acid isomers are below the limit of quantitation.

Acidic deposition, cation mobilization, and biochemical indicators of stress in healthy red spruce

USGS Publications Warehouse

Shortle, W.C.; Smith, K.T.; Minocha, R.; Lawrence, G.B.; David, M.B.

1997-01-01

Dendrochemical and biochemical markers link stress in apparently healthy red spruce trees (Picea rubens) to acidic deposition. Acidic deposition to spruce forests of the northeastern USA increased sharply during the 1960s. Previous reports related visible damage of trees at high elevations to root and soil processes. In this report, dendrochemical and foliar biochemical markers indicate perturbations in biological processes in healthy red spruce trees across the northeastern USA. Previous research on the dendrochemistry of red spruce stemwood indicated that under uniform environmental conditions, stemwood concentrations of Ca and Mg decreased with increasing radial distance from the pith. For nine forest locations, frequency analysis shows that 28 and 52% of samples of red spruce stemwood formed in the 1960s are enriched in Ca and Mg, respectively, relative to wood formed prior to and after the 1960s. This enrichment in trees throughout the northeastern USA may be interpretable as a signal of increased availability of essential cations in forest soils. Such a temporary increase in the availability of Ca and Mg could be caused by cation mobilization, a consequence of increased acidic deposition. During cation mobilization, essential Ca and Mg as well as potentially harmful Al become more available for interaction with binding sites in the soil and absorbing roots. As conditions which favor cation mobilization continue, Ca and Mg can be leached or displaced from the soil. A measure of the interaction between Ca and Al is the Al/Ca binding ratio (molar charge ratio of exchangeable Al to exchangeable Ca). As the Al/Ca binding ratio in the root zone increased from 0.3 to 1.9, the foliar concentration of the biochemical stress marker putrescine also increased from 45 to 145 nm g-1. The correlation of the putrescine concentration to the Al/Ca binding ratio (adj. r2 = 0.68, P < 0.027) suggests that foliar stress may be linked to soil chemistry.

Vibrational spectroscopic study on polymorphism of erucic acid and palmitoleic acid: γ1→α1 and γ→α reversible solid state phase transitions

NASA Astrophysics Data System (ADS)

Kaneko, Fumitoshi; Yamazaki, Kazuhiro; Kobayashi, Masamichi; Sato, Kiyotaka; Suzuki, Masao

1994-08-01

The infrared and Raman spectra of four polymorphic phases (α, α1, γ and γ1) of erucic acid ( cis-13-docosenoic acid) and those of two polymorphic phases (α and γ) of palmitoleic acid ( cis-9-hexadecenoic acid) were investigated. The γ and γ1 phases of erucic acid were analyzed on the basis of crystal structures determined by us. There were large spectral differences between γ and γ1 phases, which could be ascribed to the differences in the conformation of cis-olefin groups and the subcell structure. Two types of reversible solid state phase transitions (γ→α and γ1→α1 transitions) were followed by the infrared and Raman spectra. It was concluded that the mechanism of the γ→α phase transition of erucic and palmitoleic acids is essentially the same as that of oleic acid previously reported by us [ J. Phys. Chem.90, 6371 (1986)], i.e. this phase transition is of order-disorder type accompanied by a conformational disordering at the methyl-terminal chain. Spectral changes on the γ1→α1 transition suggested that a similar structural change took place during this transition but there were large structural differences between α and α1.

Polar silica-based stationary phases. Part II- Neutral silica stationary phases with surface bound maltose and sorbitol for hydrophilic interaction liquid chromatography.

PubMed

Rathnasekara, Renuka; El Rassi, Ziad

2017-07-28

Two neutral polyhydroxylated silica bonded stationary phases, namely maltose-silica (MALT-silica) and sorbitol-silica (SOR-silica), have been introduced and chromatographically characterized in hydrophilic interaction liquid chromatography (HILIC) for a wide range of polar compounds. The bonding of the maltose and sorbitol to the silica surface was brought about by first converting bare silica to an epoxy-activated silica surface via reaction with γ-glycidoxypropyltrimethoxysilane (GPTMS) followed by attaching maltose and sorbitol to the epoxy surface in the presence of the Lewis acid catalyst BF 3 .ethereate. Both silica based columns offered the expected retention characteristics usually encountered for neutral polar surface. The retention mechanism is majorly based on solute' differential partitioning between an organic rich hydro-organic mobile phase (e.g., ACN rich mobile phase) and an adsorbed water layer on the surface of the stationary phase although additional hydrogen bonding was also responsible in some cases for solute retention. The MALT-silica column proved to be more hydrophilic and offered higher retention, separation efficiency and resolution than the SOR-silica column among the tested polar solutes such as derivatized mono- and oligosaccharides, weak phenolic acids, cyclic nucleotide monophosphate and nucleotide-5'-monophosphates, and weak bases, e.g., nucleobases and nucleosides. Copyright © 2017 Elsevier B.V. All rights reserved.

77 FR 9655 - Mobility Fund Phase I Auction Updated List of Potentially Eligible Census Blocks

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-17

... Updated List of Potentially Eligible Census Blocks AGENCY: Federal Communications Commission. ACTION... Bureaus provide an updated list of potentially eligible census blocks for Auction 901 scheduled to... summary of the Mobility Fund Phase I Auction Updated List of Potentially Eligible Census Blocks Public...

77 FR 38061 - Mobility Fund Phase I Auction Supplemental Short-Form Instructions and Other Information

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-26

... FEDERAL COMMUNICATIONS COMMISSION [AU Docket No. 12-25; DA 12-947] Mobility Fund Phase I Auction Supplemental Short-Form Instructions and Other Information AGENCY: Federal Communications Commission. ACTION... number, for example, DA 12-947. The Supplemental Filing Instructions Public Notice and related documents...

Nonequilibrium phase diagram of a one-dimensional quasiperiodic system with a single-particle mobility edge

NASA Astrophysics Data System (ADS)

Purkayastha, Archak; Dhar, Abhishek; Kulkarni, Manas

2017-11-01

We investigate and map out the nonequilibrium phase diagram of a generalization of the well known Aubry-André-Harper (AAH) model. This generalized AAH (GAAH) model is known to have a single-particle mobility edge which also has an additional self-dual property akin to that of the critical point of the AAH model. By calculating the population imbalance, we get hints of a rich phase diagram. We also find a fascinating connection between single particle wave functions near the mobility edge of the GAAH model and the wave functions of the critical AAH model. By placing this model far from equilibrium with the aid of two baths, we investigate the open system transport via system size scaling of nonequilibrium steady state (NESS) current, calculated by fully exact nonequilibrium Green's function (NEGF) formalism. The critical point of the AAH model now generalizes to a `critical' line separating regions of ballistic and localized transport. Like the critical point of the AAH model, current scales subdiffusively with system size on the `critical' line (I ˜N-2 ±0.1 ). However, remarkably, the scaling exponent on this line is distinctly different from that obtained for the critical AAH model (where I ˜N-1.4 ±0.05 ). All these results can be understood from the above-mentioned connection between states near the mobility edge of the GAAH model and those of the critical AAH model. A very interesting high temperature nonequilibrium phase diagram of the GAAH model emerges from our calculations.

Behavior of new complexes of tetrakis(4-methoxylphenyl)porphyrin with heavy rare earth elements in reversed-phase high performance liquid chromatography.

PubMed

Zhang, Jun-Feng; Wang, Hong; Hou, An-Xin; Wang, Chang-Fa; Zhang, Hua-Shan

2004-08-01

An HPLC method has been developed for the separation of new complexes of tetrakis(4-methoxylphenyl)porphyrin (TMOPP) with four heavy rare earth elements (RE = Y, Er, Tm, and Yb). The function of amine and acid in the mobile phase has been investigated and a reasonable explanation is presented. Successful separation of the RE-TMOPP-Cl complexes is accomplished in 10 min with a mobile phase consisting of methanol-water-acetic acid-triethanolamine. The detection limits (S/N= 3) for the four complexes are 0.01 microg/mL. This method is rapid, sensitive, and simple.

Molecularly imprinted polymer for caffeic acid by precipitation polymerization and its application to extraction of caffeic acid and chlorogenic acid from Eucommia ulmodies leaves.

PubMed

Miura, Chitose; Matsunaga, Hisami; Haginaka, Jun

2016-08-05

Molecularly imprinted polymers (MIPs) for caffeic acid (CA) were prepared using 4-vinylpyridine and methacrylamide (MAM) as functional monomers, divinylbenzene as a crosslinker and acetonitrile-toluene (3:1, v/v) as a porogen by precipitation polymerization. The use of MAM as the co-monomer resulted in the formation of microsphere MIPs and non-imprinted polymers (NIPs) with ca. 3- and 5-μm particle diameters, respectively. Binding experiments and Scatchard analyses revealed that the binding capacity and affinity of the MIP to CA are higher than those of the NIP. The retention and molecular-recognition properties of the prepared MIPs were evaluated using water-acetonitrile and sodium phosphate buffer-acetonitrile as mobile phases in hydrophilic interaction chromatography (HILIC) and reversed-phase chromatography, respectively. In HILIC mode, the MIP showed higher molecular-recognition ability for CA than in reversed-phase mode. In addition to shape recognition, hydrophilic interactions seem to work for the recognition of CA on the MIP in HILIC mode, while hydrogen bonding and hydrophobic interactions seem to work for the recognition of CA in reversed-phase mode. The MIP had a specific molecular-recognition ability for CA in HILIC mode, while other structurally related compounds, such as chlorogenic acid （CGA), gallic acid, protocatechuic acid and vanillic acid, could not be recognized by the MIP. Furthermore, the MIP was successfully applied for extraction of CA and CGA in the leaves of Eucommia ulmodies in HILIC mode. Copyright © 2015 Elsevier B.V. All rights reserved.

Syntrophic acetate oxidation in two-phase (acid-methane) anaerobic digesters.

PubMed

Shimada, T; Morgenroth, E; Tandukar, M; Pavlostathis, S G; Smith, A; Raskin, L; Kilian, R E

2011-01-01

The microbial processes involved in two-phase anaerobic digestion were investigated by operating a laboratory-scale acid-phase (AP) reactor and analyzing two full-scale, two-phase anaerobic digesters operated under mesophilic (35 °C) conditions. The digesters received a blend of primary sludge and waste activated sludge (WAS). Methane levels of 20% in the laboratory-scale reactor indicated the presence of methanogenic activity in the AP. A phylogenetic analysis of an archaeal 16S rRNA gene clone library of one of the full-scale AP digesters showed that 82% and 5% of the clones were affiliated with the orders Methanobacteriales and Methanosarcinales, respectively. These results indicate that substantial levels of aceticlastic methanogens (order Methanosarcinales) were not maintained at the low solids retention times and acidic conditions (pH 5.2-5.5) of the AP, and that methanogenesis was carried out by hydrogen-utilizing methanogens of the order Methanobacteriales. Approximately 43, 31, and 9% of the archaeal clones from the methanogenic phase (MP) digester were affiliated with the orders Methanosarcinales, Methanomicrobiales, and Methanobacteriales, respectively. A phylogenetic analysis of a bacterial 16S rRNA gene clone library suggested the presence of acetate-oxidizing bacteria (close relatives of Thermacetogenium phaeum, 'Syntrophaceticus schinkii,' and Clostridium ultunense). The high abundance of hydrogen consuming methanogens and the presence of known acetate-oxidizing bacteria suggest that acetate utilization by acetate oxidizing bacteria in syntrophic interaction with hydrogen-utilizing methanogens was an important pathway in the second-stage of the two-phase digestion, which was operated at high ammonium-N concentrations (1.0 and 1.4 g/L). A modified version of the IWA Anaerobic Digestion Model No. 1 (ADM1) with extensions for syntrophic acetate oxidation and weak-acid inhibition adequately described the dynamic profiles of volatile acid production

Mobile Clinical Decision Support System for Acid-base Balance Diagnosis and Treatment Recommendation

PubMed Central

Mandzuka, Mensur; Begic, Edin; Boskovic, Dusanka; Begic, Zijo; Masic, Izet

2017-01-01

Introduction: This paper presents mobile application implementing a decision support system for acid-base disorder diagnosis and treatment recommendation. Material and methods: The application was developed using the official integrated development environment for the Android platform (to maximize availability and minimize investments in specialized hardware) called Android Studio. Results: The application identifies disorder, based on the blood gas analysis, evaluates whether the disorder has been compensated, and based on additional input related to electrolyte imbalance, provides recommendations for treatment. Conclusion: The application is a tool in the hands of the user, which provides assistance during acid-base disorders treatment. The application will assist the physician in clinical practice and is focused on the treatment in intensive care. PMID:28883678

Determination of the microenvironment-pH and charge and size characteristics of amino acids through their electrophoretic mobilities determined by CZE.

PubMed

Piaggio, Maria V; Peirotti, Marta B; Deiber, Julio A

2007-10-01

Effective electrophoretic mobility data of 20 amino acids reported in the literature are analyzed and interpreted through simple physicochemical models, which are able to provide estimates of coupled quantities like hydrodynamic shape factor, equivalent hydrodynamic radius (size), net charge, actual pK values of ionizing groups, partial charges of ionizing groups, hydration number, and pH near molecule (microenvironment-pH of the BGE). It is concluded that the modeling of the electrophoretic mobility of these analytes requires a careful consideration of hydrodynamic shape coupled to hydration. In the low range of pH studied here, distinctive hydrodynamic behaviors of amino acids are found. For instance, amino acids with basic polar and ionizing side chain remain with prolate shape for pH values varying from 1.99 to 3.2. It is evident that as the pH increases from low values, amino acids get higher hydrations as a consequence each analyte total charge also increases. This result is consistent with the monotonic increase of the hydrodynamic radius, which accounts for both the analyte and the quite immobilized water molecules defining the electrophoretic kinematical unit. It is also found that the actual or effective pK value of the alpha-carboxylic ionizing group of amino acids increases when the pH is changed from 1.99 to 3.2. Several limitations concerning the simple modeling of the electrophoretic mobility of amino acids are presented for further research.

Modelling by partial least squares the relationship between the HPLC mobile phases and analytes on phenyl column.

PubMed

Markopoulou, Catherine K; Kouskoura, Maria G; Koundourellis, John E

2011-06-01

Twenty-five descriptors and 61 structurally different analytes have been used on a partial least squares (PLS) to latent structure technique in order to study chromatographically their interaction mechanism on a phenyl column. According to the model, 240 different retention times of the analytes, expressed as Y variable (log k), at different % MeOH mobile-phase concentrations have been correlated with their theoretical most important structural or molecular descriptors. The goodness-of-fit was estimated by the coefficient of multiple determinations r(2) (0.919), and the root mean square error of estimation (RMSEE=0.1283) values with a predictive ability (Q(2)) of 0.901. The model was further validated using cross-validation (CV), validated by 20 response permutations r(2) (0.0, 0.0146), Q(2) (0.0, -0.136) and validated by external prediction. The contribution of certain mechanism interactions between the analytes, the mobile phase and the column, proportional or counterbalancing is also studied. Trying to evaluate the influence on Y of every variable in a PLS model, VIP (variables importance in the projection) plot provides evidence that lipophilicity (expressed as Log D, Log P), polarizability, refractivity and the eluting power of the mobile phase are dominant in the retention mechanism on a phenyl column. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of a series of chlorogenic acid isomers using differential ion mobility and tandem mass spectrometry.

PubMed

Willems, Jamie L; Khamis, Mona M; Mohammed Saeid, Waleed; Purves, Randy W; Katselis, George; Low, Nicholas H; El-Aneed, Anas

2016-08-24

Chlorogenic acids are among the most abundant phenolics found in the human diet. Of these, the mono-caffeoylquinic acids are the predominant phenolics found in fruits, such as apples and pears, and products derived from them. In this research, a comprehensive study of the electrospray ionization (ESI) tandem mass spectrometric (MS/MS) dissociation behavior of the three most common mono-caffeoylquinic acids, namely 5-O-caffeoylquinic acid (5-CQA), 3-O-caffeoylquinic acid (3-CQA) and 4-O-caffeoylquinic acid (4-CQA), were determined using both positive and negative ionization. All proposed structures of the observed product ions were confirmed with second-generation MS(3) experiments. Similarities and differences between the dissociation pathways in the positive and negative ion modes are discussed, confirming the proposed structures and the established MS/MS fingerprints. MS/MS dissociation was primarily driven via the cleavage of the ester bond linking the quinic acid moiety to the caffeic acid moiety within tested molecules. Despite being structural isomers with the same m/z values and dissociation behaviors, the MS/MS data in the negative ion mode was able to differentiate the three isomers based on ion intensity for the major product ions, observed at m/z 191, 179 and 173. This differentiation was consistent among various MS instruments. In addition, ESI coupled with high-field asymmetric waveform ion mobility spectrometry-mass spectrometry (ESI-FAIMS-MS) was employed for the separation of these compounds for the first time. By combining MS/MS data and differential ion mobility, a method for the separation and identification of mono-caffeoylquinic in apple/pear juice samples was developed with a run time of less than 1 min. It is envisaged that this methodology could be used to identify pure juices based on their chlorogenic acid profile (i.e., metabolomics), and could also be used to detect juice-to-juice adulteration (e.g., apple juice addition to pear juice

A validated UHPLC method for the determination of caffeoylquinic and di-caffeoylquinic acids in green coffee extracts using an RP-Amide fused-core column.

PubMed

Fibigr, Jakub; Majorová, Michaela; Kočová Vlčková, Hana; Solich, Petr; Šatínský, Dalibor

2018-03-20

The presented work describes the development and validation of a rapid UHPLC-UV method using a fused core particle column with an RP-Amide stationary phase for the separation and quantitative analysis of caffeoylquinic and di-caffeoylquinic acids in green coffee extracts. Three caffeoylquinic acids (3-caffeoylquinic acid, 4-caffeoylquinic acid, and 5-caffeoylquinic acid) and two di-caffeoylquinic acids (1,3-di-caffeoylquinic acid, and 3,5-di-caffeoylquinic acid) were separated and analyzed in 8 min. That was possible due to the unique selectivity of the RP-Amide stationary phase for the analyzed acids. The retention behavior of all analytes under different compositions of the mobile phase on different columns was evaluated in this study. The optimal chromatographic separation was performed using an Ascentis Express RP-Amide (100 × 2.1 mm) fused-core column with a particle size of 2.7 μm at a temperature of 30 °C. For validation of the newly developed method, acetonitrile was used as mobile phase B and 5% formic acid, filtrated through a 0.22 μm filter, was used as mobile phase A. They were delivered at a flow rate of 0.9 mL min -1 according to the elution gradient program. The detection wavelength was set at 325 nm. A solid-liquid extraction with a solution of methanol and a 5% water solution of formic acid (25 + 75 v/v) using an ultrasonic bath was chosen for the preparation of the available commercial samples of food supplements containing a green coffee extract. Recoveries for all analyzed acids were 98.2-101.0% and the relative standard deviation ranged from 0.3% to 1.4% for intra-day and from 0.3% to 3.0% for inter-day repeatability. The limits of detection were in the range of 0.30-0.53 μg mL -1 . Copyright © 2018. Published by Elsevier B.V.

Improvement in HPLC separation of acetic acid and levulinic acid in the profiling of biomass hydrolysate.

PubMed

Xie, Rui; Tu, Maobing; Wu, Yonnie; Adhikari, Sushil

2011-04-01

5-Hydroxymethylfurfural (HMF) and furfural could be separated by the Aminex HPX-87H column chromatography, however, the separation and quantification of acetic acid and levulinic acid in biomass hydrolysate have been difficult with this method. In present study, the HPLC separation of acetic acid and levulinic acid on Aminex HPX-87H column has been investigated by varying column temperature, flow rate, and sulfuric acid content in the mobile phase. The column temperature was found critical in resolving acetic acid and levulinic acid. The resolution for two acids increased dramatically from 0.42 to 1.86 when the column temperature was lowered from 60 to 30 °C. So did the capacity factors for levulinic acid that was increased from 1.20 to 1.44 as the column temperature dropped. The optimum column temperature for the separation was found at 45 °C. Variation in flow rate and sulfuric acid concentration improved not as much as the column temperature did. Published by Elsevier Ltd.

Development of a simple method for quantitation of methanesulfonic acid at low ppm level using hydrophilic interaction chromatography coupled with ESI-MS.

PubMed

Huang, Zongyun; Francis, Robert; Zha, Yan; Ruan, Joan

2015-01-01

A simple, sensitive and robust method using HILIC-ESI-MS has been developed for the determination of methane sulfonic acid (MSA) at low ppm level in order to verify the effectiveness of controlling the formation of genotoxic sulfonate esters in the downstream synthetic step, by which produces active pharmaceutical ingredient (API). Stationary phases with positively charged functional groups such as triazole and amino phases were evaluated for the retention of alkyl sulfonic acids. The MSA was quantitated at 1-10 ppm relative to the API using a Cosmosil column (triazole stationary phase) in HILIC mode and the control of MSA can be monitored effectively using the HILIC-ESI-MS methodology. In addition, to provide general guidance for the HILIC-ESI-MS method development, the retention behavior of propanesulfonic acid (PSA) in HILIC mode was investigated using a Unison UK-Amino column to have a better understanding of the HILIC separation mechanism. The results showed reasonable evidence that the combined effect of surface adsorption and ion-exchange played a dominant role for sulfonic acids when using a mobile phase within typical HILIC operation range (0.05-0.20 aqueous volume fraction) while the ion-exchange effect becomes increasingly important in a mobile phase with higher water content. The advantage of using ESI-MS detection in HILIC mode was also demonstrated by the observation that the sensitivity of PSA increased substantially with increasing acetonitrile fraction in mobile phase from 0.80 to 0.95. Copyright © 2014 Elsevier B.V. All rights reserved.

[Determination of triterpenoic acids in fruits of Ziziphus jujuba using HPLC-MS with polymeric ODS column].

PubMed

Zhang, Yong; Zhou, An; Xie, Xiao-Mei

2013-03-01

A simple and sensitive method has been developed to simultaneously determine betunilic acid, oleanolic acid and ursolic acid in the fruits of Ziziphus jujuba from different regions by HPLC-MS. This HPLC assay was performed on PAH polymeric C18 bonded stationary phase column with mobile phase contained acetonitrile-water (90: 10) and with negative ESI detection mode. The developed approach was characterized by short time consumption for chromatographic separation, high sensitivity and good reliability so as to meet the requirements for rapid analysis of large-batch fruits of Z. jujuba from different habitats.

Improvement of Nicotinic Acid and Nicotinamide Analysis in Meats and Meat Products by HPLC and LC-MS/MS with Solid-Phase Extraction.

PubMed

Hiki, Asako; Yamajima, Yukiko; Uematsu, Yoko

2016-01-01

A method for nicotinic acid (NA) and nicotinamide (NAA) analysis in meats was developed. NA and NAA were extracted from meats or meat products with metaphosphate aqueous solution. The extract was cleaned up with an Oasis MCX cartridge. The cartridge was washed with 2% acetic acid (v/v) and acetic acid-methanol solution. NA and NAA were eluted with ammonia-methanol solution. NA and NAA in the eluate were chromatographed on a Scherzo SM-C18 (3.0×150 mm, 3.0 μm) column with 20 mmol/L ammonium acetate containing 0.1% acetic acid-acetonitrile (97 : 3) as a mobile phase and were monitored at 261 nm. Quantification was performed by LC and LC-MS/MS. Calibration curves showed high linearity (correlation coefficient>0.998) between 1-25 μg/mL for LC and LC-MS/MS. Recoveries were 84-108% (CV≦5.8%) by HPLC and 79-105% (CV≦9.0%) by LC-MS/MS. The limit of quantitation for NA was 0.005-0.01 g/kg and that for NAA was 0.01-0.02 g/kg.

New stationary phase for hydrophilic interaction chromatography to separate chito-oligosaccharides with degree of polymerization 2-6.

PubMed

Zhai, Xingchen; Zhao, Haitian; Zhang, Min; Yang, Xin; Sun, Jingming; She, Yongxin; Dong, Aijun; Zhang, Hua; Yao, Lei; Wang, Jing

2018-04-01

A new 3‑aminophenylboronic acid-functionalized stationary phase based on silica for hydrophilic interaction liquid chromatography (HILIC) was developed and showed great HILIC characteristics on separation for chito‑oligosaccharides. The material was synthesized by grafting 3‑aminophenylboronic acid group to silica, and it was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), elemental analysis and thermal gravimetric analysis (TGA). Nucleobases and nucleosides were used to evaluate the retention property and to investigate retention mechanism by the models designed for description of partitioning and surface adsorption through adjusting ratio of water in the mobile phase. Parameters affecting chromatography behavior such as ionic strength, buffer pH and column temperature were also investigated. Results have indicated that the retention mechanism was a combination of partitioning and surface adsorption, and the hydrogen bond seemed to be the main force for the retention behavior. Finally, the new 3‑aminophenylboronic acid-functionalized based on silica stationary phase was applied to separate chito-oligosaccharide samples with optimized mobile phase conditions and showed acceptable chromatograms. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparing the selectivity and chiral separation of d- and l- fluorenylmethyloxycarbonyl chloride protected amino acids in analytical high performance liquid chromatography and supercritical fluid chromatography; evaluating throughput, economic and environmental impact.

PubMed

Vera, C M; Shock, D; Dennis, G R; Farrell, W; Shalliker, R A

2017-04-14

The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO 2 , there is a reduction in organic solvent consumption, which minimises the economic and environmental costs. Copyright © 2017. Published by Elsevier B.V.

Optimization of a new mobile phase to know the complex and real polyphenolic composition: towards a total phenolic index using high-performance liquid chromatography.

PubMed

Tsao, Rong; Yang, Raymond

2003-11-07

An HPLC method is reported for the separation and quantification of five major polyphenolic groups found in fruits and related products: single ring phenolic acids (hydroxybenzoic acid and hydroxycinnamic acid derivatives), flavan-3-ols, flavonols, anthocyanins, and dihydrochalcones. A binary mobile phase consisting of 6% acetic acid in 2 mM sodium acetate aqueous solution (v/v, final pH 2.55) (solvent A) and acetonitrile (solvent B) was used. The use of sodium acetate was new and key to the near baseline separation of 25 phenolics commonly found in fruits. A photodiode array detector was used and data were collected at four wavelengths (280, 320, 360, and 520 nm). This method was sensitive and gave good separation of polyphenolics in apple, cherry, strawberry, blackberry, grape, apple juice, and a processing by-product. The improved separation has led to better understanding of the polyphenolic profiles of these fruits. Individual as well as total phenolic content was obtained, and the latter was close to and correlated well with that obtained by the Folin-Ciocalteu method (FC). The HPLC data can be used as a total phenolic index (TPI) for quantification of fruit phenolics, which is advantageous over the FC because it has more information on individual compounds.

Distinguishing d- and l-aspartic and isoaspartic acids in amyloid β peptides with ultrahigh resolution ion mobility spectrometry.

PubMed

Zheng, Xueyun; Deng, Liulin; Baker, Erin S; Ibrahim, Yehia M; Petyuk, Vladislav A; Smith, Richard D

2017-07-11

While α-linked amino acids in the l-form are exclusively utilized in mammalian protein building, β-linked and d-form amino acids also have important biological roles. Unfortunately, the structural elucidation and separation of these different amino acid types in peptides has been analytically challenging to date due to the numerous isomers present, limiting our knowledge about their existence and biological roles. Here, we utilized an ultrahigh resolution ion mobility spectrometry platform coupled with mass spectrometry (IMS-MS) to separate amyloid β (Aβ) peptides containing l-aspartic acid, d-aspartic acid, l-isoaspartic acid, and d-isoaspartic acid residues which span α- and β-linked amino acids in both d- and l-forms. The results illustrate how IMS-MS could be used to better understand age-related diseases or protein folding disorders resulting from amino acid modifications.

78 FR 56875 - Tribal Mobility Fund Phase I Auction Rescheduled for December 19, 2013; Notice and Filing...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-16

... of comparing bids and measuring the performance of Tribal Mobility Fund Phase I support recipients..., EV-DO Rev A, UMTS/HSPA, HSPA+, WiMAX, and LTE. If the Mosaik data did not show such coverage, the...

The role of pegmatites and acid fluids for REE/HFSE mobilization in the Strange Lake peralkaline granitic pluton, Canada

NASA Astrophysics Data System (ADS)

Gysi, A. P.; Williams-Jones, A.

2012-12-01

The Strange Lake pluton in Canada is a mid-Proterozoic peralkaline granitic intrusion that is host to a world-class rare earth element (REE), yttrium (Y) and high-field strength element (HFSE) deposit containing more than 50 Mt ore at >1.5 wt.% REE and >3 wt.% Zr. The highest REE/HFSE concentrations are found in pegmatite-rich zones characterized by intense alteration. Previous studies of Strange Lake and other peralkaline and alkaline intrusions, such as Khan Bogd (Mongolia) and Tamazeght (Morocco) plutons have shown that hydrothermal alteration may play an important role in the mobility of the REE/HFSE. However, the fluid chemistry and conditions of alteration (i.e., P, T, pH, fO2, ligand activity) in these systems still need to be constrained to evaluate the importance and scale of such hydrothermal mobilization. We present new data from the B-zone, a pegmatite-rich zone located in NW Strange Lake. The pegmatites are generally zoned and form two main types. The border-type pegmatites consist of quartz, K-feldspar and hematized aegirine, whereas volatile-rich pegmatites consist of hydrothermal quartz and fluorite. Transitions between both types were also observed, with the K-feldspar being partly altered and replaced by Al-Si-rich phyllosilicates. The heavy (H)REE and Zr were primarily concentrated in zirconosilicates such as elpidite, now pseudomorphed by zircon or gittinsite, whereas light (L)REE and Y were concentrated in REE-F-(CO2)-minerals such as fluocerite and bastnäsite. Textural and mineralogical observations indicate that these minerals are primary and were partly to completely leached upon fluid-rock interaction in the pegmatites. Secondary phases include Ca-F-Y-rich minerals, mainly hydrothermal fluorite, that fill vugs and replaced primary REEHFSE minerals. The presence of hydrothermal fluorite veins, micro-veins, vugs and micro-breccia in the most altered parts of the B-zone are interpreted to reflect interaction of the rocks with a F-rich fluid

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

The dynamics of solvation dictates the conformation of polyethylene oxide in aqueous, isobutyric acid and binary solutions.

PubMed

Dahal, Udaya R; Dormidontova, Elena E

2017-04-12

Polymers hydrogen-bonding with solvent represent an important broad class of polymers, properties of which depend on solvation. Using atomistic molecular dynamics simulations with the OPLS/AA force field we investigate the effect of hydrogen bonding on PEO conformation and chain mobility by comparing its behavior in isobutyric acid and aqueous solutions. In agreement with experimental data, we found that in isobutyric acid PEO forms a rather rigid extended helical structure, while in water it assumes a highly flexible coil conformation. We show that the difference in PEO conformation and flexibility is the result of the hydrogen bond stability and overall solvent dynamics near PEO. Isobutyric acid forms up to one hydrogen bond per repeat unit of PEO and interacts with PEO for a prolonged period of time, thereby stabilizing the helical structure of the polymer and reducing its segmental mobility. In contrast, water forms on average 1.2 hydrogen bonds per repeat unit of PEO (with 60% of water forming a single hydrogen bond and 40% of water forming two hydrogen bonds) and resides near PEO for a noticeably shorter time than isobutyric acid, leading to the well-documented high segmental mobility of PEO in water. We also analyze PEO conformation, hydrogen bonding and segmental mobility in binary water/isobutyric acid solutions and find that in the phase separated region PEO resides in the isobutyric-rich phase forming about 25% of its hydrogen bonds with isobutyric acid and 75% with water. We show that the dynamics of solvation affects the equilibrium properties of macromolecules, such as conformation, and by mixing of hydrogen bond-donating solvents one can significantly alter both polymer conformation and its local dynamics.

Estimation of thermodynamic acidity constants of some penicillinase-resistant penicillins.

PubMed

Demiralay, Ebru Çubuk; Üstün, Zehra; Daldal, Y Doğan

2014-03-01

In this work, thermodynamic acidity constants (pssKa) of methicillin, oxacillin, nafcillin, cloxacilin, dicloxacillin were determined with reverse phase liquid chromatographic method (RPLC) by taking into account the effect of the activity coefficients in hydro-organic water-acetonitrile binary mixtures. From these values, thermodynamic aqueous acidity constants of these drugs were calculated by different approaches. The linear relationships established between retention factors of the species and the polarity parameter of the mobile phase (ET(N)) was proved to predict accurately retention in LC as a function of the acetonitrile content (38%, 40% and 42%, v/v). Copyright © 2013 Elsevier B.V. All rights reserved.

Phase Diagram for a Four-Component System of Pentanedioic, Hexanedioic, Nonanedioic, and Decanedioic Acids

NASA Astrophysics Data System (ADS)

Kolyado, A. V.; Alenova, S. M.; Garkushin, I. K.

2018-05-01

Phase equilibria in a four-component system of pentanedioic, hexanedioic, nonanedioic, and decanedioic acids are studied via differential thermal analysis. The determined eutectic composition is pentanedioic acid, 48.1 wt %; hexanedioic acid, 10.0 wt %; nonanedioic acid, 25.7 wt %; and decanedioic acid, 16.2 wt %. The melting point of the eutectic mixture is 63.1°C.

Automated solid-phase extraction of phenolic acids using layered double hydroxide-alumina-polymer disks.

PubMed

Ghani, Milad; Palomino Cabello, Carlos; Saraji, Mohammad; Manuel Estela, Jose; Cerdà, Víctor; Turnes Palomino, Gemma; Maya, Fernando

2018-01-26

The application of layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks for solid-phase extraction is reported for the first time. Al 2 O 3 is embedded in a polymer matrix followed by an in situ metal-exchange process to obtain a layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disk with excellent flow-through properties. The extraction performance of the prepared disks is evaluated as a proof of concept for the automated extraction using sequential injection analysis of organic acids (p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid) following an anion-exchange mechanism. After the solid-phase extraction, phenolic acids were quantified by reversed-phase high-performance liquid chromatography with diode-array detection using a core-shell silica-C18 stationary phase and isocratic elution (acetonitrile/0.5% acetic acid in pure water, 5:95, v/v). High sensitivity and reproducibility were obtained with limits of detection in the range of 0.12-0.25 μg/L (sample volume, 4 mL), and relative standard deviations between 2.9 and 3.4% (10 μg/L, n = 6). Enrichment factors of 34-39 were obtained. Layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks had an average lifetime of 50 extractions. Analyte recoveries ranged from 93 to 96% for grape juice and nonalcoholic beer samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of the intermixed phase and the channel network on the carrier mobility of nanostructured solar cells

NASA Astrophysics Data System (ADS)

Woellner, Cristiano F.; Freire, José A.

2016-02-01

We analyzed the impact of the complex channel network of donor and acceptor domains in nanostructured solar cells on the mobility of the charge carriers moving by thermally activated hopping. Particular attention was given to the so called intermixed phase, or interface roughness, that has recently been shown to promote an increase in the cell efficiency. The domains were obtained from a Monte Carlo simulation of a two-species lattice gas. We generated domain morphologies with controllable channel size and interface roughness. The field and density dependence of the carrier hopping mobility in different morphologies was obtained by solving a master equation. Our results show that the mobility decreases with roughness and increases with typical channel sizes. The deleterious effect of the roughness on the mobility is quite dramatic at low carrier densities and high fields. The complex channel network is shown to be directly responsible for two potentially harmful effects to the cell performance: a remarkable decrease of the mobility with increasing field and the accumulation of charge at the domains interface, which leads to recombination losses.

Retention prediction of highly polar ionizable solutes under gradient conditions on a mixed-mode reversed-phase and weak anion-exchange stationary phase.

PubMed

Balkatzopoulou, P; Fasoula, S; Gika, H; Nikitas, P; Pappa-Louisi, A

2015-05-29

In the present work the retention of three highly polar and ionizable solutes - uric acid, nicotinic acid and ascorbic acid - was investigated on a mixed-mode reversed-phase and weak anion-exchange (RP/WAX) stationary phase in buffered aqueous acetonitrile (ACN) mobile phases. A U-shaped retention behavior was observed for all solutes with respect to the eluent organic modifier content studied in a range of 5-95% (v/v). This retention behavior clearly demonstrates the presence of a HILIC-type retention mechanism at ACN-rich hydro-organic eluents and an RP-like retention at aqueous-rich hydro-organic eluents. Hence, this column should be promising for application under both RP and HILIC gradient elution modes. For this reason, a series of programmed elution runs were carried out with increasing (RP) and decreasing (HILIC) organic solvent concentration in the mobile phase. This dual gradient process was successfully modeled by two retention models exhibiting a quadratic or a cubic dependence of the logarithm of the solute retention factor (lnk) upon the organic modifier volume fraction (φ). It was found that both models produced by gradient retention data allow the prediction of solute retention times for both types of programmed elution on the mixed-mode column. Four, in the case of the quadratic model, or five, in the case of the cubic model, initial HILIC- and RP-type gradient runs gave satisfactory retention predictions of any similar kind elution program, even with different flow rate, with an overall error of only 2.5 or 1.7%, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Organic Acids Regulation of Chemical-Microbial Phosphorus Transformations in Soils.

PubMed

Menezes-Blackburn, Daniel; Paredes, Cecilia; Zhang, Hao; Giles, Courtney D; Darch, Tegan; Stutter, Marc; George, Timothy S; Shand, Charles; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Blackwell, Martin; Wearing, Catherine; Haygarth, Philip M

2016-11-01

We have used an integrated approach to study the mobility of inorganic phosphorus (P) from soil solid phase as well as the microbial biomass P and respiration at increasing doses of citric and oxalic acid in two different soils with contrasting agronomic P status. Citric or oxalic acids significantly increased soil solution P concentrations for doses over 2 mmol kg -1 . However, low organic acid doses (<2 mmol kg -1 ) were associated with a steep increase in microbial biomass P, which was not seen for higher doses. In both soils, treatment with the tribasic citric acid led to a greater increase in soil solution P than the dibasic oxalic acid, likely due to the rapid degrading of oxalic acids in soils. After equilibration of soils with citric or oxalic acids, the adsorbed-to-solution distribution coefficient (K d ) and desorption rate constants (k -1 ) decreased whereas an increase in the response time of solution P equilibration (T c ) was observed. The extent of this effect was shown to be both soil and organic acid specific. Our results illustrate the critical thresholds of organic acid concentration necessary to mobilize sorbed and precipitated P, bringing new insight on how the exudation of organic acids regulate chemical-microbial soil phosphorus transformations.

A rapid method for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet by ultra performance liquid chromatography-tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Wabaidur, Saikh Mohammad; Alothman, Zeid Abdullah; Khan, Mohammad Rizwan

2013-05-01

In present study, a rapid and sensitive method using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet. The optimum chromatographic separation was carried out on a reversed phase Waters® Acquity UPLC BEH C18 column (1.7 μm particle size, 100 mm × 2.1 mm ID) with an isocratic elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile (75:25, v/v, pH 3.5) at flow rate of 0.5 mL min-1. The influences of mobile phase composition, flow rate and pH on chromatographic resolution were investigated. The total chromatographic analysis time was as short as 2 min with excellent resolution. Detection and quantification of the target compounds were carried out with a triple quadrupole mass spectrometer using negative electrospray ionization (ESI) and multiple reaction monitoring (MRM) modes. The performance of the method was evaluated and very low limits of detection less than 0.09 μg g-1, excellent coefficient correlation (r2 > 0.999) with liner range over a concentration range of 0.1-1.0 μg g-1 for both L-ascorbic acid and acetylsalicylic acid, and good intraday and interday precisions (relative standard deviations (R.S.D.) <3%), were obtained. Comparison of system performance with traditional liquid chromatography-photo diode array detector (HPLC-PDA) was made with respect to analysis time, sensitivity, linearity and precisions. The proposed UPLC-MS/MS method was found to be reproducible and appropriate for quantitative analysis of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet.

Ultra high performance supercritical fluid chromatography coupled with tandem mass spectrometry for screening of doping agents. I: Investigation of mobile phase and MS conditions.

PubMed

Nováková, Lucie; Grand-Guillaume Perrenoud, Alexandre; Nicoli, Raul; Saugy, Martial; Veuthey, Jean-Luc; Guillarme, Davy

2015-01-01

The conditions for the analysis of selected doping substances by UHPSFC-MS/MS were optimized to ensure suitable peak shapes and maximized MS responses. A representative mixture of 31 acidic and basic doping agents was analyzed, in both ESI+ and ESI- modes. The best compromise for all compounds in terms of MS sensitivity and chromatographic performance was obtained when adding 2% water and 10mM ammonium formate in the CO2/MeOH mobile phase. Beside mobile phase, the nature of the make-up solvent added for interfacing UHPSFC with MS was also evaluated. Ethanol was found to be the best candidate as it was able to compensate for the negative effect of 2% water addition in ESI- mode and provided a suitable MS response for all doping agents. Sensitivity of the optimized UHPSFC-MS/MS method was finally assessed and compared to the results obtained in conventional UHPLC-MS/MS. Sensitivity was improved by 5-100-fold in UHPSFC-MS/MS vs. UHPLC-MS/MS for 56% of compounds, while only one compound (bumetanide) offered a significantly higher MS response (4-fold) under UHPLC-MS/MS conditions. In the second paper of this series, the optimal conditions for UHPSFC-MS/MS analysis will be employed to screen >100 doping agents in urine matrix and results will be compared to those obtained by conventional UHPLC-MS/MS. Copyright © 2014 Elsevier B.V. All rights reserved.

Heavy metal speciation in solid-phase materials from a bacterial sulfate reducing bioreactor using sequential extraction procedure combined with acid volatile sulfide analysis.

PubMed

Jong, Tony; Parry, David L

2004-04-01

Heavy metal mobility, bioavailability and toxicity depends largely on the chemical form of metals and ultimately determines potential for environmental pollution. For this reason, determining the chemical form of heavy metals and metalloids, immobilized in sludges by biological mediated sulfate reduction, is important to evaluate their mobility and bioavailability. A modified Tessier sequential extraction procedure (SEP), complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, were applied to determine the partitioning of five heavy metals (defined as Fe, Ni, Zn and Cu, and the metalloid As) in anoxic solid-phase material (ASM) from an anaerobic, sulfate reducing bioreactor into six operationally defined fractions. These fractions were water soluble, exchangeable, bound to carbonates (acid soluble), bound to Fe-Mn oxides (reducible), bound to organic matter and sulfides (oxidizable) and residual. It was found that the distribution of Fe, Ni, Zn, Cu and As in ASM was strongly influenced by its association with the above solid fractions. The fraction corresponding to organic matter and sulfides appeared to be the most important scavenging phases of As, Fe, Ni, Zn and Cu in ASM (59.8-86.7%). This result was supported by AVS and SEM (Sigma Zn, Ni and Cu) measurements, which indicated that the heavy metals existed overwhelmingly as sulfides in the organic matter and sulfide fraction. A substantial amount of Fe and Ni at 16.4 and 20.1%, respectively, were also present in the carbonate fraction, while an appreciable portion of As (18.3%) and Zn (19.4%) was bound to Fe-Mn oxides. A significant amount of heavy metals was also associated with the residual fraction, ranging from 2.1% for Zn to 18.8% for As. Based on the average total extractable heavy metal (TEHM) values, the concentration of heavy metals in the ASM was in the order of Cu > Ni > Zn > Fe > As. If the mobility and bioavailability of heavy metals are assumed to be

Change in the plasmid copy number in acetic acid bacteria in response to growth phase and acetic acid concentration.

PubMed

Akasaka, Naoki; Astuti, Wiwik; Ishii, Yuri; Hidese, Ryota; Sakoda, Hisao; Fujiwara, Shinsuke

2015-06-01

Plasmids pGE1 (2.5 kb), pGE2 (7.2 kb), and pGE3 (5.5 kb) were isolated from Gluconacetobacter europaeus KGMA0119, and sequence analyses revealed they harbored 3, 8, and 4 genes, respectively. Plasmid copy numbers (PCNs) were determined by real-time quantitative PCR at different stages of bacterial growth. When KGMA0119 was cultured in medium containing 0.4% ethanol and 0.5% acetic acid, PCN of pGE1 increased from 7 copies/genome in the logarithmic phase to a maximum of 12 copies/genome at the beginning of the stationary phase, before decreasing to 4 copies/genome in the late stationary phase. PCNs for pGE2 and pGE3 were maintained at 1-3 copies/genome during all phases of growth. Under a higher concentration of ethanol (3.2%) the PCN for pGE1 was slightly lower in all the growth stages, and those of pGE2 and pGE3 were unchanged. In the presence of 1.0% acetic acid, PCNs were higher for pGE1 (10 copies/genome) and pGE3 (6 copies/genome) during the logarithmic phase. Numbers for pGE2 did not change, indicating that pGE1 and pGE3 increase their PCNs in response to acetic acid. Plasmids pBE2 and pBE3 were constructed by ligating linearized pGE2 and pGE3 into pBR322. Both plasmids were replicable in Escherichia coli, Acetobacter pasteurianus and G. europaeus, highlighting their suitability as vectors for acetic acid bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Rapid, simultaneous and nanomolar determination of pyroglutamic acid and cis-/trans-urocanic acid in human stratum corneum by hydrophilic interaction liquid chromatography (HILIC)-electrospray ionization tandem mass spectrometry.

PubMed

Joo, Kyung-Mi; Han, Ji Yeon; Son, Eui Dong; Nam, Gae-Won; Chung, Han Young; Jeong, Hye-Jin; Cho, Jun-Cheol; Lim, Kyung-Min

2012-05-15

A rapid, sensitive and specific hydrophilic interaction liquid chromatography coupled to tandem mass spectrometric (HILIC-MS/MS) method for the simultaneous determination of pyroglutamic acid, cis- and trans-urocanic acid in human skin stratum corneum (SC) were developed and validated. This method was carried out without derivatization or addition of ion-pair additives in mobile phase. The analytes were extracted by PBS buffer solution and analyzed using an electrospray positive ionization mass spectrometry in the multiple reaction monitoring (MRM) mode. Chromatographic separation was performed on an AQUITY UPLC amide column using gradient elution with the mobile phase of water and acetonitrile. The standard curves were linear over the concentration range of 1.0-250 ng/mL with a correlation coefficient higher than 0.999 with an LLOQ of 0.5 ng/mL. The lower limits of detection (LLOD) of these analytes were lower than 0.2 ng/mL. The intra- and inter-day precisions were measured to be below 7.7% and accuracies were within the range of 94.3-102.6%. The validated method was successfully applied to determine the level of pyroglutamic acid and cis-/trans-urocanic acid in the SC samples from forearm and forehead region of 19 human volunteers. Copyright © 2012 Elsevier B.V. All rights reserved.

Chromatographic behavior of small organic compounds in low-temperature high-performance liquid chromatography using liquid carbon dioxide as the mobile phase.

PubMed

Motono, Tomohiro; Nagai, Takashi; Kitagawa, Shinya; Ohtani, Hajime

2015-07-01

Low-temperature high-performance liquid chromatography, in which a loop injector, column, and detection cell were refrigerated at -35ºC, using liquid carbon dioxide as the mobile phase was developed. Small organic compounds (polyaromatic hydrocarbons, alkylbenzenes, and quinones) were separated by low-temperature high-performance liquid chromatography at temperatures from -35 to -5ºC. The combination of liquid carbon dioxide mobile phase with an octadecyl-silica (C18 ) column provided reversed phase mode separation, and a bare silica-gel column resulted in normal phase mode separation. In both the cases, nonlinear behavior at approximately -15ºC was found in the relationship between the temperature and the retention factors of the analytes (van't Hoff plots). In contrast to general trends in high-performance liquid chromatography, the decrease in temperature enhanced the separation efficiency of both the columns. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Third phase formation in the extraction of phosphotungstic acid by TBP in n-octane.

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

Antonio, M. R.; Chiarizia, R.; Jaffrennou, F.

2010-08-30

The solvent extraction of 12-phosphotungstic acid, also known as 12-tungstophosphoric acid-H{sub 3}PW{sub 12}O{sub 40}, the so-called Keggin heteropolyacid - by 0.73 M (20%v/v) tri-n-butyl phosphate (TBP) in n-octane under conditions comparable to those used previously for the extraction of conventional inorganic mineral acids is described. A simplified phase diagram for the pentanary system comprised of H{sub 3}PW{sub 12}O{sub 40}, HNO{sub 3}, H{sub 2}O, TBP, and n-octane reveals an extremely low initial concentration of H{sub 3}PW{sub 12}O{sub 40} (1.1 mM) at the LOC (limiting organic concentration) condition, far lower than the most effective third-phase-forming inorganic acid, namely HClO{sub 4}. The resultsmore » from small-angle neutron scattering (SANS) indicate that the interparticle attraction energy - U(r) calculated through application of the Baxter sticky sphere model to the SANS data at the LOC condition - does not approach the -2 k{sub B} T value associated with phase splitting in previous studies of TBP third-phase formation. The third-phase formation model based on attractive interactions between polar cores of reverse micelles, successfully developed for TBP and other extraction systems does not apply to the extraction of H{sub 3}PW{sub 12}O{sub 40}. Rather, the separation of a third-phase from the TBP organic phase stems from the limited solubility of the heavy and highly polar H{sub 3}PW{sub 12}O{sub 40}-TBP species in the alkane diluent.« less

Mixture-mixture design for the fingerprint optimization of chromatographic mobile phases and extraction solutions for Camellia sinensis.

PubMed

Borges, Cleber N; Bruns, Roy E; Almeida, Aline A; Scarminio, Ieda S

2007-07-09

A composite simplex centroid-simplex centroid mixture design is proposed for simultaneously optimizing two mixture systems. The complementary model is formed by multiplying special cubic models for the two systems. The design was applied to the simultaneous optimization of both mobile phase chromatographic mixtures and extraction mixtures for the Camellia sinensis Chinese tea plant. The extraction mixtures investigated contained varying proportions of ethyl acetate, ethanol and dichloromethane while the mobile phase was made up of varying proportions of methanol, acetonitrile and a methanol-acetonitrile-water (MAW) 15%:15%:70% mixture. The experiments were block randomized corresponding to a split-plot error structure to minimize laboratory work and reduce environmental impact. Coefficients of an initial saturated model were obtained using Scheffe-type equations. A cumulative probability graph was used to determine an approximate reduced model. The split-plot error structure was then introduced into the reduced model by applying generalized least square equations with variance components calculated using the restricted maximum likelihood approach. A model was developed to calculate the number of peaks observed with the chromatographic detector at 210 nm. A 20-term model contained essentially all the statistical information of the initial model and had a root mean square calibration error of 1.38. The model was used to predict the number of peaks eluted in chromatograms obtained from extraction solutions that correspond to axial points of the simplex centroid design. The significant model coefficients are interpreted in terms of interacting linear, quadratic and cubic effects of the mobile phase and extraction solution components.

Satellite mobile data service for Canada

NASA Technical Reports Server (NTRS)

Egan, Glenn R.; Sward, David J.

1990-01-01

A commercial mobile satellite system which is to be constructed and operated in Canada is examined. This is done in two phases. First, mobile data services was introduced. Hub equipment and 3000 mobile data terminals were supplied. Over the satellite tests were performed. The mobile data service provides full two way digital messaging automatic vehicle location and fleet management services. The second phase is to construct, launch and make operational the MSAT satellite and associated network control facilities. The implementation is examined of the mobile data service in Canada, including the technical description. Marketing and applications are also examined.

An Experimental and Computational Study of the Gas-Phase Acidities of the Common Amino Acid Amides.

PubMed

Plummer, Chelsea E; Stover, Michele L; Bokatzian, Samantha S; Davis, John T M; Dixon, David A; Cassady, Carolyn J

2015-07-30

Using proton-transfer reactions in a Fourier transform ion cyclotron resonance mass spectrometer and correlated molecular orbital theory at the G3(MP2) level, gas-phase acidities (GAs) and the associated structures for amides corresponding to the common amino acids have been determined for the first time. These values are important because amino acid amides are models for residues in peptides and proteins. For compounds whose most acidic site is the C-terminal amide nitrogen, two ions populations were observed experimentally with GAs that differ by 4-7 kcal/mol. The lower energy, more acidic structure accounts for the majority of the ions formed by electrospray ionization. G3(MP2) calculations predict that the lowest energy anionic conformer has a cis-like orientation of the [-C(═O)NH](-) group whereas the higher energy, less acidic conformer has a trans-like orientation of this group. These two distinct conformers were predicted for compounds with aliphatic, amide, basic, hydroxyl, and thioether side chains. For the most acidic amino acid amides (tyrosine, cysteine, tryptophan, histidine, aspartic acid, and glutamic acid amides) only one conformer was observed experimentally, and its experimental GA correlates with the theoretical GA related to side chain deprotonation.

MobileSat (R): A characteristically Australian MSS

NASA Technical Reports Server (NTRS)

Wagg, Michael; Jansen, Michael

1995-01-01

Optus launched its mobile satellite telephone service MobileSat in August 1994. This provided Australia and its neighboring waters with nation-wide mobile telephone coverage and still is the world's only domestic mobile satellite telephone system. This paper provides details of Optus' experience in developing and launching the MobileSat service, including (1) a retrospective of the issues that have waxed and waned in importance during the development and implementation phases, and (2) the strategy for future activities based on the experience gained in the development phase.

Multivariate analysis of organic acids in fermented food from reversed-phase high-performance liquid chromatography data.

PubMed

Mortera, Pablo; Zuljan, Federico A; Magni, Christian; Bortolato, Santiago A; Alarcón, Sergio H

2018-02-01

Multivariate calibration coupled to RP-HPLC with diode array detection (HPLC-DAD) was applied to the identification and the quantitative evaluation of the short chain organic acids (malic, oxalic, formic, lactic, acetic, citric, pyruvic, succinic, tartaric, propionic and α-cetoglutaric) in fermented food. The goal of the present study was to get the successful resolution of a system in the combined occurrence of strongly coeluting peaks, of distortions in the time sensors among chromatograms, and of the presence of unexpected compounds not included in the calibration step. Second-order HPLC-DAD data matrices were obtained in a short time (10min) on a C18 column with a chromatographic system operating in isocratic mode (mobile phase was 20mmolL -1 phosphate buffer at pH 2.20) and a flow-rate of 1.0mLmin -1 at room temperature. Parallel factor analysis (PARAFAC) and unfolded partial least-squares combined with residual bilinearization (U-PLS/RBL) were the second-order calibration algorithms select for data processing. The performance of the analytical parameters was good with an outstanding limit of detection (LODs) for acids ranging from 0.15 to 10.0mmolL -1 in the validation samples. The improved method was applied to the analysis of many dairy products (yoghurt, cultured milk and cheese) and wine. The method was shown as an effective means for determining and following acid contents in fermented food and was characterized by reducibility with simple, high resolution and rapid procedure without derivatization of analytes. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of folic acid stability in fortified instant noodles by use of capillary electrophoresis and reversed-phase high performance liquid chromatography.

PubMed

Hau Fung Cheung, Rodney; Morrison, Paul D; Small, Darryl M; Marriott, Philip J

2008-12-05

A single enzyme treatment with alpha-amylase, prior to the quantification of added folic acid (FA) in fortified instant fried Asian noodles with analysis performed by capillary zone electrophoresis (CZE) and reversed-phase high performance liquid chromatography (RP-HPLC) with UV detection, is described. The method was validated and optimized for capillary electrophoresis (CE) with separation achieved using a 8 mM phosphate-12 mM borate run buffer with 5% MeOH at pH 9.5. FA was well separated from matrix components with nicotinic acid (NA) employed as an internal standard. In a comparative study, separation of FA was performed using HPLC with a mobile phase consisting of 27% MeOH (v/v) in aqueous potassium phosphate buffer (3.5 mM KH(2)PO(4) and 3.2 mM K(2)HPO(4)), pH 8.5, and containing 5 mM tetrabutylammonium dihydrogen phosphate as an ion-pairing agent. For both methods, excellent results were obtained for various analytical parameters including linearity, accuracy and precision. The limit of detection was calculated to be 2.2 mg/L for CE without sample stacking and 0.10 mg/L with high performance liquid chromatography (HPLC). Sample extraction involved homogenization and enzymatic extraction with alpha-amylase. Results indicated that FA was stable during four main stages of instant fried noodle manufacturing (dough crumbs, cut sheets, steaming and frying).

Use of oleic-acid functionalized nanoparticles for the magnetic solid-phase microextraction of alkylphenols in fruit juices using liquid chromatography-tandem mass spectrometry.

PubMed

Viñas, Pilar; Pastor-Belda, Marta; Torres, Aitor; Campillo, Natalia; Hernández-Córdoba, Manuel

2016-05-01

Magnetic nanoparticles of cobalt ferrite with oleic acid as the surfactant (CoFe2O4/oleic acid) were used as sorbent material for the determination of alkylphenols in fruit juices. High sensitivity and specificity were achieved by liquid chromatography and detection using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the selected reaction monitoring (SRM) mode of the negative fragment ions for alkylphenols (APs) and in positive mode for ethoxylate APs (APEOs). The optimized conditions for the different variables influencing the magnetic separation procedure were: mass of magnetic nanoparticles, 50mg, juice volume, 10mL diluted to 25mL with water, pH 6, stirring for 10min at room temperature, separation with an external neodymium magnet, desorption with 3mL of methanol and orbital shaking for 5min. The enriched organic phase was evaporated and reconstituted with 100µL acetonitrile before injecting 30µL into a liquid chromatograph with a mobile phase composed of acetonitrile/0.1% (v/v) formic acid under gradient elution. Quantification limits were in the range 3.6 to 125ngmL(-1). The recoveries obtained were in the 91-119% range, with RSDs lower than 14%. The ESI-MS/MS spectra permitted the correct identification of both APs and APEOs in the fruit juice samples. Copyright © 2016 Elsevier B.V. All rights reserved.

30 CFR 77.900 - Low- and medium-voltage circuits serving portable or mobile three-phase alternating current...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Low- and medium-voltage circuits serving... Medium-Voltage Alternating Current Circuits § 77.900 Low- and medium-voltage circuits serving portable or mobile three-phase alternating current equipment; circuit breakers. Low- and medium-voltage circuits...

30 CFR 77.900 - Low- and medium-voltage circuits serving portable or mobile three-phase alternating current...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Low- and medium-voltage circuits serving... Medium-Voltage Alternating Current Circuits § 77.900 Low- and medium-voltage circuits serving portable or mobile three-phase alternating current equipment; circuit breakers. Low- and medium-voltage circuits...

30 CFR 77.900 - Low- and medium-voltage circuits serving portable or mobile three-phase alternating current...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Low- and medium-voltage circuits serving... Medium-Voltage Alternating Current Circuits § 77.900 Low- and medium-voltage circuits serving portable or mobile three-phase alternating current equipment; circuit breakers. Low- and medium-voltage circuits...

Mobilization of arsenic and heavy metals from polluted soils by humic acid

NASA Astrophysics Data System (ADS)

Reyes, Arturo; Fuentes, Bárbara; Letelier, María Victoria; Cuevas, Jacqueline

2017-04-01

The existence of soils contaminated with harmful elements by mining activities is a global environmental concern. The northern part of Chile has several heavy metal contaminated sites due to former copper and gold artisanal mining activities. Therefore, a complete characterization of abandoned sites and the implementation of remediation technologies are of interest for regulators, the industry, and the population. The objective of the study was to test the use of humic acid as a washing treatment to reduce the heavy metal concentration of soil samples impacted by mine waste material. A stratified random sampling was conducted on the target site to determine the physical and chemical composition of mine waste and soil material. The sampling consisted of taking 37 samples at 0-20 cm depths in a 10,000 square-meter area. The samples were dried and sieved at 2 mm. The batch washing experiments were conducted in triplicate at pH 7.0. A 1:10 solid to liquid ratio and three humic acid dose (0, 50, and 100 mg/l) were used. After shaking (24 h, room temperature) and subsequently filtration (0.22 μm), the supernatants were analyzed for heavy metals, redox potential and pH. The heavy metals mobility was assessed using extraction methods before and after treatments. The soils had alkaline pH values, conductivity ranged between 8 and 35 mS/cm, with low organic matter. Total concentrations of Vanadium (V) (10.80 to 175.00 mg/kg), Lead (Pb) (7.31 to 90.10 mg/kg), Antimonium (Sb) (0.83 to 101.00 mg/kg), and Arsenic (As) (9.53 to 2691.00 mg/kg) exceeded several times the EPA`s recommended values for soils. At 100 mg/L HA the removal efficiencies for V, Pb, Sb, and As were 32, 68, 77, and 82% respectively. According to the extraction procedure V, Pb, Sb, and As species are mainly as oxidizable and residual fractions. According to the results, the target mine site is contaminated with harmful elements. It can be concluded that the use of humic acid is a good alternative as a

Analysis of carbon functional groups in mobile humic acid and recalcitrant calcium humate extracted from eight US soils

USDA-ARS?s Scientific Manuscript database

Solid state 13C nuclear magnetic resonance (NMR) spectroscopy is a common tool to study the structure of soil humic fractions; however, knowledge regarding carbon structural relationships in humic fractions is limited. In this study, mobile humic acid (MHA) and recalcitrant calcium humate (CaHA) fr...

Electron mobility enhancement in metalorganic-vapor-phase-epitaxy-grown InAlN high-electron-mobility transistors by control of surface morphology of spacer layer

NASA Astrophysics Data System (ADS)

Yamada, Atsushi; Ishiguro, Tetsuro; Kotani, Junji; Nakamura, Norikazu

2018-01-01

We demonstrated low-sheet-resistance metalorganic-vapor-phase-epitaxy-grown InAlN high-electron-mobility transistors using AlGaN spacers with excellent surface morphology. We systematically investigated the effects of AlGaN spacer growth conditions on surface morphology and electron mobility. We found that the surface morphology of InAlN barriers depends on that of AlGaN spacers. Ga desorption from AlGaN spacers was suppressed by increasing the trimethylaluminum (TMA) supply rate, resulting in the small surface roughnesses of InAlN barriers and AlGaN spacers. Moreover, we found that an increase in the NH3 supply rate also improved the surface morphologies of InAlN barriers and AlGaN spacers as long as the TMA supply rate was high enough to suppress the degradation of GaN channels. Finally, we realized a low sheet resistance of 185.5 Ω/sq with a high electron mobility of 1210 cm2 V-1 s-1 by improving the surface morphologies of AlGaN spacers and InAlN barriers.

Potential human health effects of acid rain: report of a workshop

PubMed Central

Goyer, Robert A.; Bachmann, John; Clarkson, Thomas W.; Ferris, Benjamin G.; Graham, Judith; Mushak, Paul; Perl, Daniel P.; Rall, David P.; Schlesinger, Richard; Sharpe, William; Wood, John M.

1985-01-01

This report summarizes the potential impact of the acid precipitation phenomenon on human health. There are two major components to this phenomenon: the predepositional phase, during which there is direct human exposure to acidic substances from ambient air, and the post-depositional phase, in which the deposition of acid materials on water and soil results in the mobilization, transport, and even chemical transformation of toxic metals. Acidification increases bioconversion of mercury to methylmercury, which accumulates in fish, increasing the risk to toxicity in people who eat fish. Increase in water and soil content of lead and cadmium increases human exposure to these metals which become additive to other sources presently under regulatory control. The potential adverse health effects of increased human exposure to aluminum is not known at the present time. PMID:3896772

Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

PubMed

Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

2016-08-17

We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions.

Mobile satellite service for Canada

NASA Technical Reports Server (NTRS)

Sward, David

1988-01-01

The Mobile Satellite (MSAT) system and a special program designed to provide interim mobile satellite services (IMSS) during the construction phase of MSAT are described. A mobile satellite system is a key element in extending voice and and data telecommunications to all Canadians.

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 ...

Are carboxyl groups the most acidic sites in amino acids? Gas-phase acidities, photoelectron spectra, and computations on tyrosine, p-hydroxybenzoic acid, and their conjugate bases.

PubMed

Tian, Zhixin; Wang, Xue-Bin; Wang, Lai-Sheng; Kass, Steven R

2009-01-28

Deprotonation of tyrosine in the gas phase was found to occur preferentially at the phenolic site, and the conjugate base consists of a 70:30 mixture of phenoxide and carboxylate anions at equilibrium. This result was established by developing a chemical probe for differentiating these two isomers, and the presence of both ions was confirmed by photoelectron spectroscopy. Equilibrium acidity measurements on tyrosine indicated that deltaG(acid)(o) = 332.5 +/- 1.5 kcal mol(-1) and deltaH(acid)(o) = 340.7 +/- 1.5 kcal mol(-1). Photoelectron spectra yielded adiabatic electron detachment energies of 2.70 +/- 0.05 and 3.55 +/- 0.10 eV for the phenoxide and carboxylate anions, respectively. The H/D exchange behavior of deprotonated tyrosine was examined using three different alcohols (CF3CH2OD, C6H5CH2OD, and CH3CH2OD), and incorporation of up to three deuterium atoms was observed. Two pathways are proposed to account for these results, and all of the experimental findings are supplemented with B3LYP/aug-cc-pVDZ and G3B3 calculations. In addition, it was found that electrospray ionization of tyrosine from a 3:1 (v/v) CH3OH/H2O solution using a commercial source produces a deprotonated [M-H]- anion with the gas-phase equilibrium composition rather than the structure of the ion that exists in aqueous media. Electrospray ionization from acetonitrile, however, leads largely to the liquid-phase (carboxylate) structure. A control molecule, p-hydroxybenzoic acid, was found to behave in a similar manner. Thus, the electrospray conditions that are employed for the analysis of a compound can alter the isomeric composition of the resulting anion.

Ionic liquids as stationary phases for fatty acid analysis by gas chromatography.

PubMed

Fanali, C; Micalizzi, G; Dugo, P; Mondello, L

2017-12-04

The present paper provides an overview of the application of ionic liquid (IL) columns for GC analysis of fatty acid methyl esters (FAMEs). Although their separation can be carried out utilizing GC columns containing polar stationary phases, some ILs have been employed as stationary phases, either commercial or laboratory made, in GC analysis. Monodimensional and bidimensional GC methods have been optimized in order to achieve the best separation especially considering the geometric and positional isomers of unsaturated fatty acids. Several methods for the analysis of trans-fatty acids have also been reported. The use of GC-GC, using either the same IL columns or different columns in the first and second dimensions, allowed the separation of a large number of FAMEs. The application of the IL columns for GC analysis of FAMEs in different types of real samples is described, e.g., oil of different nature (fish, flaxseed, and olive), margarine and butter, biodiesel, milk, bacteria etc.

Mobile contingency locus controlling Escherichia coli K1 polysialic acid capsule acetylation.

PubMed

Vimr, Eric R; Steenbergen, Susan M

2006-05-01

Escherichia coli K1 is part of a reservoir of adherent, invasive facultative pathogens responsible for a wide range of human and animal disease including sepsis, meningitis, urinary tract infection and inflammatory bowel syndrome. A prominent virulence factor in these diseases is the polysialic acid capsular polysaccharide (K1 antigen), which is encoded by the kps/neu accretion domain inserted near pheV at 67 map units. Some E. coli K1 strains undergo form (phase) variation involving loss or gain of O-acetyl esters at carbon positions 7 or 9 of the individual sialic acid residues of the polysialic acid chains. Acetylation is catalysed by the receptor-modifying acetyl coenzyme-A-dependent O-acetyltransferase encoded by neuO, a phase variable locus mapping near the integrase gene of the K1-specific prophage, CUS-3, which is inserted in argW at 53.1 map units. As the first E. coli contingency locus shown to operate by a translational switch, further investigation of neuO should provide a better understanding of the invasive K1 pathotype. Minimal estimates of morbidity and economic costs associated with human infections caused by extraintestinal pathogenic E. coli strains such as K1 indicate at least 6.5 million cases with attendant medical costs exceeding 2.5 billion US dollars annually in the United States alone.

Efficient counter-current chromatographic isolation and structural identification of two new cinnamic acids from Echinacea purpurea.

PubMed

Lu, Ying; Li, JiaYin; Li, MiLu; Hu, Xia; Tan, Jun; Liu, Zhong Hua

2012-10-01

Two new cinnamic acids, 2-O-caffeoyl-3-O-isoferuloyltartaric (3), and 2, 3-di-O-isoferuloyltartaric acid (5), along with three known caffeic acids, cichoric acid (1), 2-O-caffeoyl-3-O-feruloyltartaric acid (2) and 2-O-caffeoyl-3-O-p-coumaroyltartaric acid (4), have been successfully isolated and purified from Echinacea purpurea. In this study, we investigated an efficient method for the preparative isolation and purification of cinnamic acids from E. purpurea by high-speed counter-current chromatography (HSCCC). The separation was performed using a two-phase solvent composed of n-hexane-ethyl-acetate-methanol-0.5% aqueous acetic acid (1:3:1:4, v/v). The upper phase was used as the stationary phase and the lower phase as the mobile phase, with a flow rate of 1.6 mL/min. From 250 mg of crude extracts, 65.1 mg of 1, 8.3 mg of 2, 4.0 mg of 3, 4.5 mg of 4, and 4.3 mg of 5 were isolated in one-step, with purities of 98.5%, 97.7%, 94.6%, 94.3%, and 98.6%, respectively, as evaluated by HPLC-DAD. The chemical structures were identified by electro spray ionization mass spectrometry (ESI-MS) and one- and two-dimensional NMR spectra. HSCCC was very efficient for the separation and purification of the cinnamic acids from

Chromatographic behaviour of synthetic high pressure high temperature diamond in aqueous normal phase chromatography.

PubMed

Peristyy, Anton; Paull, Brett; Nesterenko, Pavel N

2016-10-28

The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated under the conditions of hydrophilic interaction liquid chromatography (HILIC). A 50×4.6mm ID stainless steel column packed with HPHT particles of mean diameter 1.6μm and specific surface area 5.1m 2 g -1 is used. According to the results of acid-base titration with NaOH the purified HPHT batch contains 4.59μeqg -1 of protogenic, mainly carboxyl- and hydroxyl-, groups, which make this polar adsorbent suitable for use as a stationary phase in HILIC. The retention behaviour of several classes of polar compounds including benzoic and benzenesulfonic acids, nitro- and chlorophenols, various organic bases, and quaternary ammonium compounds are studied using acetonitrile and methanol based mobile phases containing 5-30v/v% of water. The effects of the buffer pH and concentration, column temperature and organic solvent content on retention of model compounds are also investigated. It is shown that both pH and acetonitrile/methanol ratio in the mobile phase can be used to vary the separation selectivity. Molecular adsorption mechanism (related to aqueous normal phase mode), rather than partitioning is established to be responsible for the retention. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of salicylic acid by HPLC in plasma and saliva from children with juvenile chronic arthritis.

PubMed

Legaz, M E; Acitores, E; Valverde, F

1992-12-01

A high performance liquid chromatography (HPLC) method has been developed for measuring salicylic acid in the plasma and saliva of children with juvenile chronic arthritis (JCA). Samples were extracted with diethyl ether and, after drying, redissolved in methanol to be chromatographed. Quantitation of salicylic acid was performed by reverse phase HPLC on a spherisorb ODS-2 column, using methanol: water: acetic acid as mobile phase. Phenolic was monitored by absorbance at 237 nm. Linearity between the amount of mass injected and the response in the detector was determined. This method was applied to compare concentrations of salivary and plasma salicylic acid. The method also permitted the quantitation of salivary salicylate as a non-invasive, indirect method for monitoring the concentration of plasma salicylate in patients with JCA.

Phase transformations of 4,4'-biphenyldicarboxylic acid on Cu(001)

NASA Astrophysics Data System (ADS)

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Harold J. W.; Poelsema, Bene

2012-06-01

The growth and structure of 4,4'-biphenyldicarboxylic-acid (BDA) on Cu(001) at temperatures between 300 and 400 K was studied by low energy electron microscopy and μ-LEED. First, the adsorbed BDA molecules form a disordered dilute phase. Once this phase reaches a sufficiently high density, a crystalline phase nucleates, in which the molecules form a hydrogen-bonded two-dimensional (2D) supramolecular c(8×8) network. By a careful analysis of the bright-field image intensity, we can measure the density in the dilute phase, which is up to 30% of that in the crystalline phase. From the respective equilibrium densities at different temperatures, we determine the 2D phase diagram and extract a cohesive energy of 0.35 eV. We also analyze the island decay behavior and estimate the BDA molecule diffusion constants. Steps are found to be highly transparent for diffusing BDA molecules. In the temperature range of 362-400 K, we find chemical diffusion constants between 850-1700nm2s-1.

Chemical associations and mobilization of heavy metals in fly ash from municipal solid waste incineration.

PubMed

Weibel, Gisela; Eggenberger, Urs; Schlumberger, Stefan; Mäder, Urs K

2017-04-01

This study focusses on chemical and mineralogical characterization of fly ash and leached filter cake and on the determination of parameters influencing metal mobilization by leaching. Three different leaching processes of fly ash from municipal solid waste incineration (MSWI) plants in Switzerland comprise neutral, acidic and optimized acidic (+ oxidizing agent) fly ash leaching have been investigated. Fly ash is characterized by refractory particles (Al-foil, unburnt carbon, quartz, feldspar) and newly formed high-temperature phases (glass, gehlenite, wollastonite) surrounded by characteristic dust rims. Metals are carried along with the flue gas (Fe-oxides, brass) and are enriched in mineral aggregates (quartz, feldspar, wollastonite, glass) or vaporized and condensed as chlorides or sulphates. Parameters controlling the mobilization of neutral and acidic fly ash leaching are pH and redox conditions, liquid to solid ratio, extraction time and temperature. Almost no depletion for Zn, Pb, Cu and Cd is achieved by performing neutral leaching. Acidic fly ash leaching results in depletion factors of 40% for Zn, 53% for Cd, 8% for Pb and 6% for Cu. The extraction of Pb and Cu are mainly limited due to a cementation process and the formation of a PbCu 0 -alloy-phase and to a minor degree due to secondary precipitation (PbCl 2 ). The addition of hydrogen peroxide during acidic fly ash leaching (optimized acidic leaching) prevents this reduction through oxidation of metallic components and thus significantly higher depletion factors for Pb (57%), Cu (30%) and Cd (92%) are achieved. The elevated metal depletion using acidic leaching in combination with hydrogen peroxide justifies the extra effort not only by reduced metal loads to the environment but also by reduced deposition costs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Gas-Phase Amidation of Carboxylic Acids with Woodward’s Reagent K Ions

PubMed Central

Peng, Zhou; Pilo, Alice L.; Luongo, Carl A.; McLuckey, Scott A.

2015-01-01

Gas-phase amidation of carboxylic acids in multiply-charged peptides is demonstrated via ion/ion reactions with Woodward’s reagent K (wrk) in both positive and negative mode. Woodward’s reagent K, N-ethyl-3-phenylisoxazolium-3′-sulfonate, is a commonly used reagent that activates carboxylates to form amide bonds with amines in solution. Here, we demonstrate that the analogous gas-phase chemistry occurs upon reaction of the wrk ions and doubly protonated (or doubly deprotonated) peptide ions containing the carboxylic acid functionality. The reaction involves the formation of the enol ester intermediate in the electrostatic complex. Upon collisional activation, the ethyl amine on the reagent is transferred to the activated carbonyl carbon on the peptide, resulting in the formation of an ethyl amide (addition of 27 Da to the peptide) with loss of a neutral ketene derivative. Further collision-induced dissociation (CID) of the products and comparison with solution-phase amidation product confirms the structure of the ethyl amide. PMID:26122523

In-house SIRAS phasing of the polyunsaturated fatty-acid isomerase from Propionibacterium acnes

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

Liavonchanka, Alena; Hornung, Ellen; Feussner, Ivo

2006-02-01

Low iodide concentrations were sufficient to allow SAD and SIRAS phasing of cubic crystals of a novel fatty acid isomerase using Cu Kα radiation. The polyenoic fatty-acid isomerase from Propionibacterium acnes (PAI) catalyzes the double-bond isomerization of linoleic acid to conjugated linoleic acid, which is a dairy- or meat-derived fatty acid in the human diet. PAI was overproduced in Escherichia coli and purified to homogeneity as a yellow-coloured protein. The nature of the bound cofactor was analyzed by absorption and fluorescence spectroscopy. Single crystals of PAI were obtained in two crystal forms. Cubic shaped crystals belong to space group I2{submore » 1}3, with a unit-cell parameter of 160.4 Å, and plate-like crystals belong to the monoclinic space group C2, with unit-cell parameters a = 133.7, b = 60.8, c = 72.2 Å, β = 115.8°. Both crystal forms contain one molecule per asymmetric unit and diffract to a resolution of better than 2.0 Å. Initial phases were obtained by SIRAS from in-house data from a cubic crystal that was soaked with an unusually low KI concentration of 0.25 M.« less

Self-assembled Lyotropic Liquid Crystalline Phase Behavior of Monoolein-Capric Acid-Phospholipid Nanoparticulate Systems.

PubMed

Zhai, Jiali; Tran, Nhiem; Sarkar, Sampa; Fong, Celesta; Mulet, Xavier; Drummond, Calum J

2017-03-14

We report here the lyotropic liquid crystalline phase behavior of two lipid nanoparticulate systems containing mixtures of monoolein, capric acid, and saturated diacyl phosphatidylcholines dispersed by the Pluronic F127 block copolymer. Synchrotron small-angle X-ray scattering (SAXS) was used to screen the phase behavior of a library of lipid nanoparticles in a high-throughput manner. It was found that adding capric acid and phosphatidylcholines had opposing effects on the spontaneous membrane curvature of the monoolein lipid layer and hence the internal mesophase of the final nanoparticles. By varying the relative concentration of the three lipid components, we were able to establish a library of nanoparticles with a wide range of mesophases including at least the inverse bicontinuous primitive and double diamond cubic phases, the inverse hexagonal phase, the fluid lamellar phase, and possibly other phases. Furthermore, the in vitro cytotoxicity assay showed that the endogenous phospholipid-containing nanoparticles were less toxic to cultured cell lines compared to monoolein-based counterparts, improving the potential of the nonlamellar lipid nanoparticles for biomedical applications.

Distinguishing d - and l -aspartic and isoaspartic acids in amyloid β peptides with ultrahigh resolution ion mobility spectrometry

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

Zheng, Xueyun; Deng, Liulin; Baker, Erin S.

2017-01-01

Ion mobility spectrometry (IMS) was utilized to separate Aβ peptide variants containing isomeric asparic and isoaspartic acid residues with either al- ord-form. The abundance of each variant is of great interest in Alzheimer's disease studies and also to evaluate how often these modifications are occurring in other environmental and biological samples.

Phenylboronic acid modified solid-phase extraction column: Preparation, characterization, and application to the analysis of amino acids in sepia capsule by removing the maltose.

PubMed

Guo, Mengzhe; Yin, Dengyang; Han, Jie; Zhang, Liyan; Li, Xiao; He, Dandan; Du, Yan; Tang, Daoquan

2016-09-01

Maltose, a common auxiliary material of pharmaceutical preparation, may disturb the analysis of total amino acids in sepia capsule by aldolization. Therefore, it is necessary to remove the maltose through a convenient method. In this work, a phenylboronic acid modified solid-phase extraction column has been synthesized and used to remove the maltose. The materials were synthesized by one step "thiol-ene" reaction and the parameters of the column such as absorption capacity, recovery, and absorption specificity have been investigated. The results showed the column (0.5 cm of length × 0.5 cm of inner diameter) can absorb 4.6 mg maltose with a linear absorption and absorption specificity. Then this technique was applied in the quantification of amino acids in sepia capsule. After the optimization of the method, four kinds of amino acids, which were the most abundant, were quantified by high-performance liquid chromatography with diode array detection. The amounts of the four kinds of amino acids are 1.5∼2 times more than that without the treatment of solid-phase extraction column, which almost overcomes the influence of the maltose. All the results indicate that the phenylboronic acid modified solid-phase extraction column can successfully help to accurately quantify the total amino acids in sepia capsule. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene oxide for solid-phase extraction of bioactive phenolic acids.

PubMed

Hou, Xiudan; Wang, Xusheng; Sun, Yingxin; Wang, Licheng; Guo, Yong

2017-05-01

A solid-phase extraction (SPE) method for the efficient analysis of trace phenolic acids (PAs, caffeic acid, ferulic acid, protocatechuic acid, cinnamic acid) in urine was established. In this work, a graphene oxide (GO) coating was grafted onto pure silica to be investigated as SPE material. The prepared GO surface had a layered and wrinkled structure that was rough and well organized, which could provide more open adsorption sites. Owing to its hydrophilicity and polarity, GO showed higher extraction efficiency toward PAs than reduced GO did, in agreement with the theoretical calculation results performed by Gaussian 09 software. The adsorption mechanism of PAs on GO@Sil was also investigated through static state and kinetic state adsorption experiments, which showed a monolayer surface adsorption. Extraction capacity of the as-prepared material was optimized using the response surface methodology. Under the optimized conditions, the as-established method provided wide linearity range (2-50 μg L -1 for protocatechuic acid and 1-50 μg L -1 for caffeic acid, ferulic acid, and cinnamic acid) and low limits of detection (0.25-1 μg L -1 ). Finally, the established method was applied for the analysis of urine from two healthy volunteers. The results indicate that the prepared material is a practical, cost-effective medium for the extraction and determination of phenolic acids in complex matrices. Graphical Abstract A graphene oxide coating was grafted onto pure silica as the SPE material for the extraction of phenolic acids in urines and the extraction mechanism was also mainly investigated.

A Nitrogen-concentrated Phase in IA Iron Meteorite Acid Residue

NASA Astrophysics Data System (ADS)

Hashizume, K.; Sugiura, N.

1993-07-01

Introduction: Iron meteorites are considered to have experienced a complex history, which is indicated by the variations in trace element chemistry (e.g., [1]). Among iron meteorite groups, the so called nonmagmatic groups, such as IAB, IIE, and IIICD, may have passed through different formation paths compared to others. Nitrogen isotopes can be a useful tool to understand the origin and formation processes of iron meteorites. Nikogen isotopes in a number of iron meteorites are measured [2,3], although trapping sites of nitrogen in iron meteorites are not yet clear. This is an important issue because nitrogen, a typical mobile element, may well reflect thermal history of their parent bodies (c.f., [4]). Generally, a major portion of nitrogen in iron meteorites is expected to be in a solid solution in Fe-Ni, especially in f.c.c. Fe-Ni (taenite). Franchi et al. [3] report that at least 25 to 35% of nitrogen in magmatic iron meteorites is in acid insoluble phases, however, not in those of non-magmatic meteorites. This result contradicts with the result [5] who report that a significant portion of nitrogen seems to be trapped in acid residues not only of magmatic meteorites but also of non- magmatic meteorites. To resolve the contradiction described above, and to identify the trapping site, we started measuring nitrogen isotopes in acid residues of iron metcorites. We report here preliminary results on acid residues of Canyon Diablo (IA). Procedures: Acid residues were prepared by Dr. J.-I. Matsuda and his colleagues. Different blocks of Canyon Diablo, "Can-1" and "Can-2" were treated by 14M HCl, 10M-HF + 1M-HCl, 1M-HCl, and by aqua regia, which destroyed Fe-Ni, sulfides, silicates, and shreibersite. Acid residues of these two blocks, "Can-1bn" and "Can-2b," yielded 0.102 wt% and 0.299 wt% of their original masses, respectively These residues seem to consist mostly of graphite No diamond was detected by powder X-ray analysis [6]. Preliminary Results: A predominant

Low-temperature phase behavior of fatty acid methyl esters by differential scanning calorimetry (DSC)

USDA-ARS?s Scientific Manuscript database

Fatty acid methyl ester (FAME) mixtures have many uses including biodiesel, lubricants, metal-working fluids, surfactants, polymers, coatings, green solvents and phase-change materials. The physical properties of a FAME mixture depends on the fatty acid concentration (FAC) profile. Some products hav...

Combined effects of potassium chloride and ethanol as mobile phase modulators on hydrophobic interaction and reversed-phase chromatography of three insulin variants.

PubMed

Johansson, Karolina; Frederiksen, Søren S; Degerman, Marcus; Breil, Martin P; Mollerup, Jørgen M; Nilsson, Bernt

2015-02-13

The two main chromatographic modes based on hydrophobicity, hydrophobic interaction chromatography (HIC) and reversed-phase chromatography (RPC), are widely used for both analytical and preparative chromatography of proteins in the pharmaceutical industry. Despite the extensive application of these separation methods, and the vast amount of studies performed on HIC and RPC over the decades, the underlying phenomena remain elusive. As part of a systematic study of the influence of mobile phase modulators in hydrophobicity-based chromatography, we have investigated the effects of both KCl and ethanol on the retention of three insulin variants on two HIC adsorbents and two RPC adsorbents. The focus was on the linear adsorption range, separating the modulator effects from the capacity effects, but some complementary experiments at higher load were included to further investigate observed phenomena. The results show that the modulators have the same effect on the two RPC adsorbents in the linear range, indicating that the modulator concentration only affects the activity of the solute in the mobile phase, and not that of the solute-ligand complex, or that of the ligand. Unfortunately, the HIC adsorbents did not show the same behavior. However, the insulin variants displayed a strong tendency toward self-association on both HIC adsorbents; on one in particular. Since this causes peak fronting, the retention is affected, and this could probably explain the lack of congruity. This conclusion was supported by the results from the non-linear range experiments which were indicative of double-layer adsorption on the HIC adsorbents, while the RPC adsorbents gave the anticipated increased tailing at higher load. Copyright © 2015 Elsevier B.V. All rights reserved.

Phase transition and epitaxies between hydrated orthorhombic and anhydrous monoclinic uric acid crystals

NASA Astrophysics Data System (ADS)

Boistelle, R.; Rinaudo, C.

1981-05-01

Anhydrous monoclinic and hydrated orthorhombic uric acid crystals can be nucleated and grown from pure water solutions either separately or together with epitaxial relationships. When crystals of one modification exist in the solution they can act as nucleation substrate for the crystals of the other modification. In both cases the new phase grows epitaxially on the substrate; the mutual orientations are the same but the contact planes are different. In addition, the anhydrous modification grows into the hydrated one which undergoes a phase transition by a dissolution-recrystallization process. It is likely that the same processes occur in human stones made up of uric acids.

Liquid-liquid phase separation in internally mixed magnesium sulfate/glutaric acid particles

NASA Astrophysics Data System (ADS)

Wu, Feng-Min; Wang, Xiao-Wei; Jing, Bo; Zhang, Yun-Hong; Ge, Mao-Fa

2018-04-01

The confocal Raman microscopy is utilized to investigate the liquid-liquid phase separation (LLPS) of mixed magnesium sulfate/glutaric acid (MgSO4/GA) droplets deposited on a hydrophobic polytetrafluoroethylene (PTFE) substrate and a hydrophilic quartz substrate. Raman spectra collected from different regions of the mixed droplets provide detailed information of component distributions for MgSO4 and GA. During the dehydration process, the MgSO4/GA mixed particles show the initial liquid-liquid phase separation between 85% and 80% relative humidity (RH) on both the hydrophobic and hydrophilic substrates. For the droplets deposited on the two substrates, the inner phase of droplets is dominated by aqueous MgSO4, which is surrounded by a rich GA organic layer due to the surface tension effects. In addition, the crystallization of GA could be observed in the organic aqueous phase while it is inhibited in the inner MgSO4 phase due to the effects of gel formation of MgSO4 at low RH. The Raman spectra reveal that with decreasing RH the morphology of the mixed droplet evolves from a uniform droplet to the structure of LLPS with the GA crystallizing in the outer layer and MgSO4 gel formed in the inner phase. These findings contribute to the further understanding of the role of interactions between inorganic salts and organic acids on the morphological evolution and environmental effects of atmospheric aerosols under ambient RH conditions.

It is all about the solvent: on the importance of the mobile phase for ZIC-HILIC glycopeptide enrichment.

PubMed

Alagesan, Kathirvel; Khilji, Sana Khan; Kolarich, Daniel

2017-01-01

Glycopeptide enrichment is a crucial step in glycoproteomics for which hydrophilic interaction chromatography (HILIC) has extensively been applied due to its low bias towards different glycan types. A systematic evaluation of applicable HILIC mobile phases on glycopeptide enrichment efficiency and selectivity is, to date, however, still lacking. Here, we present a novel, simplified technique for HILIC enrichment termed "Drop-HILIC", which was applied to systematically evaluate the mobile phase effect on ZIC-HILIC (zwitterionic type of hydrophilic interaction chromatography) glycopeptide enrichment. The four most commonly used MS compatible organic solvents were investigated: (i) acetonitrile, (ii) methanol, (iii) ethanol and (iv) isopropanol. Glycopeptide enrichment efficiencies were evaluated for each solvent system using samples of increasing complexity ranging from well-defined synthetic glycopeptides spiked into different concentrations of tryptic BSA peptides, followed by standard glycoproteins, and a complex sample derived from human (depleted and non-depleted) serum. ZIC-HILIC glycopeptide efficiency largely relied upon the used solvent. Different organic mobile phases enriched distinct glycopeptide subsets in a peptide backbone hydrophilicity-dependant manner. Acetonitrile provided the best compromise for the retention of both hydrophilic and hydrophobic glycopeptides, whereas methanol was confirmed to be unsuitable for this purpose. The enrichment efficiency of ethanol and isopropanol towards highly hydrophobic glycopeptides was compromised as considerable co-enrichment of unmodified peptides occurred, though for some hydrophobic glycopeptides isopropanol showed the best enrichment properties. This study shows that even minor differences in the peptide backbone and solvent do significantly influence HILIC glycopeptide enrichment and need to be carefully considered when employed for glycopeptide enrichment. Graphical Abstract The organic solvent plays a

Optimization of a reversed-phase-high-performance thin-layer chromatography method for the separation of isoniazid, ethambutol, rifampicin and pyrazinamide in fixed-dose combination antituberculosis tablets.

PubMed

Shewiyo, D H; Kaale, E; Risha, P G; Dejaegher, B; Smeyers-Verbeke, J; Vander Heyden, Y

2012-10-19

This paper presents the development of a new RP-HPTLC method for the separation of pyrazinamide, isoniazid, rifampicin and ethambutol in a four fixed-dose combination (4 FDC) tablet formulation. It is a single method with two steps in which after plate development pyrazinamide, isoniazid and rifampicin are detected at an UV wavelength of 280 nm. Then ethambutol is derivatized and detected at a VIS wavelength of 450 nm. Methanol, ethanol and propan-1-ol were evaluated modifiers to form alcohol-water mobile phases. Systematic optimization of the composition of each alcohol in the mobile phase was carried out using the window diagramming concept to obtain the best separation. Examination of the Rf distribution of the separated compounds showed that separation of the compounds with the mobile phase containing ethanol at the optimal fraction was almost situated within the optimal Rf-values region of 0.20-0.80. Therefore, ethanol was selected as organic modifier and the optimal mobile phase composition was found to be ethanol, water, glacial acetic acid (>99% acetic acid) and 37% ammonia solution (70/30/5/1, v/v/v/v). The method is new, quick and cheap compared to the actual method in the International Pharmacopoeia for the assay of the 4 FDC tablets, which involves the use of two separate HPLC methods. Copyright © 2012 Elsevier B.V. All rights reserved.

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 1. Separation behavior of aromatic carboxylic acids

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

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

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 has been investigated. The retention mechanism of aromatic carboxylic acids was discussed on the basis of both ion-pair partition model and ion-exchange model. The retention behavior of aromatic carboxylic acids possessing one (or two) carboxylic acid group(s) followed the ion-pair partition model, where linear free energy relationship was observed between the capacity factor and the extraction equilibrium constants of benzoic acid and naphthalene carboxylic acid.more » Besides, the retention behavior followed ion-exchange model with increasing the number of carboxylic acids, where the capacity factor of benzene polycarboxylic acids is proportional to the association constants between aromatic acids and quaternary ammonium ions calculated on the basis of an electrostatic interaction model.« less

[Preparation of L-phenylalanine chiral ligand-exchange chromatographic stationary phase by atom transfer radical polymerization and resolution of racemates].

PubMed

Sun, Yang; Xu, Fei; Gong, Bolin

2011-09-01

A novel stationary phase was synthesized for chiral ligand-exchange chromatography via atom transfer radical polymerization (ATRP). Glycidyl methacrylate (GMA) was grafted onto the surface of the silica by ATRP using bromoisobutyryl bromide as an initiator, and the organic metal compound formed in the CuCl/2,2'-bipyridine(Bpy) system as a catalyst at room temperature. The chiral stationary phase was then synthesized by grafting L-phenylalanine on the surface of the silica. The stationary phase was characterized by means of elementary analysis and evaluated in detail to determine its separability. The amount of L-phenylalanine on the surface of silica was calculated to be 4.32 mg/m2. The results showed that the good enantioseparations of some DL-amino acids were obtained using ligand-exchange chromatography on the synthesized chiral stationary phase (50 degrees C) with 0.05 mol/L KH2PO4 and 0.1 mmol/L Cu(Ac)2 solution (pH 4.5) as the mobile phase at a flow rate of 1.0 mL/min and a wavelength of 223 nm. The influences of the mobile phase pH, concentration of Cu (II), and temperature of column on the resolution of DL-amino acids by ligand-exchange chromatography were investigated. The results showed that these conditions could affect the resolution of racemates. Compared with the column prepared by radical method using L-phenylalanine directly bonded onto the surface of the silica, the synthesized stationary phase showed a better separation ability, and the DL-aspartic acids and DL-asparagines could be separated at baseline.

Safety and mobility impacts of winter weather - phase 3.

DOT National Transportation Integrated Search

2014-09-01

Highway agencies spend millions of dollars to ensure safe and efficient winter travel. However, the effectiveness of winter-weather : maintenance practices on safety and mobility are somewhat difficult to quantify. Safety and Mobility Impacts of Wint...

Ratchet Effects, Negative Mobility, and Phase Locking for Skyrmions on Periodic Substrates

NASA Astrophysics Data System (ADS)

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

We examine the dynamics of skyrmions interacting with 1D and 2D periodic substrates in the presence of dc and ac drives. We find that the Magnus term strongly affects the skyrmion dynamics and that new kinds of phenomena can occur which are absent for overdamped ac and dc driven particles interacting with similar substrates. We show that it is possible to realize a Magnus induced ratchet for skyrmions interacting with an asymmetric potential, where the application of an ac drive can produce quantized dc motion of the skyrmions even when the ac force is perpendicular to the substrate asymmetry direction. For symmetric substrates it is also possible to achieve a negative mobility effect where the net skyrmion motion runs counter to an applied dc drive. Here, as a function of increasing dc drive, the velocity-force curves show a series of locking phases that have different features from the classic Shapiro steps found in overdamped systems. In the phase locking and ratcheting states, the skyrmions undergo intricate 2D orbits induced by the Magnus term.

Mutations Enhancing Amino Acid Catabolism Confer a Growth Advantage in Stationary Phase

PubMed Central

Zinser, Erik R.; Kolter, Roberto

1999-01-01

Starved cultures of Escherichia coli undergo successive rounds of population takeovers by mutants of increasing fitness. These mutants express the growth advantage in stationary phase (GASP) phenotype. Previous work identified the rpoS819 allele as a GASP mutation allowing cells to take over stationary-phase cultures after growth in rich media (M. M. Zambrano, D. A. Siegele, M. A. Almirón, A. Tormo, and R. Kolter, Science 259:1757–1760, 1993). Here we have identified three new GASP loci from an aged rpoS819 strain: sgaA, sgaB, and sgaC. Each locus is capable of conferring GASP on the rpoS819 parent, and they can provide successively higher fitnesses for the bacteria in the starved cultures. All four GASP mutations isolated thus far allow for faster growth on both individual and mixtures of amino acids. Each mutation confers a growth advantage on a different subset of amino acids, and these mutations act in concert to increase the overall catabolic capacity of the cell. We present a model whereby this enhanced ability to catabolize amino acids is responsible for the fitness gain during carbon starvation, as it may allow GASP mutants to outcompete the parental cells when growing on the amino acids released by dying cells. PMID:10482523

Design of aqueous two-phase systems for purification of hyaluronic acid produced by metabolically engineered Lactococcus lactis.

PubMed

Rajendran, Vivek; Puvendran, Kirubhakaran; Guru, Bharath Raja; Jayaraman, Guhan

2016-02-01

Hyaluronic acid has a wide range of biomedical applications and its commercial value is highly dependent on its purity and molecular weight. This study highlights the utility of aqueous two-phase separation as a primary recovery step for hyaluronic acid and for removal of major protein impurities from fermentation broths. Metabolically engineered cultures of a lactate dehydrogenase mutant strain of Lactococcus lactis (L. lactis NZ9020) were used to produce high-molecular-weight hyaluronic acid. The cell-free fermentation broth was partially purified using a polyethylene glycol/potassium phosphate system, resulting in nearly 100% recovery of hyaluronic acid in the salt-rich bottom phase in all the aqueous two-phase separation experiments. These experiments were optimized for maximum removal of protein impurities in the polyethylene glycol rich top phase. The removal of protein impurities resulted in substantial reduction of membrane fouling in the subsequent diafiltration process, carried out with a 300 kDa polyether sulfone membrane. This step resulted in considerable purification of hyaluronic acid, without any loss in recovery and molecular weight. Diafiltration was followed by an adsorption step to remove minor impurities and achieve nearly 100% purity. The final hyaluronic acid product was characterized by Fourier-transform IR and NMR spectroscopy, confirming its purity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

NASA Astrophysics Data System (ADS)

Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

2016-04-01

One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric

Selective detection of underivatized 2,4-dichlorophenoxyacetic acid in soil by supercritical fluid chromatography with ion mobility detection.

PubMed

Morrissey, M A; Hill, H H

1989-09-01

A simplified procedure was developed for the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in soils. Soil samples were separated by supercritical fluid chromatography after extraction without derivatization and without the use of column chromatography for cleanup. Interferences in the chromatographic separation were eliminated by using a tunably selective ion mobility detector. An atmospheric pressure ion formed by the free acid was selectively monitored so the detector could monitor 2,4-D in the presence of other electron-capturing compounds. For a randomly chosen soil sample, the level of 2,4-D detected was estimated at 500 ppb.

Tellurium Mobility Through Mine Environments

NASA Astrophysics Data System (ADS)

Dorsk, M.

2015-12-01

Tellurium is a rare metalloid that has received minimal research regarding environmental mobility. Observations of Tellurium mobility are mainly based on observations of related metalloids such as selenium and beryllium; yet little research has been done on specific Tellurium behavior. This laboratory work established the environmental controls that influence Tellurium mobility and chemical speciation in aqueous driven systems. Theoretical simulations show possible mobility of Te as Te(OH)3[+] at highly oxidizing and acidic conditions. Movement as TeO3[2-] under more basic conditions may also be possible in elevated Eh conditions. Mobility in reducing environments is theoretically not as likely. For a practical approach to investigate mobility conditions for Te, a site with known Tellurium content was chosen in Colorado. Composite samples were selected from the top, center and bottom of a tailings pile for elution experiments. These samples were disintegrated using a rock crusher and pulverized with an automated mortar and pestle. The material was then classified to 70 microns. A 10g sample split was digested in concentrated HNO3 and HF and analyzed by Atomic Absorption Spectroscopy to determine initial Te concentrations. Additional 10g splits from each location were subjected to elution in 100 mL of each of the following solutions; nitric acid to a pH of 1.0, sulfuric acid to a pH of 2.0, sodium hydroxide to a pH of 12, ammonium hydroxide to a pH of 10, a pine needle/soil tea from material within the vicinity of the collection site to a pH of 3.5 and lastly distilled water to serve as control with a pH of 7. Sulfuric acid was purposefully chosen to simulate acid mine drainage from the decomposition of pyrite within the mine tailings. Sample sub sets were also inundated with 10mL of a 3% hydrogen peroxide solution to induce oxidizing conditions. All collected eluates were then analyzed by atomic absorption spectroscopy (AAS) to measure Tellurium concentrations in

Understanding the spreading patterns of mobile phone viruses.

PubMed

Wang, Pu; González, Marta C; Hidalgo, César A; Barabási, Albert-László

2009-05-22

We modeled the mobility of mobile phone users in order to study the fundamental spreading patterns that characterize a mobile virus outbreak. We find that although Bluetooth viruses can reach all susceptible handsets with time, they spread slowly because of human mobility, offering ample opportunities to deploy antiviral software. In contrast, viruses using multimedia messaging services could infect all users in hours, but currently a phase transition on the underlying call graph limits them to only a small fraction of the susceptible users. These results explain the lack of a major mobile virus breakout so far and predict that once a mobile operating system's market share reaches the phase transition point, viruses will pose a serious threat to mobile communications.

Simultaneous flame ionization and absorbance detection of volatile and nonvolatile compounds by reversed-phase liquid chromatography with a water mobile phase.

PubMed

Bruckner, C A; Ecker, S T; Synovec, R E

1997-09-01

A flame ionization detector (FID) is used to detect volatile organic compounds that have been separated by water-only reversed-phase liquid chromatography (WRP-LC). The mobile phase is 100% water at room temperature, without use of organic solvent modifiers. An interface between the LC and detector is presented, whereby a helium stream samples the vapor of volatile components from individual drops of the LC eluent, and the vapor-enriched gas stream is sent to the FID. The design of the drop headspace cell is simple because the water-only nature of the LC separation obviates the need to do any organic solvent removal prior to gas phase detection. Despite the absence of organic modifier, hydrophobic compounds can be separated in a reasonable time due to the low phase volume ratio of the WRP-LC columns. The drop headspace interface easily handles LC flows of 1 mL/min, and, in fact, compound detection limits are improved at faster liquid flow rates. The transfer efficiency of the headspace interface was estimated at 10% for toluene in water at 1 mL/min but varies depending on the volatility of each analyte. The detection system is linear over more than 5 orders of 1-butanol concentration in water and is able to detect sub-ppb amounts of o-xylene and other aromatic compounds in water. In order to analyze volatile and nonvolatile analytes simultaneously, the FID is coupled in series to a WRP-LC system with UV absorbance detection. WRP-LC improves UV absorbance detection limits because the absence of organic modifier allows the detector to be operated in the short-wavelength UV region, where analytes generally have significantly larger molar absorptivities. The selectivity the headspace interface provides for flame ionization detection of volatiles is demonstrated with a separation of 1-butanol, 1,1,2-trichloroethane (TCE), and chlorobenzene in a mixture of benzoic acid in water. Despite coelution of butanol and TCE with the benzoate anion, the nonvolatile benzoate anion

Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

PubMed

Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

2007-10-15

The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.

Raman microspectroscopy of noncancerous and cancerous human breast tissues. Identification and phase transitions of linoleic and oleic acids by Raman low-temperature studies.

PubMed

Brozek-Pluska, Beata; Kopec, Monika; Surmacki, Jakub; Abramczyk, Halina

2015-04-07

We present the results of Raman studies in the temperature range of 293-77 K on vibrational properties of linoleic and oleic acids and Raman microspectroscopy of human breast tissues at room temperature. Our results confirmed the significant role of unsaturated fatty acids in differentiation of noncancerous and cancerous breast tissues and the role of vibrational spectroscopy in phase transition identification. We have found that vibrational properties are very sensitive indicators to specify phases and phase transitions typical of unsaturated fatty acids at the molecular level. Using Raman spectroscopy we have identified high-temperature, middle-temperature and low-temperature phases of linoleic acid. Results obtained for linoleic acid were compared with parameters characteristic of α and γ phases of oleic acid - the parent compound of polyunsaturated fatty acids.

Surface radical chain-transfer reaction in deep eutectic solvents for preparation of silica-grafted stationary phases in hydrophilic interaction chromatography.

PubMed

Yang, Beibei; Cai, Tianpei; Li, Zhan; Guan, Ming; Qiu, Hongdeng

2017-12-01

In this paper, deep eutectic solvents (DESs) were firstly used as new and green solvents for the preparation of polymer-grafted silica stationary phases. 1-Vinylimidazole and acrylic acid were homopolymerized and copolymerized on silica via surface radical chain-transfer reaction in the DESs. Three stationary phases including poly(1-vinylimidazole)-, poly(acrylic acid)-, poly(1-vinylimidazole-co-acrylic acid)-grafted silica were obtained and characterized by elemental analysis and Fourier transform infrared spectroscopy. Their hydrophilic interaction chromatographic properties were investigated for separation of nucleosides, nucleobases, saccharides and amino acids. The retention changes of nucleosides and nucleobases on these columns were investigated under different chromatographic conditions including acetonitrile content, salt concentration, pH of mobile phase and column temperature. The repeatability of these columns was also investigated. The results demonstrate that DESs can be used as new media for the synthesis of silica-based stationary phases by homopolymerization and copolymerization on the surface of porous silica particles. Copyright © 2017 Elsevier B.V. All rights reserved.

Application and comparison of high performance liquid chromatography and high speed counter-current chromatography in enantioseparation of (±)-2-phenylpropionic acid.

PubMed

Tong, Shengqiang; Zheng, Ye; Yan, Jizhong

2013-03-15

High performance liquid chromatography (HPLC) and high speed counter-current chromatography (HSCCC) were applied and compared in enantioseparation of 2-phenylpropionic acid (2-PPA) when hydroxypropyl-β-cyclodextrin (HP-β-CD) was used as chiral mobile phase additive. For HPLC, the enantioseparation was achieved on ODS C(18) reverse phase column and the mobile phase was 25 mmol L(-1) HP-β-CD aqueous buffer solution (pH 4.0, adjusted with triethylamine): methanol: glacial acetic acid (85:15:0.5 (v/v/v)). For HSCCC, the two-phase solvent system was composed of n-hexane-ethyl acetate-0.1 mol L(-1) phosphate buffer solution pH2.67 (5:5:10 for isocratic elution and 8:2:10 for recycling elution (v/v/v)) added with 0.1 mol L(-1) HP-β-CD. The key parameters, such as a substitution degree of HP-β-CD, the concentration of HP-β-CD, pH value of the aqueous phase and the temperature were optimized for both separation methods. Using the optimum conditions a complete HSCCC enantioseparation of 40 mg of 2-propylpropionic acid in a recycling elution mode gave 15-18 mg of (+)-2-PPA and (-)-2-PPA enantiomers with 95-98% purity and 85-93% recovery. Copyright © 2013 Elsevier B.V. All rights reserved.

Direct injection analysis of fatty and resin acids in papermaking process waters by HPLC/MS.

PubMed

Valto, Piia; Knuutinen, Juha; Alén, Raimo

2011-04-01

A novel HPLC-atmospheric pressure chemical ionization/MS (HPLC-APCI/MS) method was developed for the rapid analysis of selected fatty and resin acids typically present in papermaking process waters. A mixture of palmitic, stearic, oleic, linolenic, and dehydroabietic acids was separated by a commercial HPLC column (a modified stationary C(18) phase) using gradient elution with methanol/0.15% formic acid (pH 2.5) as a mobile phase. The internal standard (myristic acid) method was used to calculate the correlation coefficients and in the quantitation of the results. In the thorough quality parameters measurement, a mixture of these model acids in aqueous media as well as in six different paper machine process waters was quantitatively determined. The measured quality parameters, such as selectivity, linearity, precision, and accuracy, clearly indicated that, compared with traditional gas chromatographic techniques, the simple method developed provided a faster chromatographic analysis with almost real-time monitoring of these acids. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Advantages of using tetrahydrofuran-water as mobile phases in the quantitation of cyclosporin A in monkey and rat plasma by liquid chromatography-tandem mass spectrometry.

PubMed

Li, Austin C; Li, Yinghe; Guirguis, Micheal S; Caldwell, Robert G; Shou, Wilson Z

2007-01-04

A new analytical method is described here for the quantitation of anti-inflammatory drug cyclosporin A (CyA) in monkey and rat plasma. The method used tetrahydrofuran (THF)-water mobile phases to elute the analyte and internal standard, cyclosporin C (CyC). The gradient mobile phase program successfully eluted CyA into a sharp peak and therefore improved resolution between the analyte and possible interfering materials compared with previously reported analytical approaches, where CyA was eluted as a broad peak due to the rapid conversion between different conformers. The sharp peak resulted from this method facilitated the quantitative calculation as multiple smoothing and large number of bunching factors were not necessary. The chromatography in the new method was performed at 30 degrees C instead of 65-70 degrees C as reported previously. Other advantages of the method included simple and fast sample extraction-protein precipitation, direct injection of the extraction supernatant to column for analysis, and elimination of evaporation and reconstitution steps, which were needed in solid phase extraction or liquid-liquid extraction reported before. This method is amenable to high-throughput analysis with a total chromatographic run time of 3 min. This approach has been verified as sensitive, linear (0.977-4000 ng/mL), accurate and precise for the quantitation of CyA in monkey and rat plasma. However, compared with the usage of conventional mobile phases, the only drawback of this approach was the reduced detection response from the mass spectrometer that was possibly caused by poor desolvation in the ionization source. This is the first report to demonstrate the advantages of using THF-water mobile phases to elute CyA in liquid chromatography.

The role of cassiterite controlling arsenic mobility in an abandoned stanniferous tailings impoundment at Llallagua, Bolivia.

PubMed

Romero, Francisco Martín; Canet, Carles; Alfonso, Pura; Zambrana, Rubén N; Soto, Nayelli

2014-05-15

The surface water contamination by potentially toxic elements (PTE) leached from mine tailings is a major environmental concern. However, the formation of insoluble solid phases can control the mobility of PTE, with subsequent decrease of the risk that tailings suppose to the environment. We characterized the tailings from a tin inactive mine in Llallagua, Bolivia in order to assess the risk for surface water quality. These tailings contain high concentrations of PTE, with up to 94,344 mg/kg Fe, 9,135 mg/kg Sn, 4,606 mg/kg As, 1,362 mg/kg Cu, 1,220 mg/kg Zn, 955 mg/kg Pb and 151 mg/kg Cd. Oxidation of sulfide minerals in these tailings generates acid leachates (pH=2.5-3.5), rich in SO4(2-) and dissolved PTE, thereby releasing contaminants to the surface waters. Nevertheless, the concentrations of dissolved Sn, As and Pb in acid leachates are low (Sn<0.01 mg/L; As=0.25-2.55 mg/L; Pb<0.05 mg/L). This indicates that, for the most part, Sn, As and Pb are being retained by the solid phases in the impoundment, so that these elements are not reaching the surface waters. Fe-bearing cassiterite-an insoluble and weathering-resistant oxide mineral-is abundant in the studied tailing deposits; it should be the main solid phase controlling Sn and As mobility in the impoundment. Additionally, jarosite and plumbojarosite, identified among the secondary minerals, could also play an important role controlling the mobility of As and Pb. Taking into account (a) the low solubility constants of cassiterite (Ksp=10(-64.2)), jarosite (Ksp=10(-11)) and plumbojarosite (Ksp=10(-28.66)), and (b) the stability of these minerals under acidic conditions, we can conclude that they control the long-term fate of Sn, As and Pb in the studied tailings. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

Silver-modified mobile phase for normal-phase liquid chromatographic determination of prostaglandins and their 5,6-trans isomers in prostaglandin bulk drugs and triacetin solutions.

PubMed

Kissinger, L D; Robins, R H

1985-03-15

A silver-modified, normal-phase, high-performance liquid chromatographic system has been developed for prostaglanding bulk drugs and triacetin solutions. Silver nitrate present in the mobile phase results in high selectivity for cis/trans isomers with conventional silica columns. Prostaglandins were esterified with alpha-bromo-2'-acetonaphthone prior to chromatography to provide high detectability at 254 nm. For dilute triacetin solutions, a sample preparation scheme based on gravity-flow chromatography with silica columns was developed to isolate the prostaglandin from triacetin prior to derivatization. The analytical technique was applied to triacetin solutions containing as little as 10 micrograms/ml arbaprostil [15-(R)-methyl-PGE2].

Fatty acid synthase inhibition triggers apoptosis during S phase in human cancer cells.

PubMed

Zhou, Weibo; Simpson, P Jeanette; McFadden, Jill M; Townsend, Craig A; Medghalchi, Susan M; Vadlamudi, Aravinda; Pinn, Michael L; Ronnett, Gabriele V; Kuhajda, Francis P

2003-11-01

C75, an inhibitor of fatty acid synthase (FAS), induces apoptosis in cultured human cancer cells. Its proposed mechanism of action linked high levels of malonyl-CoA after FAS inhibition to potential downstream effects including inhibition of carnitine palmitoyltransferase-1 (CPT-1) with resultant inhibition of fatty acid oxidation. Recent data has shown that C75 directly stimulates CPT-1 increasing fatty acid oxidation in MCF-7 human breast cancer cells despite inhibitory concentrations of malonyl-CoA. In light of these findings, we have studied fatty acid metabolism in MCF7 human breast cancer cells to elucidate the mechanism of action of C75. We now report that: (a) in the setting of increased fatty acid oxidation, C75 inhibits fatty acid synthesis; (b) C273, a reduced form of C75, is unable to inhibit fatty acid synthesis and is nontoxic to MCF7 cells; (c) C75 and 5-(tetradecyloxy)-2-furoic acid (TOFA), an inhibitor of acetyl-CoA carboxylase, both cause a significant reduction of fatty acid incorporation into phosphatidylcholine, the major membrane phospholipid, within 2 h; (d) pulse chase studies with [(14)C]acetate labeling of membrane lipids show that both C75 and TOFA accelerate the decay of (14)C-labeled lipid from membranes within 2 h; (e) C75 also promotes a 2-3-fold increase in oxidation of membrane lipids within 2 h; and (f) because interference with phospholipid synthesis during S phase is known to trigger apoptosis in cycling cells, we performed double-labeled terminal deoxynucleotidyltransferase-mediated nick end labeling and BrdUrd analysis with both TOFA and C75. C75 triggered apoptosis during S phase, whereas TOFA did not. Moreover, application of TOFA 2 h before C75 blocked the C75 induced apoptosis, whereas etomoxir did not. Taken together these data indicate that FAS inhibition and its downstream inhibition of phospholipid production is a necessary part of the mechanism of action of C75. CPT-1 stimulation does not likely play a role in the

Lactose behaviour in the presence of lactic acid and calcium.

PubMed

Wijayasinghe, Rangani; Vasiljevic, Todor; Chandrapala, Jayani

2016-08-01

Physical properties of lactose appeared influenced by presence of lactic acid in the system. Some other components such as Ca may further attenuate lactose behaviour and impact its phase transition. A model-based study was thus implemented with varying concentrations of Ca (0·12, 0·072 or 0·035% w/w) and lactic acid (0·05, 0·2, 0·4 or 1% w/w) in establishing the effects of these two main acid whey constituents on lactose phase behaviour. Concentrated solutions (50% w/w) containing lactose, lactic acid and Ca were analysed for thermal behaviour and structural changes by Differential Scanning Colorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR), respectively. Presence of 1% (w/w) lactic acid and 0·12% (w/w) Ca in lactose solution significantly increased the evaporation enthalpy of water, delayed and increased the energy required for lactose crystallisation as compared to pure lactose. FTIR analysis indicated a strong hydration layer surrounding lactose molecules, restricting water mobility and/or inducing structural changes of lactose, hindering its crystallisation. The formation of calcium lactate, which restricts the diffusion of lactose molecules, is also partly responsible. It appears that Ca removal from acid whey may be a necessary step in improving the processability of acid whey.

NASA mobile satellite program

NASA Technical Reports Server (NTRS)

Knouse, G.; Weber, W.

1985-01-01

A three phase development program for ground and space segment technologies which will enhance and enable the second and third generation mobile satellite systems (MSS) is outlined. Phase 1, called the Mobile Satellite Experiment (MSAT-X), is directed toward the development of ground segment technology needed for future MSS generations. Technology validation and preoperational experiments with other government agencies will be carried out during the two year period following launch. The satellite channel capacity needed to carry out these experiments will be obtained from industry under a barter type agreement in exchange for NASA provided launch services. Phase 2 will develop and flight test the multibeam spacecraft antenna technology needed to obtain substantial frequency reuse for second generation commercial systems. Industry will provide the antenna, and NASA will fly it on the Shuttle and test it in orbit. Phase 3 is similar to Phase 2 but will develop an even larger multibeam antenna and test it on the space station.

NASA mobile satellite program

NASA Astrophysics Data System (ADS)

Knouse, G.; Weber, W.

1985-04-01

A three phase development program for ground and space segment technologies which will enhance and enable the second and third generation mobile satellite systems (MSS) is outlined. Phase 1, called the Mobile Satellite Experiment (MSAT-X), is directed toward the development of ground segment technology needed for future MSS generations. Technology validation and preoperational experiments with other government agencies will be carried out during the two year period following launch. The satellite channel capacity needed to carry out these experiments will be obtained from industry under a barter type agreement in exchange for NASA provided launch services. Phase 2 will develop and flight test the multibeam spacecraft antenna technology needed to obtain substantial frequency reuse for second generation commercial systems. Industry will provide the antenna, and NASA will fly it on the Shuttle and test it in orbit. Phase 3 is similar to Phase 2 but will develop an even larger multibeam antenna and test it on the space station.

Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system

NASA Astrophysics Data System (ADS)

Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.

2012-12-01

Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic

Observation of Wigner crystal phase and ripplon-limited mobility behavior in monolayer CVD MoS2 with grain boundary.

PubMed

Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong

2018-06-01

Two-dimensional electron gas (2DEG) is crucial in condensed matter physics and is present on the surface of liquid helium and at the interface of semiconductors. Monolayer MoS 2 of 2D materials also contains 2DEG in an atomic layer as a field effect transistor (FET) ultrathin channel. In this study, we synthesized double triangular MoS 2 through a chemical vapor deposition method to obtain grain boundaries for forming a ripple structure in the FET channel. When the temperature was higher than approximately 175 K, the temperature dependence of the electron mobility μ was consistent with those in previous experiments and theoretical predictions. When the temperature was lower than approximately 175 K, the mobility behavior decreased with the temperature; this finding was also consistent with that of the previous experiments. We are the first research group to explain the decreasing mobility behavior by using the Wigner crystal phase and to discover the temperature independence of ripplon-limited mobility behavior at lower temperatures. Although these mobility behaviors have been studied on the surface of liquid helium through theories and experiments, they have not been previously analyzed in 2D materials and semiconductors. We are the first research group to report the similar temperature-dependent mobility behavior of the surface of liquid helium and the monolayer MoS 2 .

Observation of Wigner crystal phase and ripplon-limited mobility behavior in monolayer CVD MoS2 with grain boundary

NASA Astrophysics Data System (ADS)

Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong

2018-06-01

Two-dimensional electron gas (2DEG) is crucial in condensed matter physics and is present on the surface of liquid helium and at the interface of semiconductors. Monolayer MoS2 of 2D materials also contains 2DEG in an atomic layer as a field effect transistor (FET) ultrathin channel. In this study, we synthesized double triangular MoS2 through a chemical vapor deposition method to obtain grain boundaries for forming a ripple structure in the FET channel. When the temperature was higher than approximately 175 K, the temperature dependence of the electron mobility μ was consistent with those in previous experiments and theoretical predictions. When the temperature was lower than approximately 175 K, the mobility behavior decreased with the temperature; this finding was also consistent with that of the previous experiments. We are the first research group to explain the decreasing mobility behavior by using the Wigner crystal phase and to discover the temperature independence of ripplon-limited mobility behavior at lower temperatures. Although these mobility behaviors have been studied on the surface of liquid helium through theories and experiments, they have not been previously analyzed in 2D materials and semiconductors. We are the first research group to report the similar temperature-dependent mobility behavior of the surface of liquid helium and the monolayer MoS2.

Advances in silver ion chromatography for the analysis of fatty acids and triacylglycerols-2001 to 2011.

PubMed

Momchilova, Svetlana M; Nikolova-Damyanova, Boryana M

2012-01-01

An effort is made to critically present the achievements in silver ion chromatography during the last decade. Novelties in columns, mobile-phase compositions and detectors are described. Recent applications of silver ion chromatography in the analysis of fatty acids and triacylglycerols are presented while stressing novel analytical strategies or new objects. The tendencies in the application of the method in complementary ways with reversed-phase chromatography, chiral chromatography and, especially, mass detection are outlined.

Development and Validation of a Reversed Phase HPLC Method for Determination of Anacardic Acids in Cashew (Anacardium occidentale) Nut Shell Liquid.

PubMed

Oiram Filho, Francisco; Alcântra, Daniel Barbosa; Rodrigues, Tigressa Helena Soares; Alexandre E Silva, Lorena Mara; de Oliveira Silva, Ebenezer; Zocolo, Guilherme Julião; de Brito, Edy Sousa

2018-04-01

Cashew nut shell liquid (CNSL) contains phenolic lipids with aliphatic chains that are of commercial interest. In this work, a chromatographic method was developed to monitor and quantify anacardic acids (AnAc) in CNSL. Samples containing AnAc were analyzed on a high-performance liquid chromatograph coupled to a diode array detector, equipped with a reversed phase C18 (150 × 4.6 mm × 5 μm) column using acetonitrile and water as the mobile phase both acidified with acetic acid to pH 3.0 in an isocratic mode (80:20:1). The chromatographic method showed adequate selectivity, as it could clearly separate the different AnAc. To validate this method, AnAc triene was used as an external standard at seven different concentrations varying from 50 to 1,000 μg mL-1. The Student's t-test and F-test were applied to ensure high confidence for the obtained data from the analytical calibration curve. The results were satisfactory with respect to intra-day (relative standard deviation (RSD) = 0.60%) and inter-day (RSD = 0.67%) precision, linearity (y = 2,670.8x - 26,949, r2 > 0.9998), system suitability for retention time (RSD = 1.02%), area under the curve (RSD = 0.24%), selectivity and limits of detection (19.8 μg mg-1) and quantification (60.2 μg mg-1). The developed chromatographic method was applied for the analysis of different CNSL samples, and it was deemed suitable for the quantification of AnAc.

Chlorogenic Acid Attenuates High Mobility Group Box 1 (HMGB1) and Enhances Host Defense Mechanisms in Murine Sepsis

PubMed Central

Lee, Chan-Ho; Yoon, Seong-Jin; Lee, Sun-Mee

2012-01-01

Sepsis is a complex, multifactorial, rapidly progressive disease characterized by an overwhelming activation of the immune system and the countervailing antiinflammatory response. In the current study in murine peritoneal macrophages, chlorogenic acid suppressed endotoxin-induced high mobility group box 1 (HMGB1) release in a concentration-dependent manner. Administration of chlorogenic acid also attenuated systemic HMGB1 accumulation in vivo and prevented mortality induced by endotoxemia and polymicrobial sepsis. The mechanisms of action of chlorogenic acid included attenuation of the increase in toll-like receptor (TLR)-4 expression and suppression of sepsis-induced signaling pathways, such as c-Jun NH2-terminal kinase (JNK), p38 mitogen-activated protein kinase (MAPK) and nuclear factor (NF)-κB, which are critical for cytokine release. The protection conferred by chlorogenic acid was achieved through modulation of cytokine and chemokine release, suppression of immune cell apoptosis and augmentation of bacterial elimination. Chlorogenic acid warrants further evaluation as a potential therapeutic agent for the treatment of sepsis and other potentially fatal systemic inflammatory disorders. PMID:23168580

Simultaneous Determination of Ursodeoxycholic Acid and Chenodeoxycholic Acid in Pharmaceutical Dosage Form by HPLC-UV Detection.

PubMed

Khairy, Mostafa A; Mansour, Fotouh R

2017-01-01

A reversed-phase HPLC method was developed for the simultaneous determination of ursodeoxycholic acid (UDCA) and the epimeric isomer, chenodeoxycholic acid (CDCA), in their synthetic mixtures and in tablet dosage form. The proposed HPLC method uses a C18 column and mobile phase consisting of an acetonitrile-phosphate buffer mixture (pH 2.3, 100 mM; 50 + 50, v/v) at a flow rate of 2.0 mL/min with UV detection at 210 nm. The method was validated according to the International Conference on Harmonization guidelines; and linearity, range, accuracy, precision, robustness, and system suitability were studied. The LOD and LOQ were also calculated and found to be 1.23 and 3.73 μg/mL for UDCA and 0.83 and 2.52 μg/mL for CDCA, respectively. The method was adapted for UHPLC, in which baseline separation was achieved in <2.5 min. The assay results of Ursomix tablets by the developed method were statistically compared with those obtained by the reference method using t- and F-tests, and no significant differences were observed.

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

PubMed

Flieger, Jolanta; Feder-Kubis, Joanna; Tatarczak-Michalewska, Małgorzata; Płazińska, Anita; Madejska, Anna; Swatko-Ossor, Marta

2017-06-01

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG 0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

DOE PAGES

Mincher, Bruce J.; Precek, Martin; Paulenova, Alena

2015-10-17

The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30% TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated thismore » reduction.« less

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

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

Mincher, Bruce J.; Precek, Martin; Paulenova, Alena

The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30% TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated thismore » reduction.« less

Mobility-induced persistent chimera states

NASA Astrophysics Data System (ADS)

Petrungaro, Gabriela; Uriu, Koichiro; Morelli, Luis G.

2017-12-01

We study the dynamics of mobile, locally coupled identical oscillators in the presence of coupling delays. We find different kinds of chimera states in which coherent in-phase and antiphase domains coexist with incoherent domains. These chimera states are dynamic and can persist for long times for intermediate mobility values. We discuss the mechanisms leading to the formation of these chimera states in different mobility regimes. This finding could be relevant for natural and technological systems composed of mobile communicating agents.

Recent Selected Ion Flow Tube (SIFT) Studies Concerning the Formation of Amino Acids in the Gas Phase

NASA Technical Reports Server (NTRS)

Jackson, Douglas M.; Adams, Nigel G.; Babcock, Lucia M.

2006-01-01

Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.

[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.

Interaction of Gas Phase Oxalic Acid with Ammonia and its Atmospheric Implications

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

Peng, Xiu-Qiu; Liu, Yi-Rong; Huang, Teng

Oxalic acid is believed to play an important role in the formation and growth of atmospheric organic aerosols. However, as a common organic acid, the understanding of the larger clusters formed by gas phase oxalic acid with multiple ammonia molecules is incomplete. In this work, the structural characteristics and thermodynamics of oxalic acid clusters with up to six ammonia molecules have been investigated at the PW91PW91/6-311++G(3df,3pd) level of theory. We found that oxalic acid forms relatively stable clusters with ammonia molecules, and that ionization events play a key role. The analyses of the thermodynamics and atmospheric relevance indicate that themore » heterodimer (H2C2O4)(NH3) shows an obvious relative concentration in the atmosphere, and thus likely participates in new particle formation. However, with increasing number of ammonia molecules, the concentration of clusters decreases gradually. Additionally, clusters of oxalic acid with ammonia molecules are predicted to form favorably in low temperature conditions and show high Rayleigh scattering intensities.« less

Determination of D-malic acid in apple juice by liquid chromatography: collaborative study.

PubMed

Eisele, T A

1996-01-01

Eleven laboratories collaboratively studied a liquid chromatographic (LC) method for determination of D-malic acid in apple juice. The mobile phase consisted of mM L-valine and 8 mM copper acetate adjusted to pH 5.5 with NaOH. The UV detector was set at 330 nm, and a single reversed-phase LC column was used. Seven paired samples containing various amounts of D-malic acid ranging from 0 to 188 mg/100 mL of 12 Brix pasteurized apple juice were tested by each collaborator. Repeatability and reproducibility coefficients of variation ranged from 1.0 to 3.5% and 7.7 to 11.7%, respectively, within the range of 26 to 188 mg D-malic acid/100 mL of 12 Brix apple juice. The collaborative study results demonstrated that the method could quantitate the economic adulteration of apple juice with DL-malic acid at lower levels than those reported with previous methods. The LC method for determination of D-malic acid in apple juice has been adopted first action by AOAC INTERNATIONAL.

Morphology and phase transformations of tin oxide nanostructures synthesized by the hydrothermal method in the presence of dicarboxylic acids

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

Zima, Tatyana, E-mail: zima@solid.nsc.ru; Novosibirsk State Technical University, 20 K. Marx Prospect, Novosibirsk 630092; Bataev, Ivan

A new approach to the synthesis of non-stoichiometric tin oxide structures with different morphologies and the phase compositions has been evaluated. The nanostructures were synthesized by hydrothermal treatment of the mixtures of dicarboxylic acids ― aminoterephthalic or oxalic ― with nanocrystalline SnO{sub 2} powder, which was obtained via the sol-gel technology. The products were characterized by Raman and IR spectroscopy, SEM, HRTEM, and XRD analysis. It was shown that the controlled addition of a dicarboxylic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations.more » A single-phase Sn{sub 3}O{sub 4} in the form of the well-separated hexagonal nanoplates and mixed SnO{sub 2}/Sn{sub 3}O{sub 4} phases in the form of hierarchical flower-like structures were obtained in the presence of organic additives. The effects of concentration, redox activity of the acids and heat treatment on the basic characteristics of the synthesized tin oxide nanostructures and phase transformations in the synthesized materials are discussed. - Graphical abstract: The controlled addition of aminoterephthalic or oxalic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations. - Highlights: • A new approach to the synthesis of non-stoichiometric tin oxide structures is studied. • Tin oxide structures are synthesized via hydrothermal method with dicarboxylic acids. • Morphology and phase composition are changed with redox activity and dosage of acid. • The redox activity of acid has an effect on ratio of SnO and SnO{sub 2} in crystal structure. • A pure phase Sn{sub 3}O{sub 4} nanoplates and SnO{sub 2}/Sn{sub 3}O{sub 4} hierarchical structures are formed.« less

Assessing Metal Mobilization from Industrially Lead ...

EPA Pesticide Factsheets

A series of leaching and partitioning tests (Toxicity Characteristic Leaching Procedure (TCLP), Synthetic Precipitation Leaching Procedure (SPLP), Controlled Acidity Leaching Protocol (CALP), Acid Neutralization Capacity (ANC), and sequential extraction) were applied to three different soils to study potential mobility of metals into groundwater. Two of these soils were lead (Pb)-contaminated soils (Hotspot 1 and Hotspot 2) collected from an urban site associated with lead smelting and other industrial operations. The third sample (Stockpile) was soil affected by previous contamination in the area, removed from residential properties, stockpiled, and selected to be used as fill material in the studied site. The TCLP and CALP showed that Pb could be released from both hotspots, but were not released in the acidic rainfall extraction fluid of the SPLP. The sequential extraction showed that Pb in the hotspot soils was associated with the carbonate fraction, while As was associated with the Fe and Mn oxides. The stockpile released traces of Pb or As in the TCLP and CALP, but the ANC only released Pb under acidic conditions and the SPLP did not release Pb or As. Overall, the projected repository with Stockpile would not pose imminent danger to groundwater because, under the expected environmental conditions, Pb and As tend to remain in the solid phase. The objectives of this study were to determine if the stockpiled soil was suitable for the intended fill purpo

Electric Utility Phase I Acid Rain Compliance Strategies for the Clean Air Act Amendments of 1990

EIA Publications

1994-01-01

The Acid Rain Program is divided into two time periods; Phase I, from 1995 through 1999, and Phase II, starting in 2000. Phase I mostly affects power plants that are the largest sources of SO2 and NOx . Phase II affects virtually all electric power producers, including utilities and nonutilities. This report is a study of the effects of compliance with Phase I regulations on the costs and operations of electric utilities, but does not address any Phase II impacts.

Effect of pressure on the selectivity of polymeric C18 and C30 stationary phases in reversed-phase liquid chromatography. Increased separation of isomeric fatty acid methyl esters, triacylglycerols, and tocopherols at high pressure.

PubMed

Okusa, Kensuke; Iwasaki, Yuki; Kuroda, Ikuma; Miwa, Shohei; Ohira, Masayoshi; Nagai, Toshiharu; Mizobe, Hoyo; Gotoh, Naohiro; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

2014-04-25

A high-density, polymeric C18 stationary phase (Inertsil ODS-P) or a polymeric C30 phase (Inertsil C30) provided improved resolution of the isomeric fatty acids (FAs), FA methyl esters (FAMEs), triacylglycerols (TAGs), and tocopherols with an increase in pressure of 20-70MPa in reversed-phase HPLC. With respect to isomeric C18 FAMEs with one cis-double bond, ODS-P phase was effective for recognizing the position of a double bond among petroselinic (methyl 6Z-octadecenoate), oleic (methyl 9Z-octadecenoate), and cis-vaccenic (methyl 11Z-octadecenoate), especially at high pressure, but the differentiation between oleic and cis-vaccenic was not achieved by C30 phase regardless of the pressure. A monomeric C18 phase (InertSustain C18) was not effective for recognizing the position of the double bond in monounsaturated FAME, while the separation of cis- and trans-isomers was achieved by any of the stationary phases. The ODS-P and C30 phases provided increased separation for TAGs and β- and γ-tocopherols at high pressure. The transfer of FA, FAME, or TAG molecules from the mobile phase to the ODS-P stationary phase was accompanied by large volume reduction (-30∼-90mL/mol) resulting in a large increase in retention (up to 100% for an increase of 50MPa) and improved isomer separation at high pressure. For some isomer pairs, the ODS-P and C30 provided the opposite elution order, and in each case higher pressure improved the separation. The two stationary phases showed selectivity for the isomers having rigid structures, but only the ODS-P was effective for differentiating the position of a double bond in monounsaturated FAMEs. The results indicate that the improved isomer separation was provided by the increased dispersion interactions between the solute and the binding site of the stationary phase at high pressure. Copyright © 2014 Elsevier B.V. All rights reserved.

The effect of pressure and mobile phase velocity on the retention properties of small analytes and large biomolecules in ultra-high pressure liquid chromatography.

PubMed

Fekete, Szabolcs; Veuthey, Jean-Luc; McCalley, David V; Guillarme, Davy

2012-12-28

A possible complication of ultra-high pressure liquid chromatography (UHPLC) is related to the effect of pressure and mobile phase velocity on the retention properties of the analytes. In the present work, numerous model compounds have been selected including small molecules, peptides, and proteins (such as monoclonal antibodies). Two instrumental setups were considered to attain elevated pressure drops, firstly the use of a post-column restrictor capillary at low mobile phase flow rate (pure effect of pressure) and secondly the increase of mobile phase flow rate without restrictor (i.e. a combined effect of pressure and frictional heating). In both conditions, the goal was to assess differences in retention behaviour, depending on the type or character of the analyte. An important conclusion is that the effect of pressure and mobile phase velocity on retention varied in proportion with the size of the molecule and in some cases showed very different behaviour. In isocratic mode, the pure effect of pressure (experiments with a post-column restrictor capillary) induces an increase in retention by 25-100% on small molecules (MW<300 g/mol), 150% for peptides (~1.3 kDa), 800% for insulin (~6 kDa) and up to >3000% for myoglobin (~17 kDa) for an increase in pressure from 100 bar up to 1100 bar. The important effect observed for the isocratic elution of proteins is probably related to conformational changes of the protein in addition to the effect of molecular size. Working in gradient elution mode, the pressure related effects on retention were found to be less pronounced but still present (an increase of apparent retention factor between 0.2 and 2.5 was observed). Copyright © 2012 Elsevier B.V. All rights reserved.

Development and validation of RP-UHPLC procedure for estimation of 5-amino salicyclic acid in 5-amino salicyclic acid rectal suppositories

NASA Astrophysics Data System (ADS)

Balaji, Jayagopal; Shivashankar, Murugesh

2017-11-01

The present study describes a simple and robust reverse phase ultra performance liquid chromatography (RP-UPLC) method for the quantification of 5-amino salicyclic acid in 5-amino salicyclic acid rectal capsules. Successful separation of Mesalamine peak from excipient peaks and diluent were achieved on a Acquity C8 (50 × 2.1 mm, 1.7 μm) and UV detector at 254 nm, 0.3 mL/min as a flow rate, and 3 μL as an injection volume. For the RP-UPLC method, phosphate buffer and methanol was used as mobile phases at ratio of 83:17 and the column temperature was 25 °C. Percentage recovery obtained in the range of 98.7 - 99.7 % and the method is linear for Mesalamine for specified concentration range with coefficient of variation (r) not less than 0.99. The proposed RP-UPLC method was found to be specific, linear, precise, accurate and robust.

An innovative approach to the analysis of 3-[4-(2-methylpropyl)phenyl]propanoic acid as an impurity of ibuprofen on a carbon-coated zirconia stationary phase.

PubMed

Kalafut, P; Kucera, R; Klimes, J; Sochor, J

2009-07-12

3-[4-(2-Methylpropyl)phenyl]propanoic acid has been introduced as impurity F to the European Pharmacopoeia in its Supplement 4.2. In contrast to other impurities, which are evaluated by HPLC, the content of impurity F is determined by gas chromatography after previous derivatization. Thus a novel reversed-phase HPLC method was developed to simplify the evaluation of pharmacopoeial impurity F of ibuprofen. Favourable properties of zirconia stationary phases were employed for this purpose. The HPLC separation was achieved on a Zr-CARB column (150 mm x 4.6mm i.d., 5 microm) using the mobile phase acetonitrile-phosphate buffer (pH 3.5, 25 mM) (38:62, v/v), temperature 80 degrees C and the flow rate 1.2 ml min(-1). The fluorescence detection was employed to enhance the sensitivity of the method. Optimal detection parameters were chosen on the basis of fluorescence spectra of the analytes. The excitation and emission wavelengths were 220 nm and 285 nm, respectively. The analysis was completed within 25 min. The subsequent validation of the method confirmed the applicability of method for the analytical assay of impurity F.

Pharmacokinetics of Caffeic Acid, Ferulic Acid, Formononetin, Cryptotanshinone, and Tanshinone IIA after Oral Administration of Naoxintong Capsule in Rat by HPLC-MS/MS.

PubMed

Li, Jin; Bai, Yang; Bai, Yun; Zhu, Ruichao; Liu, Wei; Cao, Jun; An, Mingrui; Tan, Zhijing; Chang, Yan-Xu

2017-01-01

Naoxintong capsule (NXTC) was a famous patent medicine of Traditional Chinese Medicine (TCM) to treat cerebrovascular diseases in China. An LC-MS/MS method was developed for simultaneous determination of 11 major ingredients (paeoniflorin, ecdysterone, amygdalin, mulberroside A, caffeic acid, ferulic acid, salvianolic acid B, astragaloside IV, formononetin, cryptotanshinone, and tanshinone IIA) in NXTC in rat plasma. All analytes were separated on an Eclipse plus C 18 column using a gradient mobile phase system of acetonitrile-0.1% formic acid aqueous solution. The lower limits of quantification of 11 ingredients were between 0.075 and 10 ng mL -1 . The precision was less than 15% and the accuracies were between 85% and 115%. The results showed that caffeic acid, ferulic acid, formononetin, cryptotanshinone, and tanshinone IIA could be detected after oral administration of NXTC. The validated method was successfully applied to pharmacokinetic study of the caffeic acid, ferulic acid, formononetin, cryptotanshinone, and tanshinone IIA in rats after oral administration of NXTC at single and triple dose.

Micro unattended mobility system (MUMS)

NASA Astrophysics Data System (ADS)

Rudakevych, Pavlo; Greiner, Helen; Pletta, Bryan

1999-07-01

This report covers work under phase one of the Micro Unattended Mobility System project investigating the addition of a mobile sensor components to existing and future ground penetrator delivered unattended sensor systems. A typical unattended sensor strategy consists of air-dropping sensor packages into a target terrain for remote observation and intelligence gathering. Existing and planned unattended systems have no control over their location after the drop is complete. We propose to augment the capability of these sensing packages by giving them a degree of local mobility. From an assumed operational scenario, vehicle design specifications are identified that would be required for mission success. Three basic mobility concepts are presented and evaluated for their strengths and weaknesses in the proposed mission. The mobility concepts are grouped into wheeled, jumping, and crawling systems. Of the three mobility concepts discussed, the system that shows the most promise is presented in a more detailed design. This design consists of two side by side wheels which drag a reaction tail behind them. The control electronics, batteries, and drive motors are housed in a central body connected to the tail and two sensor payloads can be placed in the wheel hubs. This design is proposed for further development and testing in the second phase of this project.

Simultaneous analysis and retention behavior of major isoflavonoids in Radix Puerariae lobatae and Radix Puerariae thomsonii by high performance liquid chromatography with cyclodextrins as a mobile phase modifier.

PubMed

Zeng, Aiguo; Xing, Jianfeng; Wang, Changhe; Song, Jie; Li, Cong; Yang, Xin; Yang, Guangde

2012-01-27

In order to differentiate two species of Radix Puerariae (Radix Puerariae lobatae and Radix Puerariae thomsonii) and to determine major isoflavonoids (puerarin, daidzin, daidzein and genistein) in the samples, a simple high performance liquid chromatography (HPLC) method with isocratic elution employing cyclodextrins (CDs) as mobile phase additives was developed. Various factors affecting the retention of isoflavonoids in the C(18) reversed-phase column, such as the nature of CDs, the concentration of hydroxypropyl-β-cyclodextrin (HP-β-CD) and the methanol percentage in the mobile phase, were studied. Experimental results confirmed that HP-β-CD, as a very effective mobile phase additive, could markedly reduce the retention of isoflavonoids, especially daidzein and genistein. The elution of four isoflavonoids could be achieved on a Kromasil(®) C(18) column within 56 min by using the methanol-water contained 5 mM HP-β-CD (25/75, v/v) mixture as the mobile phase. The formation of the inclusion complexes between isoflavonoids and HP-β-CD explained the modification of the retention of analytes. The apparent formation constants determined by HPLC confirmed that the stoichiometry of HP-β-CD-isoflavonoid complexes was 1:1, and the stability of the complexes depended on the size and property of isoflavonoids. The optimized method was successfully applied for the simultaneous determination of major isoflavonoids in P. lobatae and P. thomsonii samples. This work provides a useful method for the analysis of traditional Chinese herbs. Copyright © 2011 Elsevier B.V. All rights reserved.

In-Source Reduction of Disulfide-Bonded Peptides Monitored by Ion Mobility Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stocks, Bradley B.; Melanson, Jeremy E.

2018-02-01

Many peptides with antimicrobial activity and/or therapeutic potential contain disulfide bonds as a means to enhance stability, and their quantitation is often performed using electrospray ionization mass spectrometry (ESI-MS). Disulfides can be reduced during ESI under commonly used instrument conditions, which has the potential to hinder accurate peptide quantitation. We demonstrate that this in-source reduction (ISR) is predominantly observed for peptides infused from acidic solutions and subjected to elevated ESI voltages (3-4 kV). ISR is readily apparent in the mass spectrum of oxytocin—a small, single disulfide-containing peptide. However, subtle m/z shifts due to partial ISR of highly charged (z ≥ 3) peptides with multiple disulfide linkages may proceed unnoticed. Ion mobility (IM)-MS separates ions on the basis of charge and shape in the gas phase, and using insulin as a model system, we show that IM-MS arrival time distributions (ATDs) are particularly sensitive to partial ISR of large peptides. Isotope modeling allows for the relative quantitation of disulfide-intact and partially reduced states of the mobility-separated peptide conformers. Interestingly, hepcidin peptides ionized from acidic solutions at elevated ESI voltages undergo gas-phase compaction, ostensibly due to partial disulfide ISR. Our IM-MS results lead us to propose that residual acid is the likely cause of disparate ATDs recently measured for hepcidin from different suppliers [Anal. Bioanal. Chem. 409, 2559-2567 (2017)]. Overall, our results demonstrate the utility of IM-MS to detect partial ISR of disulfide-bonded peptides and reinforce the notion that peptide/protein measurements should be carried out using minimally activating instrument conditions. [Figure not available: see fulltext.

[Determination of aristolochic acid A in Guanxinsuhe preparations by RP-HPLC].

PubMed

Li, Lin; Gao, Hui-Min; Wang, Zhi-Min; Wang, Wei-Hao

2006-01-01

To establish a determination method of aristolochic acid A in Guanxisuhe preparations by RP-HPLC. The instrument used was Hewlett-Packard 1100 HPLC with a Alltech C18 column (4.6 mm x 250 mm, 5 microm). The mobile phase was methanol-water-acetic acid (68: 32:1) and the flow rate was 1.0 mL x min(-1). The UV detection wavelength was 390 nm and the column temperature was at 35 degrees C. The extracted solvent for the preparations was methanol solution contained 10% formic acid. The calibration curve was linear (r = 0.999 9) within the range of 0.119-1.89 microg for aristolochic acid A. The average recovery 99.0%, RSD 0.63%. The method with good linear relationship was convenient, quick, accurate, and suitable for the quality control of the aristolochic acid A in Guanxinsuhe and other traditional Chinese medicines containing aristolochic acid A.

Development and Validation of a HPTLC Method for Simultaneous Estimation of L-Glutamic Acid and γ-Aminobutyric Acid in Mice Brain

PubMed Central

Sancheti, J. S.; Shaikh, M. F.; Khatwani, P. F.; Kulkarni, Savita R.; Sathaye, Sadhana

2013-01-01

A new robust, simple and economic high performance thin layer chromatographic method was developed for simultaneous estimation of L-glutamic acid and γ-amino butyric acid in brain homogenate. The high performance thin layer chromatographic separation of these amino acid was achieved using n-butanol:glacial acetic acid:water (22:3:5 v/v/v) as mobile phase and ninhydrin as a derivatising agent. Quantitation of the method was achieved by densitometric method at 550 nm over the concentration range of 10-100 ng/spot. This method showed good separation of amino acids in the brain homogenate with Rf value of L-glutamic acid and γ-amino butyric acid as 21.67±0.58 and 33.67±0.58, respectively. The limit of detection and limit of quantification for L-glutamic acid was found to be 10 and 20 ng and for γ-amino butyric acid it was 4 and 10 ng, respectively. The method was also validated in terms of accuracy, precision and repeatability. The developed method was found to be precise and accurate with good reproducibility and shows promising applicability for studying pathological status of disease and therapeutic significance of drug treatment. PMID:24591747

Development and Validation of a HPTLC Method for Simultaneous Estimation of L-Glutamic Acid and γ-Aminobutyric Acid in Mice Brain.

PubMed

Sancheti, J S; Shaikh, M F; Khatwani, P F; Kulkarni, Savita R; Sathaye, Sadhana

2013-11-01

A new robust, simple and economic high performance thin layer chromatographic method was developed for simultaneous estimation of L-glutamic acid and γ-amino butyric acid in brain homogenate. The high performance thin layer chromatographic separation of these amino acid was achieved using n-butanol:glacial acetic acid:water (22:3:5 v/v/v) as mobile phase and ninhydrin as a derivatising agent. Quantitation of the method was achieved by densitometric method at 550 nm over the concentration range of 10-100 ng/spot. This method showed good separation of amino acids in the brain homogenate with Rf value of L-glutamic acid and γ-amino butyric acid as 21.67±0.58 and 33.67±0.58, respectively. The limit of detection and limit of quantification for L-glutamic acid was found to be 10 and 20 ng and for γ-amino butyric acid it was 4 and 10 ng, respectively. The method was also validated in terms of accuracy, precision and repeatability. The developed method was found to be precise and accurate with good reproducibility and shows promising applicability for studying pathological status of disease and therapeutic significance of drug treatment.

Vacuum FTIR observation on hygroscopic properties and phase transition of malonic acid aerosols

NASA Astrophysics Data System (ADS)

Shao, Xu; Zhang, Yun; Pang, Shu-Feng; Zhang, Yun-Hong

2017-02-01

A novel approach based on a combination of a pulse relative humidity (RH) controlling system and a rapid scan vacuum FTIR spectrometer was utilized to investigate the hygroscopic property and phase transition of malonic acid (MA) aerosols. By using this approach, both water vapor amount around the aerosols and water content within aerosols with sub-second time resolution were obtained. Based on the features of FTIR absorbing bands, it can be known that the evolution of hydrogen-bonding structures of malonic acid aerosols took place from (H2O)n-MA to MA-MA accompanying with phase transition in the dehumidifying process. And in present paper, the stepwise efflorescence of MA aerosols and nucleation rates at different RHs are first reported. Our observation has shown that the efflorescence of MA started at ∼17% RH and the nucleation rates increased with decreasing RH.

Determination of Phenolic Acids in Sugarcane Vinasse by HPLC with Pulse Amperometry

PubMed Central

Freitas, P. V.; Beluomini, M. A.; da Silva, J. L.; Stradiotto, N. R.

2018-01-01

A reversed-phase liquid chromatographic separation with pulsed amperometric detection of phenolic acids at a glassy carbon electrode is described. Chromatographic separation was carried out in isocratic conditions using 0.20 mol·L−1 acetic acid (pH 5.0)/water (80 : 20, v/v) as mobile phase under constant working potential mode of 0.80 V. Chromatographic peaks presented high resolution and separation. Calibration curves exhibited excellent correlation coefficients, above 0.995. Linear ranges of the analytes, in mg L−1, were of 0.018–18 (gallic acid), 0.146–19 (vanillic acid), 0.13–17 (caffeic acid), 0.016–16 (ferulic acid), and 0.008–17 (p-coumaric acid), respectively. Limits of detection ranged from 1.6 to 97 μg·L−1 and precision varied in 1.73–3.78% interval. Concentrations of 19 ± 0.51 mg·L−1 and 7.8 ± 2.5 mg·L−1 were found for vanillic and caffeic acids, respectively, in a sugarcane vinasse sample. Gallic, ferulic, and p-coumaric acids were not detected. Recovery results demonstrated that the proposed method is accurate, and it can be used to detect and quantify phenolic acids in sugarcane vinasse without any influence of interferents. PMID:29600112

Modulated optical phase conjugation in rhodamine 110 doped boric acid glass saturable absorber thin films

NASA Astrophysics Data System (ADS)

Sharma, Ramesh C.; Waigh, Thomas A.; Singh, Jagdish P.

2008-03-01

The optical phase conjugation signal in nearly nondegenerate four wave mixing was studied using a rhodamine 110 doped boric acid glass saturable absorber nonlinear medium. We have demonstrated a narrow band optical filter (2.56±0.15Hz) using an optical phase conjugation signal in the frequency modulation of a weak probe beam in the presence of two strong counterpropagating pump beams in rhodamine 110 doped boric acid glass thin films (10-4m). Both the pump beams and the probe beam are at a wavelength of 488nm (continuous-wave Ar+ laser). The probe beam frequency was detuned with a ramp signal using a piezoelectric transducer mirror.

A Three-Dimensional Pore-Scale Model for Non-Wetting Phase Mobilization with Ferrofluid

NASA Astrophysics Data System (ADS)

Wang, N.; Prodanovic, M.

2017-12-01

Ferrofluid, a stable dispersion of paramagnetic nanoparticles in water, can generate a distributed pressure difference across the phase interface in an immiscible two-phase flow under an external magnetic field. In water-wet porous media, this non-uniform pressure difference may be used to mobilize the non-wetting phase, e.g. oil, trapped in the pores. Previous numerical work by Soares et al. of two-dimensional single-pore model showed enhanced non-wetting phase recovery with water-based ferrofluid under certain magnetic field directions and decreased recovery under other directions. However, the magnetic field selectively concentrates in the high magnetic permeability ferrofluid which fills the small corners between the non-wetting phase and the solid wall. The magnetic field induced pressure is proportional to the square of local magnetic field strength and its normal component, and makes a significant impact on the non-wetting phase deformation. The two-dimensional model omitted the effect of most of these corners and is not sufficient to compute the magnetic-field-induced pressure difference or to predict the non-wetting blob deformation. Further, it is not clear that 3D effects on magnetic field in an irregular geometry can be approximated in 2D. We present a three-dimensional immiscible two-phase flow model to simulate the deformation of a non-wetting liquid blob in a single pore filled with a ferrofluid under a uniform external magnetic field. The ferrofluid is modeled as a uniform single phase because the nanoparticles are 104 times smaller than the pore. The open source CFD solver library OpenFOAM is used for the simulations based on the volume of fluid method. Simulations are performed in a converging-diverging channel model on different magnetic field direction, different initial oil saturations, and different pore shapes. Results indicate that the external magnetic field always stretches the non-wetting blob away from the solid channel wall. A magnetic

R(-)-4-(3-Isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole, a fluorescent chiral tagging reagent: sensitive resolution of chiral amines and amino acids by reversed-phase liquid chromatography.

PubMed

Toyo'oka, T; Jin, D; Tomoi, N; Oe, T; Hiranuma, H

2001-02-01

The usefulness of R(-)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole [R(-)-DBD-PyNCS], a fluorescent chiral tagging reagent, for the determination of racemic amines and amino acids, was studied. The reagent reacted with beta-blockers selected as representative secondary amines to produce corresponding fluorescent diastereomers (excitation at 460 nm and emission at 550 nm). The yields of the derivatization reaction were dependent on the stereostructure arround the NH group in beta-blockers. The resulting diastereomers were completely separated with single chromatographic run using linear gradient elutions by reversed-phase chromatography. R(-)-DBD-PyNCS was also applied to the determination of DL-amino acid, considered to be one of the primary amines, in human urine and foodstuffs. DL-amino acids tested equally reacted with the reagent, and the thiocarbamoyl derivatives were separated with an ODS column. The epimerization during the derivatization reaction was negligible judging from the resolution of opposite diastereomers on the chromatogram. The occurence of D-amino acids (D-Ala, D-Ser, D-Asp and/or D-Glu) was identified in the samples tested. The structures and the purities were elucidated with on-line HPLC-MS. The chiral reagent possessing an isothiocyanate group (-NCS) in the structure seems to be applicable to continuous sequential analysis of peptides containing D-amino acids. The thiocarbamoyl derivatives obtained from the reaction with DL-amino acids were converted to thiohydantoins via thiazolinones in acidic medium. The thiohydantoins produced from acidic, basic, neutral, hydroxyl and aromatic amino acids were completely separated with isocratic elutions using acidic mobile phase containing 0.1% TFA. The separations were sufficient for the identification of DL-amino acid in peptide sequences. Although the epimerization during the conversion reaction to thiohydantoins was not avoidable, the descrimination of D- and

Relation of fatty acid composition in lead-exposed mallards to fat mobilization, lipid peroxidation and alkaline phosphatase activity

USGS Publications Warehouse

Mateo, R.; Beyer, W.N.; Spann, J.W.; Hoffman, D.J.

2003-01-01

The increase of n-6 polyunsaturated fatty acids (PUFA) in animal tissues has been proposed as a mechanism of lead (Pb) poisoning through lipid peroxidation or altered eicosanoids metabolism. We have studied fatty acid (FA) composition in liver and brain of mallards (Anas platyrhynchos) feeding for 3 weeks on diets containing combinations of low or high levels of vitamin E (20 or 200 UI/kg) and Pb (0 or 2 g/kg). Saturated FA, n-6 PUFA and total concentrations of FA were higher in livers of Pb-exposed mallards, but not in their brains. The percentage of n-6 PUFA in liver and brain was slightly higher in Pb-exposed mallards. The increase of n-6 PUFA in liver was associated with decreased triglycerides and increased cholesterol in plasma, thus could be in part attributed to feed refusal and fat mobilization. The hepatic ratios between adrenic acid (22:4 n-6) and arachidonic acid (20:4 n-6) or between adrenic acid and linoleic acid (18:2 n-6) were higher in Pb exposed birds, supporting the existing hypothesis of increased fatty acid elongation by Pb. Among the possible consequences of increased n-6 PUFA concentration in tissues, we found increased lipid peroxidation in liver without important histopathological changes, and decreased plasma alkaline phosphatase activity that may reflect altered bone metabolism in birds.

Features of separation on polymeric reversed phase for two classes of higher saturated fatty acids esters

NASA Astrophysics Data System (ADS)

Deineka, V. I.; Lapshova, M. S.; Zakharenko, E. V.; Deineka, L. A.

2013-11-01

The principles of sorption on polymeric reversed phase (PRP) YMS C30 for members of the two classes of esters formed by higher saturated fatty acids, i.e., lutein diesters ( I) and triacylglycerols ( II), are investigated. It is shown that the logarithm of the retention factor increases nonlinearly with an increase of the length of the acid radical, although the retention on PRP is higher in the case of I and lower in the case of II, compared to their retention on traditional monomeric reversed phase (MRP) Kromasil-100 5C18; however, the equivalence of the contributions to the retention of I that correspond to an identical change in acids, does not depend on the length of the hydrocarbon radical of the second acid. It is noted that the Van't Hoff plot for PRP contains a curve break, indicating a change in the retention mechanism upon a rise in temperature.

The 17,18-epoxyeicosatetraenoic acid-G protein-coupled receptor 40 axis ameliorates contact hypersensitivity by inhibiting neutrophil mobility in mice and cynomolgus macaques.

PubMed

Nagatake, Takahiro; Shiogama, Yumiko; Inoue, Asuka; Kikuta, Junichi; Honda, Tetsuya; Tiwari, Prabha; Kishi, Takayuki; Yanagisawa, Atsushi; Isobe, Yosuke; Matsumoto, Naomi; Shimojou, Michiko; Morimoto, Sakiko; Suzuki, Hidehiko; Hirata, So-Ichiro; Steneberg, Pär; Edlund, Helena; Aoki, Junken; Arita, Makoto; Kiyono, Hiroshi; Yasutomi, Yasuhiro; Ishii, Masaru; Kabashima, Kenji; Kunisawa, Jun

2017-12-27

Metabolites of eicosapentaenoic acid exert various physiologic actions. 17,18-Epoxyeicosatetraenoic acid (17,18-EpETE) is a recently identified new class of antiallergic and anti-inflammatory lipid metabolite of eicosapentaenoic acid, but its effects on skin inflammation and the underlying mechanisms remain to be investigated. We evaluated the effectiveness of 17,18-EpETE for control of contact hypersensitivity in mice and cynomolgus macaques. We further sought to reveal underlying mechanisms by identifying the responsible receptor and cellular target of 17,18-EpETE. Contact hypersensitivity was induced by topical application of 2,4-dinitrofluorobenzene. Skin inflammation and immune cell populations were analyzed by using flow cytometric, immunohistologic, and quantitative RT-PCR analyses. Neutrophil mobility was examined by means of imaging analysis in vivo and neutrophil culture in vitro. The receptor for 17,18-EpETE was identified by using the TGF-α shedding assay, and the receptor's involvement in the anti-inflammatory effects of 17,18-EpETE was examined by using KO mice and specific inhibitor treatment. We found that preventive or therapeutic treatment with 17,18-EpETE ameliorated contact hypersensitivity by inhibiting neutrophil mobility in mice and cynomolgus macaques. 17,18-EpETE was recognized by G protein-coupled receptor (GPR) 40 (also known as free fatty acid receptor 1) and inhibited chemoattractant-induced Rac activation and pseudopod formation in neutrophils. Indeed, the antiallergic inflammatory effect of 17,18-EpETE was abolished in the absence or inhibition of GPR40. 17,18-EpETE inhibits neutrophil mobility through GPR40 activation, which is a potential therapeutic target to control allergic inflammatory diseases. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Acid Vapor Weathering of Apatite and Implications for Mars

NASA Technical Reports Server (NTRS)

Hausrath, E. M.; Golden, D. C.; Morris, R. V.; Ming, D. W.

2008-01-01

Phosphorus is an essential nutrient for terrestrial life, and therefore may be important in characterizing habitability on Mars. In addition, phosphate mobility on Mars has been postulated as an indicator of early aqueous activity [1]. Rock surfaces analyzed by the Spirit Mars Exploration Rover indicate elemental concentrations consistent with the loss of a phosphate-containing mineral [2], and the highly altered Paso Robles deposit contains 5% P2O5, modeled as 8-10 % phosphate [3]. Depending on the pH of the solution, phosphate can exist as one of four charge states, which can affect its solubility, reactivity and mobility. Phosphate may therefore prove a useful and interesting tracer of alteration conditions on Mars. Acid vapor weathering has been previously studied as a potentially important process on Mars [4-6], and Paso Robles may have been formed by reaction of volcanic vapors with phosphate-bearing rock [3, 7]. Here we present preliminary results of acid vapor reactions in a Parr vessel [6] using fluorapatite, olivine and glass as single phases and in a mixture.

Favorable Effects of Weak Acids on Negative-Ion Electrospray Ionization Mass Spectrometry

PubMed Central

Wu, Zengru; Gao, Wenqing; Phelps, Mitch A.; Wu, Di; Miller, Duane D.; Dalton, James T.

2007-01-01

Despite widespread use in pharmacokinetic, drug metabolism, and pesticide residue studies, little is known about the factors governing response during reversed-phase liquid chromatography coupled with negative-ion electrospray ionization (ESI−) mass spectrometry. We examined the effects of various mobile-phase modifiers on the ESI− response of four selective androgen receptor modulators using a postcolumn infusion system. Acetic, propionic, and butyric acid improved the ESI− responses of analytes to varying extents at low concentrations. Formic acid suppressed ionization, as did neutral salts (ammonium formate, ammonium acetate) and bases (ammonium hydroxide, triethylamine) under most conditions. Two modifiers (2,2,2-trifluoroethanol, formaldehyde) that produce anions with high gas-phase proton affinity increased ESI− responses. However, the concentrations of these modifiers required to enhance ESI− response were higher than that of acidic modifiers, which is a phenomenon likely related to their low pKa values. 2,2,2-Trifluoroethanol increased response of more hydrophobic compounds but decreased response of a more hydrophilic compound. Formaldehyde improved response of all the compounds, especially the hydrophilic compound with lower surface activity. In summary, these results suggest that an ideal ESI− modifier should provide cations that can be easily electrochemically reduced and produce anions with small molecular volume and high gas-phase proton affinity. PMID:14750883

[Determination of aspirin and free salicylic acid in lysinipirine injection by high performance liquid chromatography].

PubMed

Dong, Yu; Zhao, Yuan-zheng; Zhang, Yi-na

2002-05-01

The contents of aspirin and free salicylic acid in lysinipirine injection were determined by high performance liquid chromatography (HPLC). A Hypersil BDS C18 column was used with the mobile phase of methanol-water-acetic acid (35:65:3, volume ratio) and the detection wavelength of 280 nm. The average recoveries of aspirin and salicylic acid added were 99.27% (RSD = 0.8%) and 99.61%(RSD = 1.3%), respectively. The calibration curves had good linearity in the range of 0.028 g/L -0.141 mg/L and 0.77 mg/L -3.85 mg/L, and the correlation coefficients were 0.9999 and 0.9998 for aspirin and salicylic acid respectively.

[Trace analysis of aristolochic acid A].

PubMed

Liu, Yalin; Gao, Huimin; Wang, Zhimin; Zhang, Qiwei

2010-12-01

A HPLC method for limit detection of aristolochic acid A in the Chinese herbs containing aristolochic acid or suspected-containing aristolochic acid and their preparations was established. The samples were analyzed on an Alltima C18 column eluted with methanol-water-acetic acid (68:32:1.5) as the mobile phase. Flow rate was at 1.0 mL x min(-1) and the detection wavelength was at 390 nm. The calibration curve was linear over the range from 0.016 to 0.51 g (r = 0.9993) and LOD was 4 ng. The average recovery was 101.2% with RSD of 2.01%. The procedures of sample preparation were systematically investigated. The contents of aristolochic acid A in Radix et Rhizoma Asari bought from market or drugstore were fluctuated from 3.1 to 26.6 microg x g(-1) and 3 of 11 samples accorded with the quality requirement of current Chinese Pharmacopoeia. Among 15 batches samples of Chinese medicaments, only one sample was found to contain aristolochic acid A. The present investigation shows that the method is sensitive and repeatable and it could be used for the limit detection of aristolochic acid A in the Chinese herbal medicines containing trace amount of aristolochic acid A or suspected-containing aristolochic acid A and their preparations.

Identification of ortho-Substituted Benzoic Acid/Ester Derivatives via the Gas-Phase Neighboring Group Participation Effect in (+)-ESI High Resolution Mass Spectrometry.

PubMed

Blincoe, William D; Rodriguez-Granillo, Agustina; Saurí, Josep; Pierson, Nicholas A; Joyce, Leo A; Mangion, Ian; Sheng, Huaming

2018-04-01

Benzoic acid/ester/amide derivatives are common moieties in pharmaceutical compounds and present a challenge in positional isomer identification by traditional tandem mass spectrometric analysis. A method is presented for exploiting the gas-phase neighboring group participation (NGP) effect to differentiate ortho-substituted benzoic acid/ester derivatives with high resolution mass spectrometry (HRMS 1 ). Significant water/alcohol loss (>30% abundance in MS 1 spectra) was observed for ortho-substituted nucleophilic groups; these fragment peaks are not observable for the corresponding para and meta-substituted analogs. Experiments were also extended to the analysis of two intermediates in the synthesis of suvorexant (Belsomra) with additional analysis conducted with nuclear magnetic resonance (NMR), density functional theory (DFT), and ion mobility spectrometry-mass spectrometry (IMS-MS) studies. Significant water/alcohol loss was also observed for 1-substituted 1, 2, 3-triazoles but not for the isomeric 2-substituted 1, 2, 3-triazole analogs. IMS-MS, NMR, and DFT studies were conducted to show that the preferred orientation of the 2-substituted triazole rotamer was away from the electrophilic center of the reaction, whereas the 1-subtituted triazole was oriented in close proximity to the center. Abundance of NGP product was determined to be a product of three factors: (1) proton affinity of the nucleophilic group; (2) steric impact of the nucleophile; and (3) proximity of the nucleophile to carboxylic acid/ester functional groups. Graphical Abstract ᅟ.

Identification of ortho-Substituted Benzoic Acid/Ester Derivatives via the Gas-Phase Neighboring Group Participation Effect in (+)-ESI High Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Blincoe, William D.; Rodriguez-Granillo, Agustina; Saurí, Josep; Pierson, Nicholas A.; Joyce, Leo A.; Mangion, Ian; Sheng, Huaming

2018-02-01

Benzoic acid/ester/amide derivatives are common moieties in pharmaceutical compounds and present a challenge in positional isomer identification by traditional tandem mass spectrometric analysis. A method is presented for exploiting the gas-phase neighboring group participation (NGP) effect to differentiate ortho-substituted benzoic acid/ester derivatives with high resolution mass spectrometry (HRMS1). Significant water/alcohol loss (>30% abundance in MS1 spectra) was observed for ortho-substituted nucleophilic groups; these fragment peaks are not observable for the corresponding para and meta-substituted analogs. Experiments were also extended to the analysis of two intermediates in the synthesis of suvorexant (Belsomra) with additional analysis conducted with nuclear magnetic resonance (NMR), density functional theory (DFT), and ion mobility spectrometry-mass spectrometry (IMS-MS) studies. Significant water/alcohol loss was also observed for 1-substituted 1, 2, 3-triazoles but not for the isomeric 2-substituted 1, 2, 3-triazole analogs. IMS-MS, NMR, and DFT studies were conducted to show that the preferred orientation of the 2-substituted triazole rotamer was away from the electrophilic center of the reaction, whereas the 1-subtituted triazole was oriented in close proximity to the center. Abundance of NGP product was determined to be a product of three factors: (1) proton affinity of the nucleophilic group; (2) steric impact of the nucleophile; and (3) proximity of the nucleophile to carboxylic acid/ester functional groups. [Figure not available: see fulltext.

[Influence of microbiological quality of lactic acid cheese on water phase in conditions of hermetic packing].

PubMed

Steinka, Izabela

2005-01-01

Aim of research was to assess the influence of lactic acid cheese micro-flora on water phase fluctuation between surface of products and the packaging. Results of research showed that changes of water content could be expressed with the help of polynomial cubic equation. From linear correlation equations describing level of micro-flora in lactic acid cheese and water content it resulted micro-organisms had a significant influence on the water phase fluctuation. Values of determined coefficients of determination suggested that yeast, enterococci and staphylococci had a significant influence on water fluctuation between product and the packaging.

Thermal Characterization of Lauric-Stearic Acid/Expanded Graphite Eutectic Mixture as Phase Change Materials.

PubMed

Zhu, Hua; Zhang, Peng; Meng, Zhaonan; Li, Ming

2015-04-01

The eutectic mixture of lauric acid (LA) and stearic acid (SA) is a desirable phase change material (PCM) due to the constant melting temperature and large latent heat. However, its poor thermal conductivity has hampered its broad utilization. In the present study, pure LA, SA and the mixtures with various mass fractions of LA-SA were used as the basic PCMs, and 10 wt% expanded graphite (EG) was added to enhance the thermal conductivities. The phase change behaviors, microstructural analysis, thermal conductivities and thermal stabilities of the mixtures of PCMs were investigated by differential scanning calorimetry (DSC), scanning electronic microscope (SEM), transient plane source (TPS) and thermogravimetric analysis (TGA), respectively. The results show that the LA-SA binary mixture of mixture ratio of 76.3 wt%: 23.7 wt% forms an eutectic mixture, which melts at 38.99 °C and has a latent heat of 159.94 J/g. The melted fatty acids are well absorbed by the porous network of EG and they have a good thermal stability. Furthermore, poor thermal conductivities can be well enhanced by the addition of EG.

Self-aggregation behavior of synthetic amphiphile derived from triazolylbenzoic acid: CMC and phase transition

NASA Astrophysics Data System (ADS)

Tajuddin, Hairul Anuar; Idris, Tarmezee; Zul, Nurul Faiezin; Sadidarto, Ahmad Bayhaki; Abdullah, Zanariah; Ahmad, Noraini

2017-12-01

An anionic surfactant with intention to mimic the natural fatty acids with highly conjugated component, has been synthesized and analyzed by using NMR, FTIR and MS. The polar head group of the structure was linked to the hydrophobic tail, through triazolyl moiety that was formed from the Cu(I) cycloaddition between an azidobenzoic acid and an acetylene. The critical micellar concentration (cmc) of the surfactant was determined at 0.1 mM by measuring its conductivity at a constant pH, consistent with the UV-Visible absorption. Phase transitions of the surfactant were then observed, by gradually decreasing the pH from 10 to 7. There were two stages of phase transitions observed at pH 8.9 and 7.6 upon titration, suggesting the transition from smaller to larger size of the aggregation structures. The results indicate that the aggregation mechanism of the synthesized surfactant w a s greatly influenced by the conversion of t h e head group from -COO- to -COOH, which is similar to the natural fatty acids in aqueous form.

Rapid Quantitative Analysis of Naringenin in the Fruit Bodies of Inonotus vaninii by Two-phase Acid Hydrolysis Followed by Reversed Phase-high Performance Liquid Chromatography-ultra Violet.

PubMed

Guohua, Xia; Pan, Ruirong; Bao, Rui; Ge, Yanru; Zhou, Cunshan; Shen, Yuping

2017-01-01

Sanghuang is one of mystical traditional Chinese medicines recorded earliest 2000 years ago, that included various fungi of Inonotus genus and was well-known for antitumor effect in modern medicine. Inonotus vaninii is grown in natural forest of Northeastern China merely and used as Sanghuang commercially, but it has no quality control specification until now. This study was to establish a rapid method of two-phase acid hydrolysis followed by reversed phase-high performance liquid chromatography-ultra violet (RP-HPLC-UV) to quantify naringenin in the fruit body of I. vaninii . Sample solution was prepared by pretreatment of raw material in two-phase acid hydrolysis and the hydrolysis technology was optimized. After reconstitution, analysis was performed using RP-HPLC-UV. The method validation was investigated and the naringenin content of sample and comparison were determined. The naringenin was obtained by two-phase acid hydrolysis method, namely, 10.0 g of raw material was hydrolyzed in 200 mL of 1% sulfuric acid aqueous solution (v/v) and 400 mL of chloroform in oil bath at 110°C for 2 h. Good linearity ( r = 0.9992) was achieved between concentration of analyte and peak area. The relative standard deviation (RSD) of precision was 2.47% and the RSD of naringenin contents for repeatability was 3.13%. The accuracy was supported with recoveries at 96.37%, 97.30%, and 99.31%. The sample solution prepared using the proposed method contained higher content of naringenin than conventional method and was stable for 8 h. Due to the high efficiency of sample preparation and high reliability of the HPLC method, it is feasible to use this method for routine analysis of naringenin in the fungus. A convenient two-phase acid hydrolysis was employed to produce naringenin from raw material, and then an efficient and reliable reversed phase-high performance liquid chromatography-ultra violet method was established to monitor naringenin in the fruit bodies of Inonotus vaninii

Polarons and Mobile Impurities Near a Quantum Phase Transition

NASA Astrophysics Data System (ADS)

Shadkhoo, Shahriar

This dissertation aims at improving the current understanding of the physics of mobile impurities in highly correlated liquid-like phases of matter. Impurity problems pose challenging and intricate questions in different realms of many-body physics. For instance, the problem of ''solvation'' of charged solutes in polar solvents, has been the subject of longstanding debates among chemical physicists. The significant role of quantum fluctuations of the solvent, as well as the break down of linear response theory, render the ordinary treatments intractable. Inspired by this complicated problem, we first attempt to understand the role of non-specific quantum fluctuations in the solvation process. To this end, we calculate the dynamic structure factor of a model polar liquid, using the classical Molecular Dynamics (MD) simulations. We verify the failure of linear response approximation in the vicinity of a hydrated electron, by comparing the outcomes of MD simulations with the predictions of linear response theory. This nonlinear behavior is associated with the pronounced peaks of the structure factor, which reflect the strong fluctuations of the local modes. A cavity picture is constructed based on heuristic arguments, which suggests that the electron, along with the surrounding polarization cloud, behave like a frozen sphere, for which the linear response theory is broken inside and valid outside. The inverse radius of the spherical region serves as a UV momentum cutoff for the linear response approximation to be applicable. The problem of mobile impurities in polar liquids can be also addressed in the framework of the ''polaron'' problem. Polaron is a quasiparticle that typically acquires an extended state at weak couplings, and crossovers to a self-trapped state at strong couplings. Using the analytical fits to the numerically obtained charge-charge structure factor, a phenomenological approach is proposed within the Leggett's influence functional formalism, which

Quantitative Determination of α-Arbutin, β-Arbutin, Kojic Acid, Nicotinamide, Hydroquinone, Resorcinol, 4-Methoxyphenol, 4-Ethoxyphenol, and Ascorbic Acid from Skin Whitening Products by HPLC-UV.

PubMed

Wang, Yan-Hong; Avonto, Cristina; Avula, Bharathi; Wang, Mei; Rua, Diego; Khan, Ikhlas A

2015-01-01

An HPLC-UV method was developed for the quantitative analysis of nine skin whitening agents in a single injection. These compounds are α-arbutin, β-arbutin, kojic acid, nicotinamide, resorcinol, ascorbic acid, hydroquinone, 4-methoxyphenol, and 4-ethoxyphenol. The separation was achieved on a reversed-phase C18 column within 30 min. The mobile phase was composed of water and methanol, both containing 0.1% acetic acid (v/v). The stability of the analytes was evaluated at different pH values between 2.3 and 7.6, and the extraction procedure was validated for different types of skin whitening product matrixes, which included two creams, a soap bar, and a capsule. The best solvent system for sample preparation was 20 mM NaH2PO4 containing 10% methanol at pH 2.3. The analytical method was validated for accuracy, precision, LOD, and LOQ. The developed HPLC-UV method was applied for the quantitation of the nine analytes in 59 skin whitening products including creams, lotions, sera, foams, gels, mask sheets, soap bars, tablets, and capsules.

Micellar electrokinetic chromatography with acid labile surfactant.

PubMed

Stanley, Bob; Lucy, Charles A

2012-02-24

We present a study of a degradable surfactant, sodium 4-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxy]-1-propane sulfonate that is also known as an acid-labile surfactant (ALS). The performance of ALS as a pseudostationary phase is assessed and compared with established pseudostationary phases such as sodium dodecyl sulphate (SDS), volatile surfactants and polymeric micelles. ALS achieves separation efficiency of 100,000-145,000 theoretical plates and relative standard deviation (RSD) of electrophoretic mobility (n=5) of less than 3%. Retention factors with ALS are strongly correlated with those with SDS. This is shown by the R2=0.79 for all eleven analytes and an R2=0.992 for specifically the non-hydrogen bonding (NHB) analytes. However, ALS displays different selectivity than SDS for hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) solutes (R2 of 0.74 and 0.88, respectively). ALS is degraded to less surface active compounds in acidic solution. These less surface-active compounds are more compatible with the electrospray ionization mass spectrometry (ESI-MS). ALS has a half-life of 48 min at pH 4. ALS has the potential to couple micellar electrokinetic chromatography (MEKC) with the ESI-MS. ALS can be used as a pseudostationary phase for a high efficiency separation and later acid hydrolyzed to enable an ESI-MS analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Gas-Phase and Solution-Phase Homolytic Bond Dissociation Energies of H-N(+) Bonds in the Conjugate Acids of Nitrogen Bases.

PubMed

Liu, Wei-Zhong; Bordwell, Frederick G.

1996-07-12

The oxidation potentials of 19 nitrogen bases (abbreviated as B: six primary amines, five secondary amines, two tertiary amines, three anilines, pyridine, quinuclidine, and 1,4-diazabicyclo[2,2,2]octane), i.e., E(ox)(B) values in dimethyl sulfoxide (DMSO) and/or acetonitrile (AN), have been measured. Combination of these E(ox)(B) values with the acidity values of the corresponding acids (pK(HB)(+)) in DMSO and/or AN using the equation: BDE(HB)(+) = 1.37pK(HB)(+) + 23.1 E(ox)(B) + C (C equals 59.5 kcal/mol in AN and 73.3 kcal/mol in DMSO) gave estimates of solution phase homolytic bond dissociation energies of H-B(+) bonds. Gas-phase BDE values of H-B(+) bonds were estimated from updated proton affinities (PA) and adiabatic ionization potentials (aIP) using the equation, BDE(HB(+))(g) = PA + aIP - 314 kcal/mol. The BDE(HB)(+) values estimated in AN were found to be 5-11 kcal/mol higher than the corresponding gas phase BDE(HB(+))(g) values. These bond-strengthening effects in solution are interpreted as being due to the greater solvation energy of the HB(+) cation than that of the B(+*) radical cation.

Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters.

PubMed

Pojjanapornpun, Siriluck; Nolvachai, Yada; Aryusuk, Kornkanok; Kulsing, Chadin; Krisnangkura, Kanit; Marriott, Philip J

2018-02-17

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (T M ), programmable T M during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension ( 1 D) phase polarity combined with a lower 2 D phase polarity, for instance 1 D IL111i with 2 D IL59 gave the best result; the greater difference in 1 D/ 2 D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

PubMed

Chen, Haihan; Grassian, Vicki H

2013-09-17

Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

Laser spectroscopy and dynamics of crystal lattices of chirally pure and racemic phases of amino acids

NASA Astrophysics Data System (ADS)

Belyanchikov, M. A.; Gorelik, V. S.; Gorshunov, B. P.; Pyatyshev, A. Yu.

2017-03-01

Strong sharp lines due to the librational modes characterized by a pseudoscalar symmetry type have been found in the low-frequency Raman spectra of the lattices of glycine and tyrosine amino acids. The intensities of these lines exceed those for Raman scattering in the region of intramolecular vibrations. The spectra of chirally pure and racemic phases of amino acids differ significantly. The results obtained can be used to observe stimulated Raman scattering from the librational modes of crystalline amino acids and monitor the chiral purity of bioactive preparations containing amino acids.

The influence of humic acid and clay content on the transport of polymer-coated iron nanoparticles through sand.

PubMed

Jung, Bahngmi; O'Carroll, Denis; Sleep, Brent

2014-10-15

The introduction of nanoscale zero valent iron (nZVI) into the subsurface has recently received significant attention as a potentially effective method for remediation of source zones of chlorinated solvents present as dense nonaqueous phase liquids (DNAPL). One of the challenges in the deployment of nZVI is to achieve good subsurface nZVI mobility to permit delivery of the nZVI to the target treatment zone. Stabilization of nZVI with various polymers has shown promise for enhancing nZVI subsurface mobility, but the impact of subsurface conditions on nZVI mobility has not been fully explored. In this study, the effect of humic acid and kaolinite on the transport of polymer-stabilized nZVI (carboxylmethyl cellulose-surface modified nZVI, CMC90K-RNIP) in sand was investigated using column experiments. In addition, effects of electrolytes on the stability of CMC90K-RNIP in the presence of humic acid, and the stability of humic acid-coated reactive nanoscale iron particles (HA-RNIP) at various humic acid concentrations were investigated. Humic acid enhanced the mobility of bare RNIP, whereas the transport of CMC90K-RNIP was not significantly affected by humic acid injected as a background solution, except at the highest concentration of 500mg/L. At lower pore water velocity, the effect of humic acid on the transport of CMC90K-RNIP was greater than that at high water velocity. Adding kaolinite up to 2% by weight to the sand column reduced the retention of CMC90K-RNIP, but further increases in kaolinite content (to 5%) did not significantly affect nZVI retention. The impact of kaolinite on nZVI retention was more pronounced at lower pore water velocities. Copyright © 2014 Elsevier B.V. All rights reserved.

Phase Engineering of Perovskite Materials for High-Efficiency Solar Cells: Rapid Conversion of CH3NH3PbI3 to Phase-Pure CH3NH3PbCl3 via Hydrochloric Acid Vapor Annealing Post-Treatment.

PubMed

Zhou, Weiran; Zhou, Pengcheng; Lei, Xunyong; Fang, Zhimin; Zhang, Mengmeng; Liu, Qing; Chen, Tao; Zeng, Hualing; Ding, Liming; Zhu, Jun; Dai, Songyuan; Yang, Shangfeng

2018-01-17

Organometal halide CH 3 NH 3 PbI 3 (MAPbI 3 ) has been commonly used as the light absorber layer of perovskite solar cells (PSCs), and, especially, another halide element chlorine (Cl) has been often incorporated to assist the crystallization of perovskite film. However, in most cases, a predominant MAPbI 3 phase with trace of Cl - is obtained ultimately and the role of Cl involvement remains unclear. Herein, we develop a low-cost and facile method, named hydrochloric acid vapor annealing (HAVA) post-treatment, and realize a rapid conversion of MAPbI 3 to phase-pure MAPbCl 3 , demonstrating a new concept of phase engineering of perovskite materials toward efficiency enhancement of PSCs for the first time. The average grain size of perovskite film after HAVA post-treatment increases remarkably through an Ostwald ripening process, leading to a denser and smoother perovskite film with reduced trap states and enhanced crystallinity. More importantly, the generation of MAPbCl 3 secondary phase via phase engineering is beneficial for improving the carrier mobility with a more balanced carrier transport rate and enlarging the band gap of perovskite film along with optimized energy level alignment. As a result, under the optimized HAVA post-treatment time (2 min), we achieved a significant enhancement of the power conversion efficiency (PCE) of the MAPbI 3 -based planar heterojunction-PSC device from 14.02 to 17.40% (the highest PCE reaches 18.45%) with greatly suppressed hysteresis of the current-voltage response.

Nickel-cadmium batteries: effect of electrode phase composition on acid leaching process.

PubMed

Nogueira, C A; Margarido, F

2012-01-01

At the end of their life, Ni-Cd batteries cause a number of environmental problems because of the heavy metals they contain. Because of this, recycling of Ni-Cd batteries has been carried out by dedicated companies using, normally, pyrometallurgical technologies. As an alternative, hydrometallurgical processes have been developed based on leaching operations using several types of leachants. The effect of factors like temperature, acid concentration, reaction time, stirring speed and grinding of material on the leaching yields of metals contained in anodic and cathodic materials (nickel, cadmium and cobalt) using sulphuric acid, is herein explained based on the structural composition of the electrode materials. The nickel, cobalt and cadmium hydroxide phases, even with a small reaction time (less than 15 minutes) and low temperature (50 degrees C) and acid concentration (1.1 M H2SO4), were efficiently leached. However, leaching of the nickel metallic phase was more difficult, requiring higher values of temperature, acid concentration and reaction time (e.g. 85 degrees C, 1.1 M H2SO4 and 5 h, respectively) in order to obtain a good leaching efficiency for anodic and cathodic materials (70% and 93% respectively). The stirring speed was not significant, whereas the grinding of electrode materials seems to promote the compaction of particles, which appears to be critical in the leaching of Ni degrees. These results allowed the identification and understanding of the relationship between the structural composition of electrode materials and the most important factors that affect the H2SO4 leaching of spent Ni-Cd battery electrodes, in order to obtain better metal-recovery efficiency.

Effect of citric acid on metals mobility in pruning wastes and biosolids compost and metals uptake in Atriplex halimus and Rosmarinus officinalis.

PubMed

Tapia, Y; Eymar, E; Gárate, A; Masaguer, A

2013-05-01

To assess metal mobility in pruning waste and biosolids compost (pH 6.9 and total concentration of metals in milligram per kilogram of Cd 1.9, Cu 132, Fe 8,513, Mn 192, Pb 81, and Zn 313), shrubs species Atriplex halimus and Rosmarinus officinalis were transplanted in this substrate and irrigated with citric acid (4 g L(-1), pH 2.9) and nutrient solution daily for 60 days. Citric acid significantly increased the concentrations of soluble Mn and Fe in the nutrient substrate solution measured by suction probes, while other metals did not vary in concentration (Cu and Zn) or were not observed at detectable levels (Cd and Pb). In plants, citric acid significantly increased the concentrations of Cu (2.7 ± 0.1-3.3 ± 0.1 mg kg(-1)), Fe (49.2 ± 5.2-76.8 ± 6.8 mg kg(-1)), and Mn (7.2 ± 1.1-11.4 ± 0.7 mg kg(-1)) in leaves of R. officinalis, whereas the concentration of only Mn (25.4 ± 0.3-42.2 ± 2.9 mg kg(-1)) was increased in A. halimus. Increasing Fe and Mn solubility by citric acid addition indicates the possibility of using it to improve plant nutrition. The mobility of metals in this substrate was influenced for the concentration of the metal, the degree of humification of organic matter and its high Fe content.

Chemical Treatments for Mobilizing Arsenic from Contaminated Aquifer Solids to Accelerate Remediation

PubMed Central

Wovkulich, Karen; Mailloux, Brian J.; Lacko, Allison; Keimowitz, Alison R.; Stute, Martin; Simpson, H. James; Chillrud, Steven N.

2010-01-01

Arsenic is a prevalent contaminant at US Superfund sites where remediation by pump and treat systems is often complicated by slow desorption of As from Fe and Al (hydr)oxides in aquifer solids. Chemical amendments that either compete with As for sorption sites or dissolve Fe and Al (hydr)oxides can increase As mobility and improve pump and treat remediation efficiency. The goal of this work was to determine optimal amendments for improving pump and treat at As contaminated sites such as the Vineland Chemical Co. Superfund site in southern New Jersey. Extraction and column experiments were performed using As contaminated aquifer solids (81 ± 1 mg/kg), site groundwater, and either phosphate (NaH2PO4·H2O) or oxalic acid (C2H2O4·2H2O). In extraction experiments, phosphate mobilized between 11% and 94% of As from the aquifer solids depending on phosphate concentration and extraction time (1 mM-1 M; 1–24 h) and oxalic acid mobilized between 38 and 102% depending on oxalic acid concentration and extraction time (1–400 mM; 1–24 h). In column experiments, phosphate additions induced more As mobilization in the first few pore volumes but oxalic acid was more effective at mobilizing As overall and at lower amendment concentrations. At the end of the laboratory column experiments, 48% of As had been mobilized from the aquifer sediments with 100 mM phosphate and 88% had been mobilized with 10 mM oxalic acid compared with 5% with ambient groundwater alone. Furthermore, simple extrapolations based on pore volumes suggest that chemical treatments could lower the time necessary for clean up at the Vineland site from 600 a with ambient groundwater alone to potentially as little as 4 a with 10 mM oxalic acid. PMID:21076621

Classifying the auditory P300 using mobile EEG recordings without calibration phase.

PubMed

Zink, R; Hunyádi, B; Van Huffel, S; De Vos, M

2015-08-01

One of the major drawbacks in mobile EEG Brain Computer Interfaces (BCI) is the need for subject specific training data to train a classifier. By removing the need for supervised classification and calibration phase, new users could start immediate interaction with a BCI. We propose a solution to exploit the structural difference by means of canonical polyadic decomposition (CPD) for three-class auditory oddball data without the need for subject-specific information. We achieve this by adding average event-related-potential (ERP) templates to the CPD model. This constitutes a novel similarity measure between single-trial pairs and known-templates, which results in a fast and interpretable classifier. These results have similar accuracy to those of the supervised and cross-validated stepwise LDA approach but without the need for having subject-dependent data. Therefore the described CPD method has a significant practical advantage over the traditional and widely used approach.

[Determination of ferulic acid absorbed into human serum from oral decoction of rhizoma chuanxiong and pharmacokinetic study of ferulic acid].

PubMed

Sun, S; Huang, X; Zhang, L; Ren, P; Chang, Z

2001-10-01

To improve the HPLC method for determining ferulic acid(FA) in the human serum and to research FA clinical pharmacokinetics. Serum concentrations of FA were determined by HPLC using methanol-water-acetic acid (40:59.7:0.3, v/v) as the mobile phase and the column packed with ODS (150 mm x 4.6 mm, 5 microns) as a fixed phase and the flow rate was 1.0 ml/min. FA was detected at 320 nm wave length. The internal standard was coumarin. The serum samples were treated by the water-boiling method. Peak of FA in serum was recognized by photodiode-array detection. FA and internal standard were separated completely under the condition described as above. FA was linear in the range of (40.16-8032 ng/ml) (r = 0.9975). The CV was less than 10%, the average recovery was 100.3%, and the limit concentration in serum was 25.1 ng/ml. PK was in accordance with open bicameral model. This method can be applied to clinical pharmacokinetic study of FA.

High carrier mobility of Sn-doped polycrystalline-Ge films on insulators by thickness-dependent low-temperature solid-phase crystallization

NASA Astrophysics Data System (ADS)

Sadoh, Taizoh; Kai, Yuki; Matsumura, Ryo; Moto, Kenta; Miyao, Masanobu

2016-12-01

To realize the advanced thin-film transistors (TFTs), high-carrier-mobility semiconductor films on insulator structures should be fabricated with low-temperature processing conditions (≤500 °C). To achieve this, we investigated the solid-phase crystallization of amorphous-GeSn films on insulating substrates under a wide range of Sn concentrations (0%-20%), film thicknesses (30-500 nm), and annealing temperatures (380-500 °C). Our results reveal that a Sn concentration close to the solid solubility of Sn in Ge (˜2%) is effective in increasing the grain-size of poly-GeSn. In addition, we discovered that the carrier mobility depends on the film thickness, where the mobilities are determined by the counterbalance between two different carrier scattering mechanisms. Here, vacancy-related defects dominate the carrier scattering near the insulating substrates (≤˜120 nm), and grain-size determined by bulk nucleation dominates the grain-boundary scattering of thick films (≥˜200 nm). Consequently, we obtained the maximum mobilities in samples with a Sn concentration of 2% and a film thickness of 200 nm. The effect of increasing the grain-size of poly-GeSn by lowering the annealing temperature was also clarified. By combining these results, a very high carrier mobility of 320 cm2/Vs was obtained at a low temperature of 380 °C. This mobility is about 2.5 times as high as previously reported data for Ge and GeSn films grown at low temperatures (≤500 °C). Our technique therefore opens up the possibility of high-speed TFTs for use in the next generation of electronics.

Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases.

PubMed

Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

2012-07-01

The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Land mobile radio system phase II deployment report

DOT National Transportation Integrated Search

2007-12-28

In July 2004, the Alaska Department of Transportation and Public Facilities developed an integration methodology for Land Mobile Radio into the Departments Statewide Intelligent Transportation Systems Deployment Plan and the State Information Tech...

Acid-Base Electronic Properties in the Gas Phase: Permanent Electric Dipole Moments of a Photoacidic Substrate.

NASA Astrophysics Data System (ADS)

Fleisher, Adam J.; Morgan, Philip J.; Pratt, David W.

2009-06-01

The permanent electric dipole moments of two conformers of 2-naphthol (2HN) in their ground and electronically excited states have been experimentally determined by Stark-effect measurements in a molecular beam. When in solution, 2HN is a weak base in the S{_0} state and a strong acid in the S{_1} state. Using sequential solvation of the cis-2HN photoacid with the base ammonia, we have begun to approach condensed phase acid-base interactions with gas phase rotational resolution. Our study, void of bulk solvent perturbations, is of importance to the larger community currently describing aromatic biomolecule and "super" photoacid behavior via theoretical modeling and condensed phase solvatochromism. [2] A. Weller. Prog. React. Kinet. 5, 273 (1970). [3] D. F. Plusquellic, X. -Q. Tan, and D. W. Pratt. J. Chem. Phys. 96, 8026 (1992).

Binary Phase Behavior of Saturated-Unsaturated Mixed-Acid Triacylglycerols-A Review.

PubMed

Zhang, Lu; Ueno, Satoru; Sato, Kiyotaka

2018-06-01

Most natural lipids contain a complex mixture of individual triacylglycerols (TAGs). An in-depth knowledge of the mixing behavior of TAGs is necessary for the rational design and engineering of food materials. The binary phase diagram of TAGs is a simplified model that can be explored to help foster an understanding of the phase behavior of complex fats and oils. This article reviews recent research on the binary phase behavior of saturated-unsaturated mixed-acid TAGs, with special emphasis on the stearicunsaturated and palmitic-unsaturated diacid TAGs. The occurrence of polymorphic forms and mutual solubility of TAG mixtures are strongly related to the glycerol conformation of the saturated-oleic diacid TAGs; it appears to be most influenced by the chain-length mismatch in saturated-elaidic diacid TAGs. In addition, the polymorphism of pure enantiomers and racemic mixture of chiral TAGs was also reviewed, while the effect of chirality on mixing behavior was discussed.

Hollow porous ionic liquids composite polymers based solid phase extraction coupled online with high performance liquid chromatography for selective analysis of hydrophilic hydroxybenzoic acids from complex samples.

PubMed

Dai, Xingping; Wang, Dongsheng; Li, Hui; Chen, Yanyi; Gong, Zhicheng; Xiang, Haiyan; Shi, Shuyun; Chen, Xiaoqing

2017-02-10

Polar and hydrophilic properties of hydroxybenzoic acids usually made them coelute with interferences in high performance liquid chromatography (HPLC) analysis. Then selective analysis of them was necessary. Herein, hollow porous ionic liquids composite polymers (PILs) based solid phase extraction (SPE) was firstly fabricated and coupled online with HPLC for selective analysis of hydroxybenzoic acids from complex matrices. Hollow porous PILs were firstly synthesized using Mobil Composition of Matter No. 48 (MCM-48) spheres as sacrificial support, 1-vinyl-3-methylimidazolium chloride (VMIM + Cl - ) as monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Various parameters affecting synthesis, adsorption and desorption behaviors were investigated and optimized. Steady-state adsorption studies showed the resulting hollow porous PILs exhibited high adsorption capacity, fast adsorption kinetics, and excellent specific adsorption. Subsequently, the application of online SPE system was studied by selective analysis of protocatechuic acid (PCA), 4-hydroxybenzoic acid (4-HBA), and vanillic acid (VA) from Pollen Typha angustifolia. The obtained limit of detection (LOD) varied from 0.002 to 0.01μg/mL, the linear range (0.05-5.0μg/mL) was wide with correlation coefficient (R) from 0.9982 to 0.9994, and the average recoveries at three spiking levels ranged from 82.7 to 102.4%, with column-to-column relative standard deviation (RSD) below 8.1%. The proposed online method showed good accuracy, precision, specificity and convenience, which opened up a universal and efficient route for selective analysis of hydroxybenzoic acids from complex samples. Copyright © 2017 Elsevier B.V. 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.

Land mobile radio system phase I pilot report

DOT National Transportation Integrated Search

2003-12-15

This report presents an executive summary, the project overview, Intelligent Transportation System standards and lessons learned for implementation of an Integrated Voice and Data, Land Mobile Radio System (ITS technologies for the Alaska Department ...

Application of HPLC with ELSD Detection for the Assessment of Azelaic Acid Impurities in Liposomal Formulation

PubMed Central

Han, Stanislaw; Karlowicz-Bodalska, Katarzyna; Ozimek, Lukasz

2013-01-01

In the course of research and development of a new pharmaceutical formulation of azelaic acid in the liposomal form, we developed a rapid and accurate method for the detection of impurities using high-performance liquid chromatography. A chromatographic column from Merck (Purospher Star RP C18, 250–4 mm (5 μm) was used in the assay, and the mobile phase gradient consisted of three phases: A—methanol : water (5 : 95) + 1.5% (v/v) acetic acid; B—water : methanol (5 : 95) + 1.5% (v/v) acetic acid; and C—chloroform. Detection of the impurities and the active substance was performed by an evaporative light-scattering detector. The method was validated for selectivity, system precision, method precision, limit of detection, and response rates. The proposed method can be used to detect impurities in the liposomal formulation of azelaic acid. The method enables separation of azelaic acid from the identified and unidentified impurities and from the excipients used in the drug form. PMID:24228008

Application of HPLC with ELSD detection for the assessment of azelaic acid impurities in liposomal formulation.

PubMed

Han, Stanislaw; Karlowicz-Bodalska, Katarzyna; Szura, Dorota; Ozimek, Lukasz; Musial, Witold

2013-01-01

In the course of research and development of a new pharmaceutical formulation of azelaic acid in the liposomal form, we developed a rapid and accurate method for the detection of impurities using high-performance liquid chromatography. A chromatographic column from Merck (Purospher Star RP C18, 250-4 mm (5 μm) was used in the assay, and the mobile phase gradient consisted of three phases: A--methanol : water (5 : 95) + 1.5% (v/v) acetic acid; B--water : methanol (5 : 95) + 1.5% (v/v) acetic acid; and C--chloroform. Detection of the impurities and the active substance was performed by an evaporative light-scattering detector. The method was validated for selectivity, system precision, method precision, limit of detection, and response rates. The proposed method can be used to detect impurities in the liposomal formulation of azelaic acid. The method enables separation of azelaic acid from the identified and unidentified impurities and from the excipients used in the drug form.

Effect of moisture on the field dependence of mobility for gas-phase ions of organophosphorus compounds at atmospheric pressure with field asymmetric ion mobility spectrometry.

PubMed

Krylova, N; Krylov, E; Eiceman, G A; Stone, J A

2003-05-15

The electric field dependence of the mobilities of gas-phase protonated monomers [(MH+(H2O)n] and proton-bound dimers [M2H+(H2O)n] of organophosphorus compounds was determined at E/N values between 0 and 140 Td at ambient pressure in air with moisture between 0.1 and 15 000 ppm. Field dependence was described as alpha (E/N) and was obtained from the measurements of compensation voltage versus field amplitude in a planar high-field asymmetric waveform ion mobility spectrometer. The alpha function for protonated monomers to 140 Td was constant from 0.1 to 10 ppm moisture in air with onset of effect at approximately 50 ppm. The value of alpha increased 2-fold from 100 to 1000 ppm at all E/N values. At moisture values between 1000 and 10 000 ppm, a 2-fold or more increase in alpha (E/N) was observed. In a model proposed here, field dependence for mobility through changes in collision cross sections is governed by the degree of solvation of the protonated molecule by neutral molecules. The process of ion declustering at high E/N values was consistent with the kinetics of ion-neutral collisional periods, and the duty cycle of the waveform applied to the drift tube. Water was the principal neutral above 50 ppm moisture in air, and nitrogen was proposed as the principal neutral below 50 ppm.

Morphology and phase transformations of tin oxide nanostructures synthesized by the hydrothermal method in the presence of dicarboxylic acids

NASA Astrophysics Data System (ADS)

Zima, Tatyana.; Bataev, Ivan

2016-11-01

A new approach to the synthesis of non-stoichiometric tin oxide structures with different morphologies and the phase compositions has been evaluated. The nanostructures were synthesized by hydrothermal treatment of the mixtures of dicarboxylic acids ― aminoterephthalic or oxalic ― with nanocrystalline SnO2 powder, which was obtained via the sol-gel technology. The products were characterized by Raman and IR spectroscopy, SEM, HRTEM, and XRD analysis. It was shown that the controlled addition of a dicarboxylic acid leads not only to a change in the morphology of the nanostructures, but also to SnO2-SnO2/Sn3O4-Sn3O4-SnO phase transformations. A single-phase Sn3O4 in the form of the well-separated hexagonal nanoplates and mixed SnO2/Sn3O4 phases in the form of hierarchical flower-like structures were obtained in the presence of organic additives. The effects of concentration, redox activity of the acids and heat treatment on the basic characteristics of the synthesized tin oxide nanostructures and phase transformations in the synthesized materials are discussed.

Chelant-aided enhancement of lead mobilization in residential soils.

PubMed

Sarkar, Dibyendu; Andra, Syam S; Saminathan, Sumathi K M; Datta, Rupali

2008-12-01

Chelation of metals is an important factor in enhancing solubility and hence, availability to plants to promote phytoremediation. We compared the effects of two chelants, namely, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS) in enhancing mobilized lead (Pb) in Pb-based paint contaminated residential soils collected from San Antonio, Texas and Baltimore, Maryland. Batch incubation studies were performed to investigate the effectiveness of the two chelants in enhancing mobilized Pb, at various concentrations and treatment durations. Over a period of 1 month, the mobilized Pb pool in the San Antonio study soils increased from 52 mg kg(-1) to 287 and 114 mg kg(-1) in the presence of 15 mM kg(-1) EDTA and EDDS, respectively. Stepwise linear regression analysis demonstrated that pH and organic matter content significantly affected the mobilized Pb fraction. The regression models explained a large percentage, from 83 to 99%, of the total variation in mobilized Pb concentrations.

Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

NASA Astrophysics Data System (ADS)

Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

2018-04-01

While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

Industrial application of green chromatography--I. Separation and analysis of niacinamide in skincare creams using pure water as the mobile phase.

PubMed

Yang, Yu; Strickland, Zackary; Kapalavavi, Brahmam; Marple, Ronita; Gamsky, Chris

2011-03-15

In this work, chromatographic separation of niacin and niacinamide using pure water as the sole component in the mobile phase has been investigated. The separation and analysis of niacinamide have been optimized using three columns at different temperatures and various flow rates. Our results clearly demonstrate that separation and analysis of niacinamide from skincare products can be achieved using pure water as the eluent at 60°C on a Waters XTerra MS C18 column, a Waters XBridge C18 column, or at 80°C on a Hamilton PRP-1 column. The separation efficiency, quantification quality, and analysis time of this new method are at least comparable with those of the traditional HPLC methods. Compared with traditional HPLC, the major advantage of this newly developed green chromatography technique is the elimination of organic solvents required in the HPLC mobile phase. In addition, the pure water chromatography separations described in this work can be directly applied in industrial plant settings without further modification of the existing HPLC equipment. Copyright © 2011 Elsevier B.V. All rights reserved.

Investigating the Weak to Evaluate the Strong: An Experimental Determination of the Electron Binding Energy of Carborane Anions and the Gas phase Acidity of Carborane Acids

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

Meyer, Matthew M; Wang, Xue B; Reed, Christopher A

2009-12-23

Five CHB 11X 6Y 5 - carborane anions from the series X = Br, Cl, I and Y = H, Cl, CH 3 were generated by electrospray ionization, and their reactivity with a series of Brønsted acids and electron transfer reagents were examined in the gas phase. The undecachlorocarborane acid, H(CHB 11Cl 11), was found to be far more acidic than the former record holder, (1-C 4F 9SO 2) 2NH (i.e., ΔH° acid = 241 ± 29 vs 291.1 ± 2.2 kcal mol -1) and bridges the gas-phase acidity and basicity scales for the first time. Its conjugate base, CHBmore » 11Cl 11 -, was found by photoelectron spectroscopy to have a remarkably large electron binding energy (6.35 ± 0.02 eV) but the value for the (1-C 4F 9SO 2) 2N - anion is even larger (6.5 ± 0.1 eV). Consequently, it is the weak H-(CHB 11Cl 11) BDE (70.0 kcal mol -1, G3(MP2)) compared to the strong BDE of (1-C 4F 9SO 2) 2N-H (127.4 ± 3.2 kcal mol -1) that accounts for the greater acidity of carborane acids.« less

Solubilization of lipids and lipid phases by the styrene-maleic acid copolymer.