Digital Troposcatter Performance Model. Users Manual.

DTIC Science & Technology

1983-11-01

and Information Systems - .,- - - UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered) S REPORT DOCUIAENTATION PAGE READ...Diffraction Multipath Prediction MD-918 Modem Error Rate Prediction AN/TRC-170 Link Analysis 20. ABSTRACT (Continue en reverse esie If neceseay end...configurations used in the Defense Communications System (DCS), and prediction of the performance of both the MD-918 and AN/TRC-170 digital troposcatter modems

Ultra High-Resolution Electrospray Ionization/Ion Mobility Spectrometer System for In-Situ Detection of Organic Compounds

NASA Technical Reports Server (NTRS)

Kanik, I.; Beegle, L. W.; Hill, H. H.

2001-01-01

The potential of the high-resolution Electrospray Ionization/Ion Mobility Spectrometry (ESI/IMS) technique as analytical separation tool in analyzing bio-molecular mixtures in the search for the chemical signatures of life is demonstrated. Additional information is contained in the original extended abstract.

Evaluation of a PCR/ESI-MS platform to identify respiratory viruses from nasopharyngeal aspirates.

PubMed

Lin, Yong; Fu, Yongfeng; Xu, Menghua; Su, Liyun; Cao, Lingfeng; Xu, Jin; Cheng, Xunjia

2015-11-01

Acute respiratory tract infection is a major cause of morbidity and mortality worldwide, particularly in infants and young children. High-throughput, accurate, broad-range tools for etiologic diagnosis are critical for effective epidemic control. In this study, the diagnostic capacities of an Ibis platform based on the PCR/ESI-MS assay were evaluated using clinical samples. Nasopharyngeal aspirates (NPAs) were collected from 120 children (<5 years old) who were hospitalized with lower respiratory tract infections between November 2010 and October 2011. The respiratory virus detection assay was performed using the PCR/ESI-MS assay and the DFA. The discordant PCR/ESI-MS and DFA results were resolved with RT-PCR plus sequencing. The overall agreement for PCR/ESI-MS and DFA was 98.3% (118/120). Compared with the results from DFA, the sensitivity and specificity of the PCR/ESI-MS assay were 100% and 97.5%, respectively. The PCR/ESI-MS assay also detected more multiple virus infections and revealed more detailed subtype information than DFA. Among the 12 original specimens with discordant results between PCR/ESI-MS and DFA, 11 had confirmed PCR/ESI-MS results. Thus, the PCR/ESI-MS assay is a high-throughput, sensitive, specific and promising method to detect and subtype conventional viruses in respiratory tract infections and allows rapid identification of mixed pathogens. © 2015 Wiley Periodicals, Inc.

Nursing Perceptions of the Emergency Severity Index as a Triage Tool in the United Arab Emirates: A Qualitative Analysis.

PubMed

Mistry, Binoy; Balhara, Kamna S; Hinson, Jeremiah S; Anton, Xavier; Othman, Iman Yassin; E'nouz, Maysoon Abdel Latif; Avila, Norman Agustin; Henry, Sophia; Levin, Scott; De Ramirez, Sarah Stewart

2017-11-19

With emergency department crowding becoming an increasing problem across the globe, nursing triage to prioritize patients receiving care is ever more important. ESI is the most common triage system used in the United States and is increasingly used worldwide. This qualitative study that explores emergency nursing perceptions of the ESI identifies strengths, weaknesses, and barriers to implementation of the ESI internationally. We conducted a cross-sectional qualitative analysis using semistructured interviews of 27 emergency triage nurses. Content analysis was performed by 2 independent coders, using NVivo software to identify and analyze important themes. Interview coding revealed 7 core themes related to use of the ESI (frequencies indicated in parentheses): ease of use (90), speed and efficiency (135), patient safety (12), accuracy and reliability (30), challenging patient characteristics (123), subjectivity and variability (173), and effect of triage system on team dynamics (100). Intercoder agreement was excellent (Cohen's unweighted kappa = 0.84). Subjectivity and variability in ESI score assignment consistently emerged in all interviews and included variability in number and use of resources, definition of "high risk," nursing experience, and subjectivity in pain assessment. Although emergency nurses perceive the ESI as easy to use, there are concerns about the subjectivity and variability inherent in the ESI that can lead to a functional lack of triage and a burden of undifferentiated ESI level 3 patients. These limitations in separating critically ill patients and in stratifying patients based on anticipated required resources points to the need for improvement in the ESI algorithm or a more objective triage system that can predict patient outcomes. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular diagnosis of bloodstream infections in onco-haematology patients with PCR/ESI-MS technology.

PubMed

Jordana-Lluch, Elena; Rivaya, Belén; Marcó, Clara; Giménez, Montserrat; Quesada, Mª Dolores; Escobedo, Agustín; Batlle, Montserrat; Martró, Elisa; Ausina, Vicente

2017-02-01

Onco-haematological patients are prone to develop infections, and antibiotic prophylaxis may lead to negative blood cultures. Thus, the microbiological diagnosis and subsequent administration of a targeted antimicrobial therapy is often difficult. The goal of this study was to evaluate the usefulness of IRIDICA (PCR/ESI-MS technology) for the molecular diagnosis of bloodstream infections in this patient group. A total of 463 whole blood specimens from different sepsis episodes in 429 patients were analysed using the PCR/ESI-MS platform, comparing the results with those of blood culture and other clinically relevant information. The sensitivity of PCR/ESI-MS by specimen (excluding polymicrobial infections, n = 25) in comparison with blood culture was 64.3% overall, 69.0% in oncological patients, and 59.3% in haematological patients. When comparing with a clinical infection criterion, overall sensitivity rose to 74.7%, being higher in oncological patients (80.0%) than in haematological patients (67.7%). Thirty-one microorganisms isolated by culture were not detected by IRIDICA, whereas 42 clinically relevant pathogens not isolated by culture were detected moleculary. PCR/ESI-MS offers a reliable identification of pathogens directly from whole blood. While additional studies are needed to confirm our findings, the system showed a lower sensitivity in onco-haematological patients in comparison with previously reported results in patients from the Intensive Care Unit. Copyright © 2016 The British Infection Association. Published by Elsevier Ltd. All rights reserved.

78 FR 42723 - Airworthiness Directives; Pilatus Aircraft Ltd. Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-17

... System (ESIS). If the common ground fails both navigations systems could fail simultaneously, which could... Display (PFD) and the Electronic Standby Instrument System (ESIS). If the common ground fails both navigations systems could fail simultaneously, which could result in loss of control. We are issuing this...

78 FR 58874 - Airworthiness Directives; PILATUS AIRCRAFT LTD. Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-25

... System (ESIS). If the common ground fails both navigations systems could fail simultaneously, which could... flight display (PFD) and the Electronic Standby Instrument System (ESIS). If the common ground fails both navigation systems could fail simultaneously. We are issuing this AD to prevent simultaneous failure of both...

Developmental validation of the PowerPlex(®) ESI 16 and PowerPlex(®) ESI 17 Systems: STR multiplexes for the new European standard.

PubMed

Tucker, Valerie C; Hopwood, Andrew J; Sprecher, Cynthia J; McLaren, Robert S; Rabbach, Dawn R; Ensenberger, Martin G; Thompson, Jonelle M; Storts, Douglas R

2011-11-01

In response to the ENFSI and EDNAP groups' call for new STR multiplexes for Europe, Promega(®) developed a suite of four new DNA profiling kits. This paper describes the developmental validation study performed on the PowerPlex(®) ESI 16 (European Standard Investigator 16) and the PowerPlex(®) ESI 17 Systems. The PowerPlex(®) ESI 16 System combines the 11 loci compatible with the UK National DNA Database(®), contained within the AmpFlSTR(®) SGM Plus(®) PCR Amplification Kit, with five additional loci: D2S441, D10S1248, D22S1045, D1S1656 and D12S391. The multiplex was designed to reduce the amplicon size of the loci found in the AmpFlSTR(®) SGM Plus(®) kit. This design facilitates increased robustness and amplification success for the loci used in the national DNA databases created in many countries, when analyzing degraded DNA samples. The PowerPlex(®) ESI 17 System amplifies the same loci as the PowerPlex(®) ESI 16 System, but with the addition of a primer pair for the SE33 locus. Tests were designed to address the developmental validation guidelines issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM), and those of the DNA Advisory Board (DAB). Samples processed include DNA mixtures, PCR reactions spiked with inhibitors, a sensitivity series, and 306 United Kingdom donor samples to determine concordance with data generated with the AmpFlSTR(®) SGM Plus(®) kit. Allele frequencies from 242 white Caucasian samples collected in the United Kingdom are also presented. The PowerPlex(®) ESI 16 and ESI 17 Systems are robust and sensitive tools, suitable for the analysis of forensic DNA samples. Full profiles were routinely observed with 62.5pg of a fully heterozygous single source DNA template. This high level of sensitivity was found to impact on mixture analyses, where 54-86% of unique minor contributor alleles were routinely observed in a 1:19 mixture ratio. Improved sensitivity combined with the robustness afforded by smaller amplicons has substantially improved the quantity of data obtained from degraded samples, and the improved chemistry confers exceptional tolerance to high levels of laboratory prepared inhibitors. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Electrospray ionization mass spectrometry: a technique to access the information beyond the molecular weight of the analyte.

PubMed

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

Developmental validation of the PowerPlex(®) ESI 16/17 Fast and PowerPlex(®) ESX 16/17 Fast Systems.

PubMed

McLaren, Robert S; Bourdeau-Heller, Jeanne; Patel, Jaynish; Thompson, Jonelle M; Pagram, Jenny; Loake, Thomas; Beesley, David; Pirttimaa, Markus; Hill, Carolyn R; Duewer, David L; Kline, Margaret C; Butler, John M; Storts, Douglas R

2014-11-01

The PowerPlex(®) ESI 16 Fast, ESI 17 Fast, ESX 16 Fast, and ESX 17 Fast Systems represent faster cycling versions (50min or less) of the PowerPlex(®) ESI and ESX Systems released by Promega in 2009 to accommodate the ENFSI and EDNAP groups' call for new STR multiplexes for Europe. In addition to amplification of purified DNA samples, these new faster cycling systems allow for direct amplification from single-source blood and buccal samples deposited on FTA(®) and nonFTA paper as well as from SwabSolution™ extracts of buccal swabs without the need for purification and quantitation. There are no changes to the autosomal primer pair sequences in the PowerPlex(®) ESI Fast and ESX Fast Systems compared to the original multiplexes, and full concordance at all autosomal loci and amelogenin was observed with data generated previously with the original PowerPlex(®) ESI and ESX Systems. This paper describes the developmental validation study performed on these new fast systems following guidelines issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM) and those of the DNA Advisory Board (DAB). Validation data demonstrate that these systems are sensitive for detecting low levels of DNA while also being capable of generating robust profiles from the high amount of input DNA present in direct-amplification samples. These systems are also tolerant to both high concentrations of PCR inhibitors as well as to slight variations in the final concentration of master mix and primer pair present in the amplification reaction that might be encountered due to pipetting error. The results of this validation study demonstrate that these systems may be used on multiple thermal cyclers and capillary electrophoresis platforms. Copyright © 2014 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

Structural characterisation by both positive- and negative-ion electrospray mass spectrometry of partially methyl-esterified oligogalacturonides purified by semi-preparative high-performance anion-exchange chromatography.

PubMed

Quéméner, Bernard; Désiré, Cédric; Lahaye, Marc; Debrauwer, Laurent; Negroni, Luc

2003-01-01

The off-line coupling of high-performance anion-exchange chromatography (HPAEC) to electrospray ionisation/ion trap mass spectrometry (ESI-ITMS) is described. The Dionex carbohydrate membrane desalter (CMD) has been assessed as an on-line chromatographic desalting system to remove the high sodium concentration necessary for the HPAEC separation of partially methyl-esterified oligogalacturonides. The developed HPAEC configuration proved to be suitable for indirect coupling with ESI-ITMS. This paper provides some interesting features of positive- and negative-ion multistage tandem mass spectrometry (MS(n)) analysis of these acidic oligosaccharides. The spectra acquired in both negative- and positive-ion modes show characteristic fragment ions resulting from glycosidic bond and cross-ring cleavages. Some new mass spectrometric fragmentation routes are also described. The positive-ion mode gave more complex spectra but was as informative as the negative-ion mode. ESI-ITMS was revealed to be, as previously reported from direct use on an unseparated enzymatic digest, a powerful sequencing technique for the determination of linkage type and the methyl ester distribution of partially methyl-esterified oligogalacturonides. Moreover, unlike matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF MS), it gives valuable information on the elution behaviour of these oligomers in relation to their structure, namely the HPAEC co-elution of isomeric structures.

Fact Sheet: Best Practices Handbook for the Collection and Use of Solar Energy Applications; Best Practices Handbook for the Collection and Use of Solar Energy Applications (Fact Sheet), Energy Systems Integration (ESI), NREL (National Renewable Energy Laboratory)

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

None

2015-06-01

This fact sheet presents highlights from the Best Practices Handbook for the Collection and Use of Solar Resource Data for Solar Energy Applications, which provides detailed information about solar resource data and the resulting data products needed for planning each stage of large concentrating solar power systems, from initial site selection to system operations.

Meeting in Canada: Chlorinated vs. Chloraminated Drinking Water: Toxicity-Based Identification of Disinfection By-Products Using ESI-MS and ESI-MS/MS

EPA Science Inventory

Drinking water disinfection by-products (DBPs) are of concern because epidemiologic studies have shown that they are associated with bladder cancer and adverse reproductive/developmental effects in human populations. There is almost no information on high molecular weight DBPs (>...

Application of CE-ICP-MS and CE-ESI-MS/MS for identification of Zn-binding ligands in Goji berries extracts.

PubMed

Ruzik, Lena; Kwiatkowski, Piotr

2018-06-01

The identification of groups of ligands binding metals is a crucial issue for the better understanding of their bioaccessibility. In the current study, we have intended an approach for identification of Zn-binding ligands based on using capillary electrophoresis combined with inductively coupled plasma mass spectrometry (CE-ICP-MS) and tandem electrospray ionization mass spectrometry (CE-ESI-MS/MS). The approach, which featured the use of the coupling of capillary electrophoresis with inductively coupled plasma mass spectrometry allows to separate and observe zinc ions present in complexes with respect to their size and charge and to identify nine compounds with zinc isotopic profile. CE-ICP-MS provides us with information about presence of zinc species and elemental information about zinc distribution. CE-ESI-MS/MS provide us with information about the most favorable Zn binding ligands: amino acids, flavonols, stilbenoids, fenolic acids and carotenoids. The presented work is the continuation of previous studies based on using LC-ESI-MS/MS, though, now we presented a new solutions with the possibility of changing detectors without changing the separation techniques, what is important without re-optimizing the method. The new presented method allows to identify the zinc-binding ligands in shorter time. Copyright © 2018 Elsevier B.V. All rights reserved.

Use of Land Surface Temperature Observations in a Two-Source Energy Balance Model Towards Improved Monitoring of Evapotranspiration and Drought

NASA Astrophysics Data System (ADS)

Hain, C.; Anderson, M. C.; Otkin, J.; Semmens, K. A.; Zhan, X.; Fang, L.; Li, Z.

2014-12-01

As the world's water resources come under increasing tension due to the dual stressors of climate change and population growth, accurate knowledge of water consumption through evapotranspiration (ET) over a range in spatial scales will be critical in developing adaptation strategies. However, direct validation of ET models is challenging due to lack of available observations that are sufficiently representative at the model grid scale (10-100 km). Prognostic land-surface models require accurate information about observed precipitation, soil moisture storage, groundwater, and artificial controls on water supply (e.g., irrigation, dams, etc.) to reliably link rainfall to evaporative fluxes. In contrast, diagnostic estimates of ET can be generated, with no prior knowledge of the surface moisture state, by energy balance models using thermal-infrared remote sensing of land-surface temperature (LST) as a boundary condition. One such method, the Atmosphere Land Exchange Inverse (ALEXI) model provides estimates of surface energy fluxes through the use of mid-morning change in LST and radiation inputs. The LST inputs carry valuable proxy information regarding soil moisture and its effect on soil evaporation and canopy transpiration. Additionally, the Evaporative Stress Index (ESI) representing anomalies in the ratio of actual-to-potential ET has shown to be a reliable indicator of drought. ESI maps over the continental US show good correspondence with standard drought metrics and with patterns of precipitation, but can be generated at significantly higher spatial resolution due to a limited reliance on ground observations. Furthermore, ESI is a measure of actual stress rather than potential for stress, and has physical relevance to projected crop development. Because precipitation is not used in construction of the ESI, it provides an independent assessment of drought conditions and has particular utility for real-time monitoring in regions with sparse rainfall data or significant delays in meteorological reporting. An initial analysis of a new prototype global ALEXI system using twice-daily observations of MODIS LST will be presented. The newly generated global ET and ESI datasets will be compared to other globally available ET and drought products during a multi-year evaluation period (2000-2013).

Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

PubMed Central

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research. PMID:22611397

Metabolic profiling of roots of liquorice (Glycyrrhiza glabra) from different geographical areas by ESI/MS/MS and determination of major metabolites by LC-ESI/MS and LC-ESI/MS/MS.

PubMed

Montoro, Paola; Maldini, Mariateresa; Russo, Mariateresa; Postorino, Santo; Piacente, Sonia; Pizza, Cosimo

2011-02-20

Liquid chromatography electrospray mass spectrometry (LC-ESI/MS) has been applied to the full characterization of saponins and phenolics in hydroalcoholic extracts of roots of liquorice (Glycyrrhiza glabra). Relative quantitative analyses of the samples with respect to the phenolic constituents and to a group of saponins related to glycyrrhizic acid were performed using LC-ESI/MS. For the saponin constituents, full scan LC-MS/MS fragmentation of the protonated (positive ion mode) or deprotonated (negative ion mode) molecular species generated diagnostic fragment ions that provided information concerning the triterpene skeleton and the number and nature of the substituents. On the basis of the specific fragmentation of glycyrrhizic acid, an LC-MS/MS method was developed in order to quantify the analyte in the liquorice root samples. Chinese G. glabra roots contained the highest levels of glycyrrhizic acid, followed by those from Italy (Calabria). Copyright © 2010 Elsevier B.V. All rights reserved.

A review of nanoelectrospray ionization applications for drug metabolism and pharmacokinetics.

PubMed

Wickremsinhe, Enaksha R; Singh, Gurkeerat; Ackermann, Bradley L; Gillespie, Todd A; Chaudhary, Ajai K

2006-12-01

Although traditionally reserved for proteomic analysis, nanoESI has found increased use for small molecule applications related to drug metabolism/pharmacokinetics (DMPK). NanoESI, which refers to ESI performed at flow rates in the range of 200 to 1000 nL/min using smaller diameter emitters (10 to 100 microm id), produces smaller droplets than conventional ESI resulting in more efficient ionization. Benefits include greater sensitivity, enhanced dynamic range, and a reduced competition for ionization. These advantages may now be harnessed largely due to the introduction of a commercial system for automated nanoESI infusion. This development in turn has allowed ADME (absorption, distribution, metabolism, and excretion) scientists to consider novel approaches to mass spectrometric analysis without direct LC interfacing. While it is freely acknowledged that nanoESI infusion is not likely to supplant LC-MS as the primary analytical platform for ADME, nanoESI infusion has been successfully applied to both quantitative (bioanalysis) and qualitative (metabolite identification) applications. This review summarizes published applications of this technology and offers a perspective on where it fits best into the DMPK laboratory.

Quantitation of 5-Methyltetrahydrofolate in Cerebrospinal Fluid Using Liquid Chromatography-Electrospray Tandem Mass Spectrometry.

PubMed

Arning, Erland; Bottiglieri, Teodoro

2016-01-01

We describe a simple stable isotope dilution method for accurate and precise measurement of cerebrospinal fluid (CSF) 5-methyltetrahydrofolate (5-MTHF) as a clinical diagnostic test. 5-MTHF is the main biologically active form of folic acid and is involved in regulation of homocysteine and DNA synthesis. Measurement of 5-MTHF in CSF provides diagnostic information regarding diseases affecting folate metabolism within the central nervous system, in particular inborn errors of folate metabolism. Determination of 5-MTHF in CSF (50 μL) was performed utilizing high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). 5-MTHF in CSF is determined by a 1:2 dilution with internal standard (5-MTHF-(13)C5) and injected directly onto the HPLC-ESI-MS/MS system. Each assay is quantified using a five-point standard curve (25-400 nM) and has an analytical measurement range of 3-1000 nM.

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex† †Electronic supplementary information (ESI) available: Experimental details, characterization of cycloadducts and intermediates, computational data. CCDC 1411372 and 1411373. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02311a

PubMed Central

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J.; Bittner, Alexander M.; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I.; Miranda, José I.

2017-01-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N-metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts. PMID:29147531

Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

NASA Astrophysics Data System (ADS)

Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

2016-04-01

Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

Developing AN Emergency Response Model for Offshore Oil Spill Disaster Management Using Spatial Decision Support System (sdss)

NASA Astrophysics Data System (ADS)

Balogun, Abdul-Lateef; Matori, Abdul-Nasir; Wong Toh Kiak, Kelvin

2018-04-01

Environmental resources face severe risks during offshore oil spill disasters and Geographic Information System (GIS) Environmental Sensitivity Index (ESI) maps are increasingly being used as response tools to minimize the huge impacts of these spills. However, ESI maps are generally unable to independently harmonize the diverse preferences of the multiple stakeholders' involved in the response process, causing rancour and delay in response time. This paper's Spatial Decision Support System (SDSS) utilizes the Analytic Hierarchy Process (AHP) model to perform tradeoffs in determining the most significant resources to be secured considering the limited resources and time available to perform the response operation. The AHP approach is used to aggregate the diverse preferences of the stakeholders and reach a consensus. These preferences, represented as priority weights, are incorporated in a GIS platform to generate Environmental sensitivity risk (ESR) maps. The ESR maps provide a common operational platform and consistent situational awareness for the multiple parties involved in the emergency response operation thereby minimizing discord among the response teams and saving the most valuable resources.

Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge† †Electronic supplementary information (ESI) available: A breakdown of calculated activation free energies shown in Table 1, as well as absolute energies and Cartesian coordinates of all key species in this work are presented as ESI. See DOI: 10.1039/c5ob00309a Click here for additional data file.

PubMed Central

Carvalho, Alexandra T. P.; O'Donoghue, AnnMarie C.; Hodgson, David R. W.

2015-01-01

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism. PMID:25797408

Definitive screening design enables optimization of LC-ESI-MS/MS parameters in proteomics.

PubMed

Aburaya, Shunsuke; Aoki, Wataru; Minakuchi, Hiroyoshi; Ueda, Mitsuyoshi

2017-12-01

In proteomics, more than 100,000 peptides are generated from the digestion of human cell lysates. Proteome samples have a broad dynamic range in protein abundance; therefore, it is critical to optimize various parameters of LC-ESI-MS/MS to comprehensively identify these peptides. However, there are many parameters for LC-ESI-MS/MS analysis. In this study, we applied definitive screening design to simultaneously optimize 14 parameters in the operation of monolithic capillary LC-ESI-MS/MS to increase the number of identified proteins and/or the average peak area of MS1. The simultaneous optimization enabled the determination of two-factor interactions between LC and MS. Finally, we found two parameter sets of monolithic capillary LC-ESI-MS/MS that increased the number of identified proteins by 8.1% or the average peak area of MS1 by 67%. The definitive screening design would be highly useful for high-throughput analysis of the best parameter set in LC-ESI-MS/MS systems.

Going Global: A Model for Evaluating Empirically Supported Family-Based Interventions in New Contexts.

PubMed

Sundell, Knut; Ferrer-Wreder, Laura; Fraser, Mark W

2014-06-01

The spread of evidence-based practice throughout the world has resulted in the wide adoption of empirically supported interventions (ESIs) and a growing number of controlled trials of imported and culturally adapted ESIs. This article is informed by outcome research on family-based interventions including programs listed in the American Blueprints Model and Promising Programs. Evidence from these controlled trials is mixed and, because it is comprised of both successful and unsuccessful replications of ESIs, it provides clues for the translation of promising programs in the future. At least four explanations appear plausible for the mixed results in replication trials. One has to do with methodological differences across trials. A second deals with ambiguities in the cultural adaptation process. A third explanation is that ESIs in failed replications have not been adequately implemented. A fourth source of variation derives from unanticipated contextual influences that might affect the effects of ESIs when transported to other cultures and countries. This article describes a model that allows for the differential examination of adaptations of interventions in new cultural contexts. © The Author(s) 2012.

ESIS ions injection, holding and extraction control system

NASA Astrophysics Data System (ADS)

Donets, E. D.; Donets, E. E.; Donets, D. E.; Lyuosev, D. A.; Ponkin, D. O.; Ramsdorf, A. Yu.; Boytsov, A. Yu.; Salnikov, V. V.; Shirikov, I. V.

2018-04-01

Electron string ion source (ESIS) KRION-6T is one of the main parts of the NICA injection complex [1]. During the work on creation of a new ion source for the NICA/MPD project the new ion motion control system was developed, produced and successfully put into operation. Modules development process and operation results are described.

Improving Emergency Department Triage Classification with Computerized Clinical Decision Support at a Pediatric Hospital

ERIC Educational Resources Information Center

Kunisch, Joseph Martin

2012-01-01

Background: The Emergency Severity Index (ESI) is an emergency department (ED) triage classification system based on estimated patient-specific resource utilization. Rules for a computerized clinical decision support (CDS) system based on a patient's chief complaint were developed and tested using a stochastic model for predicting ESI scores.…

ESI activity of Br⁻, BF₄⁻ , ClO₄⁻ and BPh₄⁻ anions in the presence of Li⁺ and NBu⁴⁺ counter-ions.

PubMed

Koszinowski, K; Lissy, F

2017-03-01

To improve our understanding of the electrospray ionization (ESI) process, we have subjected equimolar mixtures of salts A + X - (A +  = Li + , NBu 4 + ; X -  = Br - , ClO 4 - , BF 4 - , BPh 4 - ) in different solvents (CH 3 CN, tetrahydrofuran, CH 3 OH, H 2 O) to negative-ion mode ESI and analyzed the relative ESI activity of the different anionic model analytes. The ESI activity of the large and hydrophobic BPh 4 - ion greatly exceeds that of the smaller and more hydrophilic anions Br - , ClO 4 - and BF 4 - , which we ascribe to its higher surface activity. Moreover, the ESI activity of the anions is modulated by the action of the counter-ions and their different tendency toward ion pairing. The tendency toward ion pairing can be reduced by the addition of the chelating ligands 12-crown-4 and 2.2.1 cryptand and is, although to a smaller degree, further influenced by the variation of the solvent. Complementary electrical conductivity measurements afford additional information on the interactions of the ionic constituents of the sample solutions. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Yield of MRI, high-density electric source imaging (HD-ESI), SPECT and PET in epilepsy surgery candidates.

PubMed

Lascano, Agustina M; Perneger, Thomas; Vulliemoz, Serge; Spinelli, Laurent; Garibotto, Valentina; Korff, Christian M; Vargas, Maria I; Michel, Christoph M; Seeck, Margitta

2016-01-01

Preoperative workup aims at localizing the epileptogenic focus to achieve postoperative seizure-freedom. We studied the predictive value of non-invasive techniques, i.e. structural magnetic resonance imaging [MRI], high-density electric source imaging [HD-ESI] and metabolic imaging (positron emission tomography [PET]; single-photon emission computed tomography [SPECT]), in surgically treated patients. A prospective study of 190 epileptic operated patients, with >12 months follow-up and analyzed with state-of-the-art algorithms. 58 patients underwent all techniques. We computed sensitivity, specificity, predictive value and diagnostic odds ratio (OR) in relation to postoperative outcome. Of 190 patients, 148 (77.9%) were seizure-free at follow-up. Resection of the epileptogenic focus was associated with favorable postsurgical outcome (p<0.05). Among 58 patients who underwent all tests, only MRI and HD-ESI were favorable outcome predictors (MRI: OR 10.9, p=0.004; HD-ESI: OR 13.1, p=0.004). Patients with concordant structural MRI and HD-ESI results had 92.3% (24/26) probability of favorable outcome. When both results were negative, probability was 0% (0/5); and when they disagreed, it was 63.0% (17/27). Combination of MRI and HD-ESI offered the highest predictive value for postoperative seizure-freedom. This finding highlights the added value of HD-ESI in the presurgical workup, in particular in combination with an informative MRI. Copyright © 2015 International Federation of Clinical Neurophysiology. Published by Elsevier Ireland Ltd. All rights reserved.

Good Effective School Improvement Practices in Spain.

ERIC Educational Resources Information Center

Murillo, F. Javier

2002-01-01

Presents case studies of five effective school improvement (ESI) programs developed in Spain. Identified characteristics of the Spanish education system that affect the way ESI programs are carried out and developed descriptions of the five programs and lessons learned from them. (SLD)

Development of a low-flow multiplexed interface for capillary electrophoresis/electrospray ion trap mass spectrometry using sequential spray.

PubMed

Chen, Chao-Jung; Li, Fu-An; Her, Guor-Rong

2008-05-01

A multiplexed CE-MS interface using four low-flow sheath liquid ESI sprayers has been developed. Because of the limited space between the low-flow sprayers and the entrance aperture of the ESI source, multichannel analysis is difficult using conventional rotating plate approaches. Instead, a multiplexed low-flow system was achieved by applying an ESI potential sequentially to the four low-flow sprayers, resulting in only one sprayer being sprayed at any given time. The synchronization of the scan event and the voltage relays was accomplished by using the data acquisition signal from the IT mass spectrometer. This synchronization resulted in the ESI voltage being sequentially applied to each of the four sprayers according to the corresponding scan event. With this design, a four-fold increase in analytical throughput was achieved. Because of the use of low-flow interfaces, this multiplexed system has superior sensitivity than a rotating plate design using conventional sheath liquid interfaces. The multiplexed design presented has the potential to be applied to other low-flow multiplexed systems, such as multiplexed capillary LC and multiplexed CEC.

Semiconductive 3-D haloplumbate framework hybrids with high color rendering index white-light emission† †Electronic supplementary information (ESI) available. CCDC 1055380 and 1055381. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02501j Click here for additional data file. Click here for additional data file.

PubMed Central

Wang, Guan-E; Wang, Ming-Sheng; Cai, Li-Zhen; Li, Wen-Hua

2015-01-01

Single-component white light materials may create great opportunities for novel conventional lighting applications and display systems; however, their reported color rendering index (CRI) values, one of the key parameters for lighting, are less than 90, which does not satisfy the demand of color-critical upmarket applications, such as photography, cinematography, and art galleries. In this work, two semiconductive chloroplumbate (chloride anion of lead(ii)) hybrids, obtained using a new inorganic–organic hybrid strategy, show unprecedented 3-D inorganic framework structures and white-light-emitting properties with high CRI values around 90, one of which shows the highest value to date. PMID:28757985

Satellite-based mapping of field-scale stress indicators for crop yield forecasting: an application over Mead, NE

NASA Astrophysics Data System (ADS)

Yang, Y.; Anderson, M. C.; Gao, F.; Wardlow, B.; Hain, C.; Otkin, J.; Sun, L.; Dulaney, W.

2017-12-01

In agricultural regions, water is one of the most widely limiting factors of crop performance and production. Evapotranspiration (ET) describes crop water use through transpiration and water lost through direct soil evaporation, which makes it a good indicator of soil moisture availability and vegetation health and thus has been an integral part of many yield estimation efforts. The Evaporative Stress Index (ESI) describes temporal anomalies in a normalized evapotranspiration metric (fRET) as derived from satellite remote sensing and has demonstrated capacity to explain regional yield variability in water limited crop growing regions. However, its performance in some regions where the vegetation cycle is intensively managed appears to be degraded. In this study we generated maps of ET, fRET, and ESI at high spatiotemporal resolution (30-m pixels, daily timesteps) using a multi-sensor data fusion method, integrating information from satellite platforms with good temporal coverage and other platforms that provide field-scale spatial detail. The study was conducted over the period 2010-2014, covering a region around Mead, Nebraska that includes both rainfed and irrigated crops. Correlations between ESI and measurements of corn yield are investigated at both the field and county level to assess the value of ESI as a yield forecasting tool. To examine the role of phenology in ESI-yield correlations, annual input fRET timeseries were aligned by both calendar day and by biophysically relevant dates (e.g. days since planting or emergence). Results demonstrate that mapping of fRET and ESI at 30-m has the advantage of being able to resolve different crop types with varying phenology. The study also suggests that incorporating phenological information significantly improves yield-correlations by accounting for effects of phenology such as variable planting date and emergence date. The yield-ESI relationship in this study well captures the inter-annual variability of yields and thus has potential to be used for yield prediction, or for ingestion into a crop simulation model as a crop-specific moisture stress function.

Determination and Isolation of Four Anti-tumour Saponins from Lonicera macranthoides by HPLC-ESI-QTOF/MS and HSCCC.

PubMed

Liu, Xuehui; Zhou, Rongrong; Shen, Bingbing; Chen, Lin; Zhou, Qingyijun; Wan, Dan; Huang, Luqi; Zhang, Shuihan

2017-01-01

Lonicera macranthoides is a Chinese herb that contains a large number of bioactive spanions possessing important pharmacological activities, such as anti-tumour activity. However, detailed information about their anti-tumor activity and bioactive compounds is limited. In order to evaluate the scientific basis, the method of high-speed counter-current chromatography (HSCCC) combined with high performance liquid chromatography mass spectrometry (HPLC-ESI-QTOF/MS) has been developed to separate, purify and analyze saponins from Lonicera macranthoides. Four main saponins, Macranthoidin B (I), Macranthoidin A (II), Macranthoides B (III) and Akebia saponin D (IV) were separated by HSCCC with the solvent systems of ethyl acetate-nbutanol- water (3:2:5) and n-butanol-water-methanol-ethyl acetate (1:6:0.5:4). The purities of these four bioactive ingredients (I-IV) identified and detected by HPLC-ESI-QTOF/MS were 95.1%, 92.7%, 91.8% and 96.3%, respectively. The separated saponins were evaluated for their cytotoxic activities against six tumor cell lines (MCF-7, Hela, A549, HepG2, HT29 and Eca109). Results show that compounds I-IV exhibited particular significant anti-tumor activities against human mammary adenocarcinoma MCF-7 cell with IC50 values ranging from 12.7 to 30.8 µM. It was demonstrated that the combinative method using HPLC-ESI-QTOF/MS and HSCCC was suitable for rapid screening and isolating saponins of Lonicera macranthoides and the isolated compounds have great potential for the development of new antitumor drugs. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Patient Ethnicity Affects Triage Assessments and Patient Prioritization in U.S. Department of Veterans Affairs Emergency Departments

PubMed Central

Vigil, Jacob M.; Coulombe, Patrick; Alcock, Joe; Kruger, Eric; Stith, Sarah S.; Strenth, Chance; Parshall, Mark; Cichowski, Sara B.

2016-01-01

Abstract Ethnic minority patients receive lower priority triage assignments in Veteran's Affairs (VA) emergency departments (EDs) compared to White patients, but it is currently unknown whether this disparity arises from generalized biases across the triage assessment process or from differences in how objective and/or subjective institution-level or person-level information is incorporated into the triage assessment process, thus contributing to disparate treatment. The VA database of electronic medical records of patients who presented to the VA ED from 2008 to 2012 was used to measure patient ethnicity, self-reported pain intensity (PI) levels, heart rate (HR), respiratory rate (RR), and nurse-provided triage assignment, the Emergency Severity Index (ESI) score. Multilevel, random effects linear modeling was used to control for demographic and clinical characteristics of patients as well as age, gender, and experience of triage nurses. A total of 359,642 patient/provider encounters between 129,991 VA patients and 774 nurses were included in the study. Patients were 61% non-Hispanic White [NHW], 28% African-American, 7% Hispanic, 2% Asian-American, <1% American Indian/Alaska Native, and 1% mixed ethnicity. After controlling for demographic characteristics of nurses and patients, African-American, Hispanic, and mixed-ethnicity patients reported higher average PI scores but lower HRs and RRs than NHW patients. NHW patients received higher priority ESI ratings with lower PI when compared against African-American patients. NHW patients with low to moderate HRs also received higher priority ESI scoring than African-American, Hispanic, Asian-American, and Mixed-ethnicity patients; however, when HR was high NHWs received lower priority ESI ratings than each of the minority groups (except for African-Americans). This study provides evidence for systemic differences in how patients’ vital signs are applied for determining ESI scores for different ethnic groups. Additional prospective research will be needed to determine how this specific person-level mechanism affects healthcare quality and outcomes. PMID:27057847

Comparison of satellite-derived LAI and precipitation anomalies over Brazil with a thermal infrared-based Evaporative Stress Index for 2003-2013

NASA Astrophysics Data System (ADS)

Anderson, Martha C.; Zolin, Cornelio A.; Hain, Christopher R.; Semmens, Kathryn; Tugrul Yilmaz, M.; Gao, Feng

2015-07-01

Shortwave vegetation index (VI) and leaf area index (LAI) remote sensing products yield inconsistent depictions of biophysical response to drought and pluvial events that have occurred in Brazil over the past decade. Conflicting reports of severity of drought impacts on vegetation health and functioning have been attributed to cloud and aerosol contamination of shortwave reflectance composites, particularly over the rainforested regions of the Amazon basin which are subject to prolonged periods of cloud cover and episodes of intense biomass burning. This study compares timeseries of satellite-derived maps of LAI from the Moderate Resolution Imaging Spectroradiometer (MODIS) and precipitation from the Tropical Rainfall Mapping Mission (TRMM) with a diagnostic Evaporative Stress Index (ESI) retrieved using thermal infrared remote sensing over South America for the period 2003-2013. This period includes several severe droughts and floods that occurred both over the Amazon and over unforested savanna and agricultural areas in Brazil. Cross-correlations between absolute values and standardized anomalies in monthly LAI and precipitation composites as well as the actual-to-reference evapotranspiration (ET) ratio used in the ESI were computed for representative forested and agricultural regions. The correlation analyses reveal strong apparent anticorrelation between MODIS LAI and TRMM precipitation anomalies over the Amazon, but better coupling over regions vegetated with shorter grass and crop canopies. The ESI was more consistently correlated with precipitation patterns over both landcover types. Temporal comparisons between ESI and TRMM anomalies suggest longer moisture buffering timescales in the deeper rooted rainforest systems. Diagnostic thermal-based retrievals of ET and ET anomalies, such as used in the ESI, provide independent information on the impacts of extreme hydrologic events on vegetation health in comparison with VI and precipitation-based drought indicators, and used in concert may provide a more reliable evaluation of natural and managed ecosystem response to variable climate regimes.

Electro-triggering and electrochemical monitoring of dopamine exocytosis from a single cell by using ultrathin electrodes based on Au nanowires

NASA Astrophysics Data System (ADS)

Kang, Mijeong; Yoo, Seung Min; Gwak, Raekeun; Eom, Gayoung; Kim, Jihwan; Lee, Sang Yup; Kim, Bongsoo

2015-12-01

A sophisticated set of an Au nanowire (NW) stimulator-Au NW detector system is developed for electrical cell stimulation and electrochemical analysis of subsequent exocytosis with very high spatial resolution. Dopamine release from a rat pheochromocytoma cell is more stimulated by a more negative voltage pulse. This system could help to improve the therapeutic efficacy of electrotherapies by providing valuable information on their healing mechanism.A sophisticated set of an Au nanowire (NW) stimulator-Au NW detector system is developed for electrical cell stimulation and electrochemical analysis of subsequent exocytosis with very high spatial resolution. Dopamine release from a rat pheochromocytoma cell is more stimulated by a more negative voltage pulse. This system could help to improve the therapeutic efficacy of electrotherapies by providing valuable information on their healing mechanism. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06021d

Re-investigation of the fragmentation of protonated carotenoids by electrospray ionization and nanospray tandem mass spectrometry.

PubMed

Neto, Fausto Carnevale; Guaratini, Thais; Costa-Lotufo, Letícia; Colepicolo, Pio; Gates, Paul J; Lopes, Norberto Peporine

2016-07-15

Carotenoids are polyene isoprenoids with an important role in photosynthesis and photoprotection. Their characterization in biological matrices is a crucial subject for biochemical research. In this work we report the full fragmentation of 16 polyenes (carotenes and xanthophylls) by electrospray ionization tandem mass spectrometry (ESI-CID-MS/MS) and nanospray tandem mass spectrometry (nanoESI-CID-MS/MS). Analyses were carried out on a quadrupole time-of-flight (QTOF) mass spectrometer coupled with a nanoESI source and on a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer with an ESI source. The formulae of the product ions were determined by accurate-mass measurements. It is demonstrated that the fragmentation routes observed for the protonated carotenoids derive essentially from charge-remote fragmentations and pericyclic rearrangements, such as electrocyclic and retro-ene eliminations (assisted or not by a sigmatropic hydrogen shift). All mechanisms are dependent on cis-trans isomerization through the formation of several conjugated polyene carbocation intermediates. Some specific ions for the carotenoid epoxides were justified through formation of cyclic oxonium ions. Complete fragmentation pathways of protonated carotenoids by ESI- and nanoESI-CID-MS/MS provided structural information about functional groups, polyene chain and double bonds, and contribute to identification of carotenoids based on MS/MS fragmentation patterns. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Sensitivity of GC-EI/MS, GC-EI/MS/MS, LC-ESI/MS/MS, LC-Ag(+) CIS/MS/MS, and GC-ESI/MS/MS for analysis of anabolic steroids in doping control.

PubMed

Cha, Eunju; Kim, Sohee; Kim, Ho Jun; Lee, Kang Mi; Kim, Ki Hun; Kwon, Oh-Seung; Lee, Jaeick

2015-01-01

This study compared the sensitivity of various separation and ionization methods, including gas chromatography with an electron ionization source (GC-EI), liquid chromatography with an electrospray ionization source (LC-ESI), and liquid chromatography with a silver ion coordination ion spray source (LC-Ag(+) CIS), coupled to a mass spectrometer (MS) for steroid analysis. Chromatographic conditions, mass spectrometric transitions, and ion source parameters were optimized. The majority of steroids in GC-EI/MS/MS and LC-Ag(+) CIS/MS/MS analysis showed higher sensitivities than those obtained with other analytical methods. The limits of detection (LODs) of 65 steroids by GC-EI/MS/MS, 68 steroids by LC-Ag(+) CIS/MS/MS, 56 steroids by GC-EI/MS, 54 steroids by LC-ESI/MS/MS, and 27 steroids by GC-ESI/MS/MS were below cut-off value of 2.0 ng/mL. LODs of steroids that formed protonated ions in LC-ESI/MS/MS analysis were all lower than the cut-off value. Several steroids such as unconjugated C3-hydroxyl with C17-hydroxyl structure showed higher sensitivities in GC-EI/MS/MS analysis relative to those obtained using the LC-based methods. The steroids containing 4, 9, 11-triene structures showed relatively poor sensitivities in GC-EI/MS and GC-ESI/MS/MS analysis. The results of this study provide information that may be useful for selecting suitable analytical methods for confirmatory analysis of steroids. Copyright © 2015 John Wiley & Sons, Ltd.

Can acyclic conformational control be achieved via a sulfur–fluorine gauche effect?† †Electronic supplementary information (ESI) available. CCDC 1048074–1048078. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00871a

PubMed Central

Thiehoff, C.; Holland, M. C.; Daniliuc, C.

2015-01-01

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC–H) and acceptor (antibonding, σ*C–F) orbitals. This model rationalises the generic conformational preference of F–Cβ–Cα–X systems (φFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F–C–C–S(O)n; φFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+–O–, SO2). PMID:29511517

Optimization of information content in a mass spectrometry based flow-chemistry system by investigating different ionization approaches.

PubMed

Martha, Cornelius T; Hoogendoorn, Jan-Carel; Irth, Hubertus; Niessen, Wilfried M A

2011-05-15

Current development in catalyst discovery includes combinatorial synthesis methods for the rapid generation of compound libraries combined with high-throughput performance-screening methods to determine the associated activities. Of these novel methodologies, mass spectrometry (MS) based flow chemistry methods are especially attractive due to the ability to combine sensitive detection of the formed reaction product with identification of introduced catalyst complexes. Recently, such a mass spectrometry based continuous-flow reaction detection system was utilized to screen silver-adducted ferrocenyl bidentate catalyst complexes for activity in a multicomponent synthesis of a substituted 2-imidazoline. Here, we determine the merits of different ionization approaches by studying the combination of sensitive detection of product formation in the continuous-flow system with the ability to simultaneous characterize the introduced [ferrocenyl bidentate+Ag](+) catalyst complexes. To this end, we study the ionization characteristics of electrospray ionization (ESI), atmospheric-pressure chemical ionization (APCI), no-discharge APCI, dual ESI/APCI, and dual APCI/no-discharge APCI. Finally, we investigated the application potential of the different ionization approaches by the investigation of ferrocenyl bidentate catalyst complex responses in different solvents. Copyright © 2011 Elsevier B.V. All rights reserved.

Validation of different pediatric triage systems in the emergency department

PubMed Central

Aeimchanbanjong, Kanokwan; Pandee, Uthen

2017-01-01

BACKGROUND: Triage system in children seems to be more challenging compared to adults because of their different response to physiological and psychosocial stressors. This study aimed to determine the best triage system in the pediatric emergency department. METHODS: This was a prospective observational study. This study was divided into two phases. The first phase determined the inter-rater reliability of five triage systems: Manchester Triage System (MTS), Emergency Severity Index (ESI) version 4, Pediatric Canadian Triage and Acuity Scale (CTAS), Australasian Triage Scale (ATS), and Ramathibodi Triage System (RTS) by triage nurses and pediatric residents. In the second phase, to analyze the validity of each triage system, patients were categorized as two groups, i.e., high acuity patients (triage level 1, 2) and low acuity patients (triage level 3, 4, and 5). Then we compared the triage acuity with actual admission. RESULTS: In phase I, RTS illustrated almost perfect inter-rater reliability with kappa of 1.0 (P<0.01). ESI and CTAS illustrated good inter-rater reliability with kappa of 0.8–0.9 (P<0.01). Meanwhile, ATS and MTS illustrated moderate to good inter-rater reliability with kappa of 0.5–0.7 (P<0.01). In phase II, we included 1 041 participants with average age of 4.7±4.2 years, of which 55% were male and 45% were female. In addition 32% of the participants had underlying diseases, and 123 (11.8%) patients were admitted. We found that ESI illustrated the most appropriate predicting ability for admission with sensitivity of 52%, specificity of 81%, and AUC 0.78 (95%CI 0.74–0.81). CONCLUSION: RTS illustrated almost perfect inter-rater reliability. Meanwhile, ESI and CTAS illustrated good inter-rater reliability. Finally, ESI illustrated the appropriate validity for triage system. PMID:28680520

[HPLC-ESI-MS(n) analysis of the water soluble extracts of Fructus Choerospondiatis].

PubMed

Shi, Run-ju; Dai, Yun; Fang, Min-feng; Zhao, Xin; Zheng, Jian-bin; Zheng, Xiao-hui

2007-03-01

To establish an HPLC-ESI-MS(n) method for analyzing the chemical ingredients in the water soluble extracts of Fructus Choerospondiatis. Water-solvable extracts of Fructus Choerospondiatis are obtained by heating recirculation. Multi-stage reaction mode (MRM) of the HPLC-ESI-MS(n) was used to determine the content of Gallic acid, the MS(n) technology was used to obtain the information of characteristic multistage fragment ions so as to identify the chemical structure of peaks in the total current spectrum. Eleven compounds were identified, and one of them is a new unknown ingredient. The method, which has high recovery and specificity, can offer the experimental evidences for the further research of the chemical ingredients extracted from the Fructus Choerospondiatis.

Assessment of a demonstration project to supply near real-time sea ice information to end users

NASA Astrophysics Data System (ADS)

Blackford, C.; Howes, Sally; Whitelaw, Alan S.; Laxon, S.; Mantripp, D.

1994-12-01

Sea ice maps are required by a diverse range of users for scientific research and operational activities. Satellite remote sensing provides opportunities for monitoring and producing sea ice maps at a range of scales, in near real time. During March 1994 ESYS Limited and the University College London Mullard Space Science Laboratory (MSSL) operated a sea ice demonstration project to supply near real time sea ice maps in the southern ocean. The sea ice information was derived from a number of data sources: DMSP SSM/I data; ERS-1 SAR and Radar Altimeter fast delivery data; NOAA AVHRR data; and PoSAT-1 imagery. The maps were supplied to three users, two involved in yacht races in the southern ocean and a ship on an oceanographic research cruise in the waters of the Princess Elizabeth Trough region of Antarctica. The demonstration was successful, supplying the users with sea ice information which they had previously not received and combining data from various sources to produce sea ice maps. The demonstration also developed operational skills within ESYS and enabled the transfer of knowledge from MSSL to ESYS.

New cardioprotective agent flokalin and its supramolecular complexes with target amino acids: An integrated mass-spectrometry and quantum-chemical study

NASA Astrophysics Data System (ADS)

Pashynska, Vlada; Stepanian, Stepan; Gömöry, Ágnes; Vékey, Károly; Adamowicz, Ludwik

2017-10-01

This study is devoted to examining the molecular structure and molecular mechanisms of action of the recently developed cardioprotective agent flokalin (Fl), a fluorine containing analogue of pinacidil, which is known as an activator of ATP sensitive potassium membrane channels. A combined experimental and computational investigation of flokalin and its biologically relevant supramolecular complexes with selected amino acids involved in KATP-channels proteins is performed by electrospray ionization mass spectrometry (ESI MS) and by B3LYP/aug-cc-pVDZ quantum-mechanical calculations. First Fl solution is probed by ESI MS and a characteristic mass spectrum of the agent is obtained. Next the intermolecular interactions of Fl with the potentially targeted aminoacids (AA), Lys and Thr, are experimentally investigated. The spectra of the model Fl:AA systems (in 1:1 M ratio) contain information on the ions characteristic to the individual components of the mixtures; though the most interesting spectral results from the biophysical view point are related to the ions of stable molecular clusters formed by flokalin with AA. The peaks of such ions are quite prominent in the spectrum for the Fl:Lys system and less prominent for Fl:Thr. The equilibrium geometries and the corresponding interaction energies of the noncovalent supramolecular complexes registered in the mass spectra are determined in the quantum chemical calculations. The formation of the stable noncovalent complexes of Fl with Lyz and Thr revealed by the ESI MS probing and by the theoretical modelling testify to a possibility of interaction of flokalin with the KATP-channel domains enriched with the two amino acids in biological systems.

Implementation Plan for Worldwide Airborne Command Post (WWABNCP) Operator Computer-Based Training (PLATO): Decision Paper.

DTIC Science & Technology

1985-10-03

Electrospace Systems, Inc. (ESI). ESI con- ducted a market search for training systems that would enhance unit level training, minimize cost-prohibitive...can be reprogrammed to simulate the UGC -129 keyboard. This keyboard is the standard keyboard used for data transmission on board the EC-135 and E-4B...with the appropriate technical order, and the functions and operation of the AN/ UGC -129 (ASR) terminals used with the AN/ASC-21 AFSATCOM system. In

Indexing of exoplanets in search for potential habitability: application to Mars-like worlds

NASA Astrophysics Data System (ADS)

Kashyap Jagadeesh, Madhu; Gudennavar, Shivappa B.; Doshi, Urmi; Safonova, Margarita

2017-08-01

Study of exoplanets is one of the main goals of present research in planetary sciences and astrobiology. Analysis of huge planetary data from space missions such as CoRoT and Kepler is directed ultimately at finding a planet similar to Earth—the Earth's twin, and answering the question of potential exo-habitability. The Earth Similarity Index (ESI) is a first step in this quest, ranging from 1 (Earth) to 0 (totally dissimilar to Earth). It was defined for the four physical parameters of a planet: radius, density, escape velocity and surface temperature. The ESI is further sub-divided into interior ESI (geometrical mean of radius and density) and surface ESI (geometrical mean of escape velocity and surface temperature). The challenge here is to determine which exoplanet parameter(s) is important in finding this similarity; how exactly the individual parameters entering the interior ESI and surface ESI are contributing to the global ESI. Since the surface temperature entering surface ESI is a non-observable quantity, it is difficult to determine its value. Using the known data for the Solar System objects, we established the calibration relation between surface and equilibrium temperatures to devise an effective way to estimate the value of the surface temperature of exoplanets. ESI is a first step in determining potential exo-habitability that may not be very similar to a terrestrial life. A new approach, called Mars Similarity Index (MSI), is introduced to identify planets that may be habitable to the extreme forms of life. MSI is defined in the range between 1 (present Mars) and 0 (dissimilar to present Mars) and uses the same physical parameters as ESI. We are interested in Mars-like planets to search for planets that may host the extreme life forms, such as the ones living in extreme environments on Earth; for example, methane on Mars may be a product of the methane-specific extremophile life form metabolism.

Collection and Retention Procedures for Electronically Stored Information (ESI) Collected Using E-Discovery Tools

EPA Pesticide Factsheets

This procedure is designed to support the collection of potentially responsive information using automated E-Discovery tools that rely on keywords, key phrases, index queries, or other technological assistance to retrieve Electronically Stored Information

Mass spectrometric methods for monitoring redox processes in electrochemical cells.

PubMed

Oberacher, Herbert; Pitterl, Florian; Erb, Robert; Plattner, Sabine

2015-01-01

Electrochemistry (EC) is a mature scientific discipline aimed to study the movement of electrons in an oxidation-reduction reaction. EC covers techniques that use a measurement of potential, charge, or current to determine the concentration or the chemical reactivity of analytes. The electrical signal is directly converted into chemical information. For in-depth characterization of complex electrochemical reactions involving the formation of diverse intermediates, products and byproducts, EC is usually combined with other analytical techniques, and particularly the hyphenation of EC with mass spectrometry (MS) has found broad applicability. The analysis of gases and volatile intermediates and products formed at electrode surfaces is enabled by differential electrochemical mass spectrometry (DEMS). In DEMS an electrochemical cell is sampled with a membrane interface for electron ionization (EI)-MS. The chemical space amenable to EC/MS (i.e., bioorganic molecules including proteins, peptides, nucleic acids, and drugs) was significantly increased by employing electrospray ionization (ESI)-MS. In the simplest setup, the EC of the ESI process is used to analytical advantage. A limitation of this approach is, however, its inability to precisely control the electrochemical potential at the emitter electrode. Thus, particularly for studying mechanistic aspects of electrochemical processes, the hyphenation of discrete electrochemical cells with ESI-MS was found to be more appropriate. The analytical power of EC/ESI-MS can further be increased by integrating liquid chromatography (LC) as an additional dimension of separation. Chromatographic separation was found to be particularly useful to reduce the complexity of the sample submitted either to the EC cell or to ESI-MS. Thus, both EC/LC/ESI-MS and LC/EC/ESI-MS are common. © 2013 The Authors. Mass Spectrometry Reviews published by Wiley Periodicals, Inc.

Mass spectrometric methods for monitoring redox processes in electrochemical cells

PubMed Central

Oberacher, Herbert; Pitterl, Florian; Erb, Robert; Plattner, Sabine

2015-01-01

Electrochemistry (EC) is a mature scientific discipline aimed to study the movement of electrons in an oxidation–reduction reaction. EC covers techniques that use a measurement of potential, charge, or current to determine the concentration or the chemical reactivity of analytes. The electrical signal is directly converted into chemical information. For in-depth characterization of complex electrochemical reactions involving the formation of diverse intermediates, products and byproducts, EC is usually combined with other analytical techniques, and particularly the hyphenation of EC with mass spectrometry (MS) has found broad applicability. The analysis of gases and volatile intermediates and products formed at electrode surfaces is enabled by differential electrochemical mass spectrometry (DEMS). In DEMS an electrochemical cell is sampled with a membrane interface for electron ionization (EI)-MS. The chemical space amenable to EC/MS (i.e., bioorganic molecules including proteins, peptides, nucleic acids, and drugs) was significantly increased by employing electrospray ionization (ESI)-MS. In the simplest setup, the EC of the ESI process is used to analytical advantage. A limitation of this approach is, however, its inability to precisely control the electrochemical potential at the emitter electrode. Thus, particularly for studying mechanistic aspects of electrochemical processes, the hyphenation of discrete electrochemical cells with ESI-MS was found to be more appropriate. The analytical power of EC/ESI-MS can further be increased by integrating liquid chromatography (LC) as an additional dimension of separation. Chromatographic separation was found to be particularly useful to reduce the complexity of the sample submitted either to the EC cell or to ESI-MS. Thus, both EC/LC/ESI-MS and LC/EC/ESI-MS are common. PMID:24338642

A novel rapid analysis using mass spectrometry to evaluate downstream refolding of recombinant human insulin-like growth factor-1 (mecasermin).

PubMed

Furuki, Kenichiro; Toyo'oka, Toshimasa; Yamaguchi, Hideto

2017-08-15

Mecasermin is used to treat elevated blood sugar as well as growth-hormone-resistant Laron-type dwarfism. Mecasermin isolated from inclusion bodies in extracts of E. coli must be refolded to acquire sufficient activity. However, there is no rapid analytical method for monitoring refolding during the purification process. We prepared mecasermin drug product, in-process samples during the oxidation of mecasermin, forced-reduced mecasermin, and aerially oxidized mecasermin after forced reduction. Desalted mecasermin samples were analyzed using MALDI-ISD. The peak intensity ratio of product to precursor ion was determined. The charge-state distribution (CSD) of mecasermin ions was evaluated using ESI-MS coupled with SEC-mode HPLC. The drift time and collision cross-sectional area (CCS) of mecasermin ions were evaluated using ESI-IMS-MS coupled with SEC-mode HPLC. MALDI-ISD data, CSD values determined using ESI-MS, and the CCS acquired using ESI-IMS-MS revealed the relationship between the folded and unfolded proteoforms of forced-reduced mecasermin and aerially oxidized mecasermin with the free-SH:protein ratio of mecasermin drug product. The CCS area, which is determined using ESI-IMS-MS, provided proteoform information through rapid monitoring (<2 min) of in-process samples during the manufacture of mecasermin. ESI-IMS-MS coupled with SEC-mode HPLC is a rapid and robust method for analyzing the free-SH:protein ratio of mecasermin that allows proteoform changes to be evaluated and monitored during the oxidation of mecasermin. ESI-IMS-MS is applicable as a process analytical technology tool for identifying the "critical quality attributes" and implementing "quality by design" for manufacturing mecasermin. Copyright © 2017 John Wiley & Sons, Ltd.

Surfactant-free microemulsion electrokinetic chromatography (SF-MEEKC) with UV and MS detection - a novel approach for the separation and ESI-MS detection of neutral compounds.

PubMed

Mohorič, Urška; Beutner, Andrea; Krickl, Sebastian; Touraud, Didier; Kunz, Werner; Matysik, Frank-Michael

2016-12-01

Microemulsion electrokinetic chromatography (MEEKC) is a powerful tool to separate neutral species based on differences in their hydrophobic and hydrophilic properties. However, as a major drawback the conventionally used SDS based microemulsions are not compatible with electrospray ionization mass spectrometry (ESI-MS). In this work, a surfactant-free microemulsion (SFME) consisting of water, ethanol, and 1-octanol is used for surfactant-free microemulsion electrokinetic chromatography (SF-MEEKC). Ammonium acetate was added to the SFME enabling electrophoretic separations. The stability of SFMEs containing ammonium acetate was investigated using small-angle X-ray scattering and dynamic light scattering. A method for the separation of a model system of hydrophobic and hydrophilic neutral vitamins, namely the vitamins B 2 and D 3 , and the cationic vitamin B 1 was developed using UV/VIS detection. The influence of the ammonium acetate concentration on the separation performance was studied in detail. The method was characterized concerning reproducibility of migration times and peak areas and concerning the linearity of the calibration data. Furthermore, SF-MEEKC was coupled to ESI-MS investigating the compatibility between SFMEs and the ESI process. The signal intensities of ESI-MS measurements of the model analytes were comparable for SFMEs and aqueous systems. Finally, the vitamin D 3 content of a drug treating vitamin D 3 deficiency was determined by SF-MEEKC coupled to ESI-MS using 25-hydroxycholecalciferol as an internal standard. Graphical abstract The concept of surfactant-free microemulsion electrokinetic chromatography coupled to electrospray ionization mass spectrometry.

A two-tiered approach to assessing the habitability of exoplanets.

PubMed

Schulze-Makuch, Dirk; Méndez, Abel; Fairén, Alberto G; von Paris, Philip; Turse, Carol; Boyer, Grayson; Davila, Alfonso F; António, Marina Resendes de Sousa; Catling, David; Irwin, Louis N

2011-12-01

In the next few years, the number of catalogued exoplanets will be counted in the thousands. This will vastly expand the number of potentially habitable worlds and lead to a systematic assessment of their astrobiological potential. Here, we suggest a two-tiered classification scheme of exoplanet habitability. The first tier consists of an Earth Similarity Index (ESI), which allows worlds to be screened with regard to their similarity to Earth, the only known inhabited planet at this time. The ESI is based on data available or potentially available for most exoplanets such as mass, radius, and temperature. For the second tier of the classification scheme we propose a Planetary Habitability Index (PHI) based on the presence of a stable substrate, available energy, appropriate chemistry, and the potential for holding a liquid solvent. The PHI has been designed to minimize the biased search for life as we know it and to take into account life that might exist under more exotic conditions. As such, the PHI requires more detailed knowledge than is available for any exoplanet at this time. However, future missions such as the Terrestrial Planet Finder will collect this information and advance the PHI. Both indices are formulated in a way that enables their values to be updated as technology and our knowledge about habitable planets, moons, and life advances. Applying the proposed metrics to bodies within our Solar System for comparison reveals two planets in the Gliese 581 system, GJ 581 c and d, with an ESI comparable to that of Mars and a PHI between that of Europa and Enceladus.

Molecular dynamics and metadynamics simulations of electrosprayed water nanodroplets including sodium bis(2-ethylhexyl)sulfosuccinate micelles.

PubMed

Longhi, Giovanna; Ceselli, Alberto; Fornili, Sandro L; Turco Liveri, Vincenzo

2017-05-28

The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) under conditions of electrospray ionization (ESI) has been investigated by molecular dynamics (MD) and well-tempered metadynamics (WTM) simulations at 300 K and 400 K. We have examined water droplets with initial fixed numbers of water molecules (1000) and AOT - anions (100), and with sodium cations in the range of 70-130. At 300 K, all charged droplets show the water evaporation rate increasing with the absolute value of the initial droplet charge state (Z), accompanied by ejection of an increasing number of solvated sodium ions or by expulsion of AOT - anions depending on the sign of Z and by fragmentation in the case of high |Z|. At 400 K, the water evaporation becomes more rapid and the fission process more extensive. In all cases, the AOTNa molecules, arranged as a direct micelle inside the aqueous system, undergo a rapid inversion in vacuo so that the hydrophilic heads and sodium ions surrounded by water molecules move toward the droplet interior. At the end of the 100-ns MD simulations, some water molecules remain within the aggregates at both temperatures. The subsequent metadynamics simulations accelerate the droplet evolution and show that all systems become anhydrous, in agreement with the experimental results of ESI mass spectrometry. This complete water loss is accompanied by sodium counterion emission for positively charged aggregates at 300 K. The analysis shows how the temperature and droplet charge state affect the populations of the generated surfactant aggregates, providing information potentially useful in designing future ESI experimental conditions.

Molecular dynamics and metadynamics simulations of electrosprayed water nanodroplets including sodium bis(2-ethylhexyl)sulfosuccinate micelles

NASA Astrophysics Data System (ADS)

Longhi, Giovanna; Ceselli, Alberto; Fornili, Sandro L.; Turco Liveri, Vincenzo

2017-05-01

The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) under conditions of electrospray ionization (ESI) has been investigated by molecular dynamics (MD) and well-tempered metadynamics (WTM) simulations at 300 K and 400 K. We have examined water droplets with initial fixed numbers of water molecules (1000) and AOT- anions (100), and with sodium cations in the range of 70-130. At 300 K, all charged droplets show the water evaporation rate increasing with the absolute value of the initial droplet charge state (Z), accompanied by ejection of an increasing number of solvated sodium ions or by expulsion of AOT- anions depending on the sign of Z and by fragmentation in the case of high |Z|. At 400 K, the water evaporation becomes more rapid and the fission process more extensive. In all cases, the AOTNa molecules, arranged as a direct micelle inside the aqueous system, undergo a rapid inversion in vacuo so that the hydrophilic heads and sodium ions surrounded by water molecules move toward the droplet interior. At the end of the 100-ns MD simulations, some water molecules remain within the aggregates at both temperatures. The subsequent metadynamics simulations accelerate the droplet evolution and show that all systems become anhydrous, in agreement with the experimental results of ESI mass spectrometry. This complete water loss is accompanied by sodium counterion emission for positively charged aggregates at 300 K. The analysis shows how the temperature and droplet charge state affect the populations of the generated surfactant aggregates, providing information potentially useful in designing future ESI experimental conditions.

The use of PCR/Electrospray Ionization-Time-of-Flight-Mass Spectrometry (PCR/ESI-TOF-MS) to detect bacterial and fungal colonization in healthy military service members.

PubMed

Vetor, Ryan; Murray, Clinton K; Mende, Katrin; Melton-Kreft, Rachel; Akers, Kevin S; Wenke, Joseph; Spirk, Tracy; Guymon, Charles; Zera, Wendy; Beckius, Miriam L; Schnaubelt, Elizabeth R; Ehrlich, Garth; Vento, Todd J

2016-07-22

The role of microbial colonization in disease is complex. Novel molecular tools to detect colonization offer theoretical improvements over traditional methods. We evaluated PCR/Electrospray Ionization-Time-of-Flight-Mass Spectrometry (PCR/ESI-TOF-MS) as a screening tool to study colonization of healthy military service members. We assessed 101 healthy Soldiers using PCR/ESI-TOF-MS on nares, oropharynx, and groin specimens for the presence of gram-positive and gram-negative bacteria (GNB), fungi, and antibiotic resistance genes. A second set of swabs was processed by traditional culture, followed by identification using the BD Phoenix automated system; comparison between PCR/ESI-TOF-MS and culture was carried out only for GNB. Using PCR/ESI-TOF-MS, at least one colonizing organism was found on each individual: mean (SD) number of organisms per subject of 11.8(2.8). The mean number of organisms in the nares, groin and oropharynx was 3.8(1.3), 3.8(1.4) and 4.2(2), respectively. The most commonly detected organisms were aerobic gram-positive bacteria: primarily coagulase-negative Staphylococcus (101 subjects: 341 organisms), Streptococcus pneumoniae (54 subjects: 57 organisms), Staphylococcus aureus (58 subjects: 80 organisms) and Nocardia asteroides (45 subjects: 50 organisms). The mecA gene was found in 96 subjects. The most commonly found GNB was Haemophilus influenzae (20 subjects: 21 organisms) and the most common anaerobe was Propionibacterium acnes (59 subjects). Saccharomyces species (30 subjects) were the most common fungi detected. Only one GNB (nares E. coli) was identified in the same subject by both diagnostic systems. PCR/ESI-TOF-MS detected common colonizing organisms and identified more typically-virulent bacteria in asymptomatic, healthy adults. PCR/ESI-TOF-MS appears to be a useful method for detecting bacterial and fungal organisms, but further clinical correlation and validation studies are needed.

Combined environmental stress and physiological strain indices for physical training guidelines.

PubMed

Moran, Daniel S; Pandolf, Kent B; Heled, Yuval; Gonzalez, Richard R

2003-01-01

The purpose of this study was to develop guidelines based on the previously described environmental stress index (ESI) and physiological strain index (PSI) for work-rest cycles (WRC) during training, especially in the military. The ESI was introduced as a potential substitute for the Wet Bulb Globe Temperature Index because of the very high correlation coefficients between them. The ESI is constructed from the fast-reading meteorological response sensors ambient temperature (Ta), relative humidity (RH), and global radiation (GR), which require only a few seconds to reach equilibrium. The ESI, the first stress index using direct measurements of solar radiation (SR), is calculated as follows: ESI = 0.63Ta - 0.03RH + 0.002SR + 0.0054 (Ta x RH) - 0.073(0.1 + SR)(-1). The PSI is based on heart rate (HR) and rectal temperature (Tre) and can indicate heat strain online and analyze databases. The PSI is constructed as follows: PSI = 5(Tret - Tre0) x (39.5 - Tre0)(-1) + 5(HRt - HR0) x (180 - HR0)(-1), where Tre0 and HR0 are the initial Tre and HR, and Tret and HRt are simultaneous measurements taken at any time. The PSI is scaled from 0 to 10, whereby the respective variables, PSIHR and PSITre, representing the cardiovascular and thermoregulation systems, can contribute up to five units to the overall strain assessment. To integrate the PSI and ESI, we decided to use only the PSIHR component, which represents the metabolic rate and the strain reflected by the cardiovascular system. Furthermore, PSIHR is easier to measure, is easier to implement, and simplifies the integration with ESI. Concomitantly, PSIHR categorizes the strain between 0 and 5, the higher the value, the higher the strain. We believe that the use of the PSI WRC values will help in decreasing the risk of future heat injuries.

Access to Care for Multiple Sclerosis in Times of Economic Crisis in Greece – the HOPE II Study

PubMed Central

Souliotis, Kyriakos; Alexopoulou, Elena; Papageorgiou, Manto; Politi, Anastasia; Litsa, Panagiota; Contiades, Xenophon

2016-01-01

Background: While there is currently no cure for multiple sclerosis (MS), treatment with biologic disease-modifying drugs (bDMDs) can reduce the impact of the condition on the lives of patients. In Greece, the regulatory change in the distribution system of bDMDs, limited their administration through the designated pharmacies of the National Organization for Healthcare Services Provision (EOPYY) or the National Health System (ESY) hospitals, thus potentially impacting access to MS treatment. In this context, the aim of this paper was to assess the barriers to bDMDs, by recording MS patients’ experiences. Methods: A survey research was conducted between January and February 2014 in Athens and 5 other major Greek cities with the methods of personal and telephone interview. A structured questionnaire was used to elicit socio-economic and medical information, information related to obstacles in accessing bDMDs and medical treatment, from MS patients that visited EOPYY pharmacies during the study period. Results: During the last year 69% of 179 participants reported that the distribution system of bDMDs has improved. Thirteen percent of participants encountered problems in accessing their medication, and 16.9% of participants in accessing their physician, with the obstacles being more pronounced for non-Athens residents. Frequent obstacles to bDMDs were the distance from EOPYY pharmacies and difficulties in obtaining a diagnosis from an EOPYY/ESY physician, while obstacles to medical care were delays in appointment booking and travel difficulties. Conclusion: Even though the major weaknesses of the distribution system of bDMDs have improved, further amelioration of the system could be achieved through the home delivery of medicines to patients living in remote areas, and through the development of a national MS registry. PMID:26927393

SDS-PAGE analysis of Aβ oligomers is disserving research into Alzheimer´s disease: appealing for ESI-IM-MS

NASA Astrophysics Data System (ADS)

Pujol-Pina, Rosa; Vilaprinyó-Pascual, Sílvia; Mazzucato, Roberta; Arcella, Annalisa; Vilaseca, Marta; Orozco, Modesto; Carulla, Natàlia

2015-10-01

The characterization of amyloid-beta peptide (Aβ) oligomer forms and structures is crucial to the advancement in the field of Alzheimer´s disease (AD). Here we report a critical evaluation of two methods used for this purpose, namely sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), extensively used in the field, and ion mobility coupled to electrospray ionization mass spectrometry (ESI-IM-MS), an emerging technique with great potential for oligomer characterization. To evaluate their performance, we first obtained pure cross-linked Aβ40 and Aβ42 oligomers of well-defined order. Analysis of these samples by SDS-PAGE revealed that SDS affects the oligomerization state of Aβ42 oligomers, thus providing flawed information on their order and distribution. In contrast, ESI-IM-MS provided accurate information, while also reported on the chemical nature and on the structure of the oligomers. Our findings have important implications as they challenge scientific paradigms in the AD field built upon SDS-PAGE characterization of Aβ oligomer samples.

Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s† †Electronic supplementary information (ESI) available. CCDC 1483959–1483967. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc02520j Click here for additional data file. Click here for additional data file.

PubMed Central

Lehnherr, Dan; Chen, Chen; Pedramrazi, Zahra; DeBlase, Catherine R.; Alzola, Joaquin M.; Keresztes, Ivan; Lobkovsky, Emil B.

2016-01-01

A Cu-catalyzed benzannulation reaction transforms ortho(arylene ethynylene) oligomers into ortho-arylenes. This approach circumvents iterative Suzuki cross-coupling reactions previously used to assemble hindered ortho-arylene backbones. These derivatives form helical folded structures in the solid-state and in solution, as demonstrated by X-ray crystallography and solution-state NMR analysis. DFT calculations of misfolded conformations are correlated with variable-temperature 1H and EXSY NMR to reveal that folding is cooperative and more favorable in halide-substituted naphthalenes. Helical ortho-arylene foldamers with specific aromatic sequences organize functional π-electron systems into arrangements ideal for ambipolar charge transport and show preliminary promise for the surface-mediated synthesis of structurally defined graphene nanoribbons. PMID:28567248

On-line two-dimensional capillary electrophoresis with mass spectrometric detection using a fully electric isolated mechanical valve.

PubMed

Kohl, Felix J; Montealegre, Cristina; Neusüß, Christian

2016-04-01

CE is becoming more and more important in many fields of bioanalytical chemistry. Besides optical detection, hyphenation to ESI-MS detection is increasingly applied for sensitive identification purposes. Unfortunately, many CE techniques and methods established in research and industry are not compatible to ESI-MS since essential components of the background electrolyte interfere in ES ionization. In order to identify unknown peaks in established CE methods, here, a heart-cut 2D-CE separation system is introduced using a fully isolated mechanical valve with an internal loop of only 20 nL. In this system, the sample is separated using potentially any non-ESI compatible method in the first separation dimension. Subsequently, the portion of interest is cut by the internal sample loop of the valve and reintroduced to the second dimension where the interfering compounds are removed, followed by ESI-MS detection. When comparing the separation efficiency of the system with the valve to a system using a continuous capillary only a slight increase in peak width is observed. Ultraviolet/visible detection is integrated in the first dimension for switching time determination, enabling reproducible cutting of peaks of interest. The feasibility of the system is successfully demonstrated by a 2D analysis of a BSA tryptic digest sample using a nonvolatile (phosphate based) background electrolyte in the first dimension. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte system strategies for anionic ITP with ESI-MS detection. 3. The ITP spacer technique in moving-boundary systems and configurations with two self-maintained ITP subsystems.

PubMed

Gebauer, Petr; Malá, Zdena; Boček, Petr

2014-03-01

This contribution is the third part of the project on strategies used in the selection and tuning of electrolyte systems for anionic ITP with ESI-MS detection. The strategy presented here is based on the creation of self-maintained ITP subsystems in moving-boundary systems and describes two new principal approaches offering physical separation of analyte zones from their common ITP stack and/or simultaneous selective stacking of two different analyte groups. Both strategic directions are based on extending the number of components forming the electrolyte system by adding a third suitable anion. The first method is the application of the spacer technique to moving-boundary anionic ITP systems, the second method is a technique utilizing a moving-boundary ITP system in which two ITP subsystems exist and move with mutually different velocities. It is essential for ESI detection that both methods can be based on electrolyte systems containing only several simple chemicals, such as simple volatile organic acids (formic and acetic) and their ammonium salts. The properties of both techniques are defined theoretically and discussed from the viewpoint of their applicability to trace analysis by ITP-ESI-MS. Examples of system design for selected model separations of preservatives and pharmaceuticals illustrate the validity of the theoretical model and application potential of the proposed techniques by both computer simulations and experiments. Both new methods enhance the application range of ITP-MS and may be beneficial particularly for complex multicomponent samples or for analytes with identical molecular mass. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Simulation-Based Structural Prediction of Protein Complexes in Mass Spectrometry: The Human Insulin Dimer

PubMed Central

Li, Jinyu; Rossetti, Giulia; Dreyer, Jens; Raugei, Simone; Ippoliti, Emiliano; Lüscher, Bernhard; Carloni, Paolo

2014-01-01

Protein electrospray ionization (ESI) mass spectrometry (MS)-based techniques are widely used to provide insight into structural proteomics under the assumption that non-covalent protein complexes being transferred into the gas phase preserve basically the same intermolecular interactions as in solution. Here we investigate the applicability of this assumption by extending our previous structural prediction protocol for single proteins in ESI-MS to protein complexes. We apply our protocol to the human insulin dimer (hIns2) as a test case. Our calculations reproduce the main charge and the collision cross section (CCS) measured in ESI-MS experiments. Molecular dynamics simulations for 0.075 ms show that the complex maximizes intermolecular non-bonded interactions relative to the structure in water, without affecting the cross section. The overall gas-phase structure of hIns2 does exhibit differences with the one in aqueous solution, not inferable from a comparison with calculated CCS. Hence, care should be exerted when interpreting ESI-MS proteomics data based solely on NMR and/or X-ray structural information. PMID:25210764

How Nurse Gender Influences Patient Priority Assignments in U.S. Emergency Departments

PubMed Central

Vigil, Jacob Miguel; Coulombe, Patrick; Alcock, Joe; Stith, Sarah See; Kruger, Eric; Cichowski, Sara

2016-01-01

The goals of this study were to compare whether emergency department (ED) patients’ pain intensity (PI) is measured differently by male and female nurses and to determine whether PI, heart rate (HR) and respiratory rate (RR) we’re used to prioritize patient urgency differently by male and female nurses. The associations between patients’ PI|HR|RR and the Emergency Severity Index (ESI) scores they were assigned by attending nurses were analyzed using a national database of electronic medical records of U.S. Veterans Affairs ED patients from 2008 to 2012. A total of 129,991 patients presenting for emergency care (Mage = 59.5, 92% males) and their triage nurses (n = 774, Mage = 47.5, 18% males) were analyzed, resulting in a total of 359,642 patient/provider interactions. Patients’ PI did not differ by nurse’s gender; however a cross-classified mixed-effects model showed that nurse gender influenced how PI and RR measurements informed the ESI levels that male patients received. Higher PI levels were associated with more urgent (higher priority) ESI levels by female nurses, yet less urgent ESI levels by male nurses. In contrast, male patients with high RR received more urgent ESI levels by male nurses, while nurse gender did not influence ESI assignments for female patients. These findings show that ED patients receive disparate treatment based on inherent characteristics of their triage nurses, and more standardized (e.g., automated) protocols that can account for implicit social factors on healthcare practice for reliably assessing and prioritizing ED patients may be currently warranted. PMID:28187101

Exploration Systems Development (ESD) Approach to Enterprise Risk Management

NASA Technical Reports Server (NTRS)

Bauder, Stephen P.

2014-01-01

The National Aeronautics and Space Administration (NASA) Exploration Systems Development (ESD) Division has implemented an innovative approach to Enterprise Risk Management under a unique governance structure and streamlined integration model. ESD's mission is to design and build the capability to extend human existence to deep space. The Enterprise consists of three Programs: Space Launch System (SLS), Orion, and Ground Systems Development and Operations (GSDO). The SLS is a rocket and launch system that will be capable of powering humans, habitats, and support systems to deep space. Orion will be the first spacecraft in history capable of taking humans to multiple destinations within deep space. GSDO is modernizing Kennedy's spaceport to launch spacecraft built and designed by both NASA and private industry. ESD's approach to Enterprise Risk Management is commensurate with affordability and a streamlined management philosophy. ESD Enterprise Risk Management leverages off of the primary mechanisms for integration within the Enterprise. The Enterprise integration approach emphasizes delegation of authority to manage and execute the majority of cross-program activities and products to the individual Programs, while maintaining the overall responsibility for all cross-program activities at the Division. The intent of the ESD Enterprise Risk Management approach is to improve risk communication, to avoid replication and/or contradictory strategies, and to minimize overhead process burden. This is accomplished by the facilitation and integration of risk information within ESD. The ESD Division risks, Orion risks, SLS risks, and GSDO risks are owned and managed by the applicable Program. When the Programs have shared risks with multiple consequences, they are jointly owned and managed. When a risk is associated with the integrated system that involves more than one Program in condition, consequence, or mitigation plan, it is considered an Exploration Systems Integration (ESI) Risk. An ESI risk may require visibility and risk handling by multiple organizations. The Integrated Risk Working Group (IRWG) is a small team of Risk experts that are responsible for collaborating and communicating best practices. In addition, the forum facilitates proper integration of risks across the Enterprise. The IRWG uses a Continuous Risk Management approach for facilitating the identification, analysis, planning, tracking, and controlling of ESI Risks. The ESD Division, Programs, and Integrated Task Teams identify ESI Risks. The IRWG maintains a set of metrics for understanding Enterprise Risk process and the overall Risk Posture. The team is also actively involved in the modeling of risk for Enterprise Performance Management. With the Enterprise being constrained in Schedule and Budget, and with significant technical complexity, the appropriate use of Risk Management techniques is crucial to the success of the Enterprise. The IRWG achieves this through the modified approach, providing a forum for collaboration on risks that cross boundaries between the separate entities.

Detection of protonated non-Watson-Crick base pairs using electrospray ionization mass spectrometry.

PubMed

Ishida, Riyoko; Iwahashi, Hideo

2018-03-01

Many studies have shown that protonated nucleic acid base pairs are involved in a wide variety of nucleic acid structures. However, little information is available on relative stability of hemiprotonated self- and non-self-dimers at monomer level. We used electrospray ionization mass spectrometry (ESI-MS) to evaluate the relative stability under various concentrations of hydrogen ion. These enable conjecture of the formation of protonated non-Watson-Crick base pairs based on DNA and RNA base sequence. In the present study, we observed that ESI-MS peaks corresponded to respective self-dimers for all examined nucleosides except for adenosine. Peak heights depended on the concentration of hydrogen ion. The ESI-MS peak heights of the hemiprotonated cytidine dimers and the hemiprotonated thymidine dimer sharply increased with increased concentration of hydrogen ion, suggesting direct participation of hydrogen ion in dimer formations. In ESI-MS measurements of the solutions containing adenosine, cytidine, thymidine and guanosine, we observed protonated cytidine-guanosine dimer (CH+-G) and protonated cytidine-thymidine dimer (CH+-T) in addition to hemiprotonated cytidine-cytidine dimer (CH+-C) with following relative peak height, (CH+-C) > (CH+-G) ≈ (CH+-T) > (CH+-A). Additionally, in the ESI-MS measurements of solutions containing adenosine, thymidine and guanosine, we observed a considerable amount of protonated adenosine-guanosine (AH+-G) and protonated adenosine-thymidine (AH+-T).

Unambiguous metabolite identification in high-throughput metabolomics by hybrid 1D 1 H NMR/ESI MS 1 approach: Hybrid 1D 1 H NMR/ESI MS 1 metabolomics method

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

Walker, Lawrence R.; Hoyt, David W.; Walker, S. Michael

We present a novel approach to improve accuracy of metabolite identification by combining direct infusion ESI MS1 with 1D 1H NMR spectroscopy. The new approach first applies standard 1D 1H NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in metabolomics library. This generates a list of candidate metabolites. The list contains false positive and ambiguous identifications. Next, we constrained the list with the chemical formulas derived from high-resolution direct infusion ESI MS1 spectrum of the same sample. Detection of the signals of a metabolitemore » both in NMR and MS significantly improves the confidence of identification and eliminates false positive identification. 1D 1H NMR and direct infusion ESI MS1 spectra of a sample can be acquired in parallel in several minutes. This is highly beneficial for rapid and accurate screening of hundreds of samples in high-throughput metabolomics studies. In order to make this approach practical, we developed a software tool, which is integrated to Chenomx NMR Suite. The approach is demonstrated on a model mixture, tomato and Arabidopsis thaliana metabolite extracts, and human urine.« less

Proteome analysis of excretory-secretory proteins of Entamoeba histolytica HM1:IMSS via LC-ESI-MS/MS and LC-MALDI-TOF/TOF.

PubMed

Ujang, Jorim Anak; Kwan, Soon Hong; Ismail, Mohd Nazri; Lim, Boon Huat; Noordin, Rahmah; Othman, Nurulhasanah

2016-01-01

Excretory-secretory (ES) proteins of E. histolytica are thought to play important roles in the host invasion, metabolism, and defence. Elucidation of the types and functions of E. histolytica ES proteins can further our understanding of the disease pathogenesis. Thus, the aim of this study is to use proteomics approach to better understand the complex ES proteins of the protozoa. E. histolytica ES proteins were prepared by culturing the trophozoites in protein-free medium. The ES proteins were identified using two mass spectrometry tools, namely, LC-ESI-MS/MS and LC-MALDI-TOF/TOF. The identified proteins were then classified according to their biological processes, molecular functions, and cellular components using the Panther classification system (PantherDB). A complementary list of 219 proteins was identified; this comprised 201 proteins detected by LC-ESI-MS/MS and 107 proteins by LC-MALDI-TOF/TOF. Of the 219 proteins, 89 were identified by both mass-spectrometry systems, while 112 and 18 proteins were detected exclusively by LC-ESI-MS/MS and LC-MALDI-TOF/TOF respectively. Biological protein functional analysis using PantherDB showed that 27% of the proteins were involved in metabolic processes. Using molecular functional and cellular component analyses, 35% of the proteins were found to be involved in catalytic activity, and 21% were associated with the cell parts. This study showed that complementary use of LC-ESI-MS/MS and LC-MALDI-TOF/TOF has improved the identification of ES proteins. The results have increased our understanding of the types of proteins excreted/secreted by the amoeba and provided further evidence of the involvement of ES proteins in intestinal colonisation and evasion of the host immune system, as well as in encystation and excystation of the parasite.

Examining the premises supporting the empirically supported intervention approach to social work practice.

PubMed

McBeath, Bowen; Briggs, Harold E; Aisenberg, Eugene

2010-10-01

Federal, state, and local policymakers and funders have increasingly organized human service delivery functions around the selection and implementation of empirically supported interventions (ESIs), under the expectation that service delivery through such intervention frameworks results in improvements in cost-effectiveness and system performance. This article examines the validity of four premises undergirding the ESI approach: ESIs are effective, relevant to common client problems and needs, culturally appropriate, and replicable and sustainable in community-based settings. In reviewing available literature, the authors found insufficient support for the uniform application of an ESI approach to social work practice in the human service sector, particularly as applied within agency contexts serving ethnic minority clients. The authors recommend that greater attention be devoted to the development and dissemination of social work interventions that respond to needs that are broadly understood and shared across diverse cultural groups, have proven clinical efficacy, and can be translated successfully for use across different agency and cultural environments. Such attention to the research and development function of the social work profession is increasingly necessary as policymakers and human service system architects require reduced costs and improved performance for programs serving historically oppressed client populations.

Epidural Steroid Injections Are Associated with Less Improvement in the Treatment of Lumbar Spinal Stenosis: A subgroup analysis of the SPORT

PubMed Central

Radcliff, Kris; Kepler, Christopher; Hilibrand, Alan; Rihn, Jeffrey; Zhao, Wenyan; Lurie, Jon; Tosteson, Tor; Vaccaro, Alexander; Albert, Todd; Weinstein, James

2013-01-01

Summary of Background Data Lumbar spinal stenosis is a common incidental finding among adults over the age of 60, The use of ESI in these patients is common, although there is little evidence in the literature to demonstrate the long-term benefit of ESI in the treatment of lumbar stenosis. Objective The hypothesis of this study was that patients who received epidural steroid injections (ESI) during initial treatment as part of the Spine Patient Outcomes Research Trial (SPORT) would have improved clinical outcomes and a lower rate of crossover to surgery compared to patients who did not receive ESI. Methods Patients with lumbar spinal stenosis who received epidural steroid injections within the first three months of enrollment in SPORT (ESI) were compared to patients who did not receive epidural injections during the first three months of the study (No ESI). Results There were 69 ESI patients and 207 No-ESI patients. There were no significant differences in demographic factors, baseline clinical outcome scores, or operative details although there was a significant increase in baseline preference for nonsurgical treatment among ESI patients (62% vs. 33%, p <0.001). There was an average 26 minute increase in operative time and an increased length of stay by 0.9 days among the ESI patients who ultimately underwent surgical treatment. Averaged over four years, there was significantly less improvement in SF36 PF among surgically treated ESI patients (ESI 14.8 vs. No-ESI 22.5, p=0.025). In addition, there was also significantly less improvement among the nonsurgically treated patients in SF36 BP (ESI 7.3 vs. No-ESI 16.7, p=0.007) and SF36 PF (ESI 5.5 vs. No-ESI 15.2, p=0.009). Of the patients assigned to surgical treatment, there was a significantly increased crossover to nonsurgical treatment among patients who received an ESI (ESI 33% vs. No ESI 11%, p=0.012). Of the patients assigned to non-operative treatment, there was a significantly increased crossover to surgical treatment in the ESI patients (ESI 58% vs. No ESI 32%, p=0.003). Conclusion Despite equivalent baseline status, ESI were associated with significantly less improvement at four years among all patients with spinal stenosis in SPORT. Furthermore, ESI were associated with longer duration of surgery and longer hospital stay. There was no improvement in outcome with ESI whether patients were treated surgically or nonsurgically. PMID:23238485

Integrated CZE-ESI-MS/MS system with an immobilized trypsin microreactor for online digestion and analysis of picogram amounts of RAW 264.7 cell lysate

PubMed Central

Sun, Liangliang; Zhu, Guijie; Dovichi, Norman J.

2013-01-01

A capillary zone electrophoresis (CZE) electrospray ionization (ESI) tandem mass spectrometry (MS/MS) system was integrated with an immobilized trypsin microreactor. The system was evaluated and then applied for online digestion and analysis of picogram loadings of RAW 264.7 cell lysate. Protein samples were dissolved in a buffer containing 50% (v/v) acetonitrile (ACN), and then directly loaded into the capillary for digestion, followed by CZE separation and MS/MS identification. The organic solvent (50% (v/v) ACN) assisted the immobilized trypsin digestion and simplified the protein sample preparation protocol. Neither protein reduction nor alkylation steps were employed, which minimized sample loss and contamination. The integrated CZE-ESI-MS/MS system generated confident identification of bovine serum albumin (BSA) with 19% sequence coverage and 14 peptide IDs when 20 fmole was loaded. When only 1 fmole BSA was injected, one BSA peptide was consistently detected. For the analysis of a standard protein mixture, the integrated system produced efficient protein digestion and confident identification for proteins with different molecular weights and isoelectric points when low fmole amount was loaded for each protein. We further applied the system for triplicate analysis of a RAW 264.7 cell lysate; 2 ± 1 and 7 ± 2 protein groups were confidently identified from only 300 pg and 3 ng loadings, respectively. The 300 pg sample loading corresponds to the protein content of three RAW 264.7 cells. In addition to high sensitivity analysis, the integrated CZE-ESI-MS/MS system produces good reproducibility in terms of peptide and protein IDs, peptide migration time, and peptide intensity. PMID:23510126

Ketones as directing groups in photocatalytic sp3 C–H fluorination† †Electronic supplementary information (ESI) available. CCDC 1556373, 1556374 and 1556555. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02703f

PubMed Central

Bume, Desta Doro; Pitts, Cody Ross; Ghorbani, Fereshte; Harry, Stefan Andrew; Capilato, Joseph N.; Siegler, Maxime A.

2017-01-01

The ubiquitous ketone carbonyl group generally deactivates substrates toward radical-based fluorinations, especially sites closest to it. Herein, ketones are used instead to direct aliphatic fluorination using Selectfluor, catalytic benzil, and visible light. Selective β- and γ-fluorination are demonstrated on rigid mono-, di-, tri-, and tetracyclic (steroidal) substrates employing both cyclic and exocyclic aliphatic ketones as directing groups. PMID:29147517

Capillary moving-boundary isotachophoresis with electrospray ionization mass-spectrometric detection and hydrogen ion used as essential terminator: Methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides in waters.

PubMed

Malá, Zdena; Gebauer, Petr

2017-10-06

Capillary isotachophoresis (ITP) is an electrophoretic technique offering high sensitivity due to permanent stacking of the migrating analytes. Its combination with electrospray-ionization mass-spectrometric (ESI-MS) detection is limited by the narrow spectrum of ESI-compatible components but can be compensated by experienced system architecture. This work describes a methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides, based on implementation of the concepts of moving-boundary isotachophoresis and of H + as essential terminating component into cationic ITP with ESI-MS detection. Theoretical description of such kind of system is given and equations for zone-related boundary mobilities are derived, resulting in a much more general definition of the effective mobility of the terminating H + zone than used so far. Explicit equations allowing direct calculation for selected simple systems are derived. The presented theory allows prediction of stacking properties of particular systems and easy selection of suitable electrolyte setups. A simple ESI-compatible system composed of acetic acid and ammonium with H + and ammonium as a mixed terminator was selected for the analysis of 2-hydroxyatrazine and 2-hydroxyterbutylazine, degradation products of s-triazine herbicides. The proposed method was tested with direct injection without any sample pretreatment and provided excellent linearity and high sensitivity with limits of detection below 100ng/L (0.5nM). Example analyses of unspiked and spiked drinking and river water are shown. Copyright © 2017 Elsevier B.V. All rights reserved.

ESIprot: a universal tool for charge state determination and molecular weight calculation of proteins from electrospray ionization mass spectrometry data.

PubMed

Winkler, Robert

2010-02-01

Electrospray ionization (ESI) ion trap mass spectrometers with relatively low resolution are frequently used for the analysis of natural products and peptides. Although ESI spectra of multiply charged protein molecules also can be measured on this type of devices, only average spectra are produced for the majority of naturally occurring proteins. Evaluating such ESI protein spectra would provide valuable information about the native state of investigated proteins. However, no suitable and freely available software could be found which allows the charge state determination and molecular weight calculation of single proteins from average ESI-MS data. Therefore, an algorithm based on standard deviation optimization (scatter minimization) was implemented for the analysis of protein ESI-MS data. The resulting software ESIprot was tested with ESI-MS data of six intact reference proteins between 12.4 and 66.7 kDa. In all cases, the correct charge states could be determined. The obtained absolute mass errors were in a range between -0.2 and 1.2 Da, the relative errors below 30 ppm. The possible mass accuracy allows for valid conclusions about the actual condition of proteins. Moreover, the ESIprot algorithm demonstrates an extraordinary robustness and allows spectral interpretation from as little as two peaks, given sufficient quality of the provided m/z data, without the necessity for peak intensity data. ESIprot is independent from the raw data format and the computer platform, making it a versatile tool for mass spectrometrists. The program code was released under the open-source GPLv3 license to support future developments of mass spectrometry software. Copyright 2010 John Wiley & Sons, Ltd.

Native ESI Mass Spectrometry Can Help to Avoid Wrong Interpretations from Isothermal Titration Calorimetry in Difficult Situations

NASA Astrophysics Data System (ADS)

Wolff, Philippe; Da Veiga, Cyrielle; Ennifar, Eric; Bec, Guillaume; Guichard, Gilles; Burnouf, Dominique; Dumas, Philippe

2017-02-01

We studied by native ESI-MS the binding of various DNA-polymerase-derived peptides onto DNA-polymerase processivity rings from Escherichia coli, Pseudomonas aeruginosa, and Mycobacterium tuberculosis. These homodimeric rings present two equivalent specific binding sites, which leads to successive formation during a titration experiment of singly- and doubly occupied rings. By using the ESI-MS free-ring spectrum as a ruler, we derived by robust linear regression the fractions of the different ring species at each step of a titration experiment. These results led to accurate Kd values (from 0.03 to 0.5 μM) along with the probability of peptide loss due to gas phase dissociation (GPD). We show that this good quality is due to the increased information content of a titration experiment with a homodimer. Isothermal titration calorimetry (ITC) led with the same binding model to Kd(ITC) values systematically higher than their ESI-MS counterparts and, often, to poor fit of the ITC curves. A processing with two competing modes of binding on the same site requiring determination of two (Kd, ΔH) pairs greatly improved the fits and yielded a second Kd(ITC) close to Kd(ESI-MS). The striking features are: (1) ITC detected a minor binding mode ( 20%) of `low-affinity' that did not appear with ESI-MS; (2) the simplest processing of ITC data with only one (Kd, ΔH) pair led wrongly to the Kd of the low-affinity binding mode but to the ΔH of the high-affinity binding mode. Analogous misleading results might well exist in published data based on ITC experiments.

Native ESI Mass Spectrometry Can Help to Avoid Wrong Interpretations from Isothermal Titration Calorimetry in Difficult Situations.

PubMed

Wolff, Philippe; Da Veiga, Cyrielle; Ennifar, Eric; Bec, Guillaume; Guichard, Gilles; Burnouf, Dominique; Dumas, Philippe

2017-02-01

We studied by native ESI-MS the binding of various DNA-polymerase-derived peptides onto DNA-polymerase processivity rings from Escherichia coli, Pseudomonas aeruginosa, and Mycobacterium tuberculosis. These homodimeric rings present two equivalent specific binding sites, which leads to successive formation during a titration experiment of singly- and doubly occupied rings. By using the ESI-MS free-ring spectrum as a ruler, we derived by robust linear regression the fractions of the different ring species at each step of a titration experiment. These results led to accurate K d values (from 0.03 to 0.5 μM) along with the probability of peptide loss due to gas phase dissociation (GPD). We show that this good quality is due to the increased information content of a titration experiment with a homodimer. Isothermal titration calorimetry (ITC) led with the same binding model to K d (ITC) values systematically higher than their ESI-MS counterparts and, often, to poor fit of the ITC curves. A processing with two competing modes of binding on the same site requiring determination of two (K d , ΔH) pairs greatly improved the fits and yielded a second K d (ITC) close to K d (ESI-MS). The striking features are: (1) ITC detected a minor binding mode (~20%) of 'low-affinity' that did not appear with ESI-MS; (2) the simplest processing of ITC data with only one (K d , ΔH) pair led wrongly to the Kd of the low-affinity binding mode but to the ΔH of the high-affinity binding mode. Analogous misleading results might well exist in published data based on ITC experiments. Graphical Abstract ᅟ.

Interim Policy to Preserve Separated Personnel’s Electronically Stored Information Subject to Litigation Holds

EPA Pesticide Factsheets

This Interim Policy is designed to ensure the preservation of electronically stored information (ESI), created or received by EPA employees, contractors or grantees with user and email accounts on EPA networks, who have ended their employment with EPA.

Protein oxidative modifications during electrospray ionization: solution phase electrochemistry or corona discharge-induced radical attack?

PubMed

Boys, Brian L; Kuprowski, Mark C; Noël, James J; Konermann, Lars

2009-05-15

The exposure of solution-phase proteins to reactive oxygen species (ROS) causes oxidative modifications, giving rise to the formation of covalent +16 Da adducts. Electrospray ionization (ESI) mass spectrometry (MS) is the most widely used method for monitoring the extent of these modifications. Unfortunately, protein oxidation can also take place as an experimental artifact during ESI, such that it may be difficult to assess the actual level of oxidation in bulk solution. Previous work has demonstrated that ESI-induced oxidation is highly prevalent when operating at strongly elevated capillary voltage V(0) (e.g., +8 kV) and with oxygen nebulizer gas in the presence of a clearly visible corona discharge. Protein oxidation under these conditions is commonly attributed to OH radicals generated in the plasma of the discharge. On the other hand, charge balancing oxidation reactions are known to take place at the metal/liquid interface of the emitter. Previous studies have not systematically explored whether such electrochemical processes could be responsible for the formation of oxidative +16 Da adducts instead of (or in combination with) plasma-generated ROS. Using hemoglobin as a model system, this work illustrates the occurrence of extensive protein oxidation even under typical operating conditions (e.g., V(0) = 3.5 kV, N(2) nebulizer gas). Surprisingly, measurements of the current flowing in the ESI circuit demonstrate that a weak corona discharge persists for these relatively gentle settings. On the basis of comparative experiments with nebulizer gases of different dielectric strength, it is concluded that ROS generated under discharge conditions are solely responsible for ESI-induced protein oxidation. This result is corroborated through off-line electrolysis experiments designed to mimic the electrochemical processes taking place during ESI. Our findings highlight the necessity of using easily oxidizable internal standards in biophysical or biomedical ESI-MS studies where knowledge of protein oxidation in bulk solution is desired. Strategies for eliminating ESI-induced oxidation artifacts are discussed.

Is a mobile emergency severity index (ESI) triage better than the paper ESI?

PubMed

Savatmongkorngul, Sorravit; Yuksen, Chaiyaporn; Suwattanasilp, Chanakarn; Sawanyawisuth, Kittisak; Sittichanbuncha, Yuwares

2017-12-01

This study aims to evaluate the mobile emergency severity index (ESI) tool in terms of validity compared with the original ESI triage. The original ESI and mobile ESI were used with patients at the Department of Emergency Medicine, Ramathibodi Hospital, Thailand. Eligible patients were evaluated by sixth-year medical students/emergency physicians using either the original or mobile ESI. The ESI results for each patient were compared with the standard ESI. Concordance and kappa statistics were calculated for pairs of the evaluators. There were 486 patients enrolled in the study; 235 patients (48.4%) were assessed using the mobile ESI, and 251 patients (51.6%) were in the original ESI group. The baseline characteristics of patients in both groups were mostly comparable except for the ED visit time. The percentages of concordance and kappa statistics in the original ESI group were lower than in the mobile group in all three comparisons (medical students vs gold standard, emergency physicians vs gold standard, and medical students vs emergency physicians). The highest kappa in the original ESI group is 0.69, comparing emergency physicians vs gold standard, while the lowest kappa in the application group is 0.84 comparing the medical students vs gold standard. Both medical students and emergency physicians are more confident with the mobile ESI application triage. In conclusion, the mobile ESI has better inter-rater reliability, and is more user-friendly than the original paper form.

Feasibility study of mid-infrared absorption spectroscopy using electrospray ionization

NASA Astrophysics Data System (ADS)

Ahmed, Tahsin; Foster, Erick; Bohn, Paul; Howard, Scott

2016-09-01

Precise detection of trace amount of molecules, such as the disease biomarkers present in biofluids or explosive residues, requires high sensitivity detection. electrospray ionization-mass spectrometry (ESI-MS) is a common and effective technique for sensitive trace molecular detection in small-volume liquid samples. In ESI-MS, nano-liter volume samples are ionized and aerosolized by ESI, and fed into MS for mass analysis. ESI-MS has proven to be a reliable ionization technique for coupling liquid phase separations like liquid chromatography (LC) and capillary zone electrophoresis (CE) with the highly specific resolving power of MS. While CE and ESI can be performed on a microfluidic chip having a footprint of a few cm2, MS is typically at least 100 times bigger in size than a micro-chip. A reduced size, weight, and power profile would enable semi-portable applications in forensics, environmental monitoring, defense, and biological/pharmaceutical applications. To achieve this goal, we present an initial study evaluating the use of mid-infrared absorption spectroscopy (MIRAS) in place of MS to create a ESI-MIRAS system. To establish feasibility, we perform ESI-MIRAS on phospholipid samples, which have been previously demonstrated to be separable by CE. Phospholipids are biomarkers of degenerative neurological, kidney, and bone diseases and can be found in biofluids such as blood, urine and cerebrospinal fluid. To establish sensitivity limits, calibration samples of 100 μM concentration are electrospray deposited on to a grounded Si wafer for different times (1 minutes to 4 minutes with a 1 minute step). The minimum detectable concentration-time product, where a FTIR globar is used as the MIR source, is found 200 μM·s.

Machine-Learning-Based Electronic Triage More Accurately Differentiates Patients With Respect to Clinical Outcomes Compared With the Emergency Severity Index.

PubMed

Levin, Scott; Toerper, Matthew; Hamrock, Eric; Hinson, Jeremiah S; Barnes, Sean; Gardner, Heather; Dugas, Andrea; Linton, Bob; Kirsch, Tom; Kelen, Gabor

2018-05-01

Standards for emergency department (ED) triage in the United States rely heavily on subjective assessment and are limited in their ability to risk-stratify patients. This study seeks to evaluate an electronic triage system (e-triage) based on machine learning that predicts likelihood of acute outcomes enabling improved patient differentiation. A multisite, retrospective, cross-sectional study of 172,726 ED visits from urban and community EDs was conducted. E-triage is composed of a random forest model applied to triage data (vital signs, chief complaint, and active medical history) that predicts the need for critical care, an emergency procedure, and inpatient hospitalization in parallel and translates risk to triage level designations. Predicted outcomes and secondary outcomes of elevated troponin and lactate levels were evaluated and compared with the Emergency Severity Index (ESI). E-triage predictions had an area under the curve ranging from 0.73 to 0.92 and demonstrated equivalent or improved identification of clinical patient outcomes compared with ESI at both EDs. E-triage provided rationale for risk-based differentiation of the more than 65% of ED visits triaged to ESI level 3. Matching the ESI patient distribution for comparisons, e-triage identified more than 10% (14,326 patients) of ESI level 3 patients requiring up triage who had substantially increased risk of critical care or emergency procedure (1.7% ESI level 3 versus 6.2% up triaged) and hospitalization (18.9% versus 45.4%) across EDs. E-triage more accurately classifies ESI level 3 patients and highlights opportunities to use predictive analytics to support triage decisionmaking. Further prospective validation is needed. Copyright © 2017 American College of Emergency Physicians. Published by Elsevier Inc. All rights reserved.

Emergency Severity Index version 4: a valid and reliable tool in pediatric emergency department triage.

PubMed

Green, Nicole A; Durani, Yamini; Brecher, Deena; DePiero, Andrew; Loiselle, John; Attia, Magdy

2012-08-01

The Emergency Severity Index version 4 (ESI v.4) is the most recently implemented 5-level triage system. The validity and reliability of this triage tool in the pediatric population have not been extensively established. The goals of this study were to assess the validity of ESI v.4 in predicting hospital admission, emergency department (ED) length of stay (LOS), and number of resources utilized, as well as its reliability in a prospective cohort of pediatric patients. The first arm of the study was a retrospective chart review of 780 pediatric patients presenting to a pediatric ED to determine the validity of ESI v.4. Abstracted data included acuity level assigned by the triage nurse using ESI v.4 algorithm, disposition (admission vs discharge), LOS, and number of resources utilized in the ED. To analyze the validity of ESI v.4, patients were divided into 2 groups for comparison: higher-acuity patients (ESI levels 1, 2, and 3) and lower-acuity patients (ESI levels 4 and 5). Pearson χ analysis was performed for categorical variables. For continuous variables, we conducted a comparison of means based on parametric distribution of variables. The second arm was a prospective cohort study to determine the interrater reliability of ESI v.4 among and between pediatric triage (PT) nurses and pediatric emergency medicine (PEM) physicians. Three raters (2 PT nurses and 1 PEM physician) independently assigned triage scores to 100 patients; k and interclass correlation coefficient were calculated among PT nurses and between the primary PT nurses and physicians. In the validity arm, the distribution of ESI score levels among the 780 cases are as follows: ESI 1: 2 (0.25%); ESI 2: 73 (9.4%); ESI 3: 289 (37%); ESI 4: 251 (32%); and ESI 5: 165 (21%). Hospital admission rates by ESI level were 1: 100%, 2: 42%, 3: 14.9%, 4: 1.2%, and 5: 0.6%. The admission rate of the higher-acuity group (76/364, 21%) was significantly greater than the lower-acuity group (4/415, 0.96%), P < 0.001. The mean ED LOS (in minutes) for the higher-acuity group was 257 (SD, 132) versus 143 (SD, 81) in the lower-acuity group, P < 0.001. The higher-acuity group also had significantly greater use of resources than the lower-acuity group, P < 0.001. The percentage of low-acuity patients receiving no resources was 54%, compared with only 26% in the higher-acuity group. Conversely, a greater percentage of higher-acuity patients utilized 2 or more resources than the lower-acuity cohorts, 43% vs 12%, respectively, P < 0.001. In the prospective reliability arm of the study, 15 PT nurses and 8 PEM attending physicians participated in the study; k among nurses was 0.92 and between the primary triage nurses and physicians was 0.78, P < 0.001. The intraclass correlation coefficient was 0.96 for PT nurses and 0.91 between the primary triage nurse and physicians, P < 0.001. Emergency Severity Index v.4 is a valid predictor of hospital admission, ED LOS, and resource utilization in the pediatric ED population. It is a reliable pediatric triage instrument with high agreement among PT nurses and between PT nurses and PEM physicians.

Prognostic performance of Emergency Severity Index (ESI) combined with qSOFA score.

PubMed

Kwak, Hyeongkyu; Suh, Gil Joon; Kim, Taegyun; Kwon, Woon Yong; Kim, Kyung Su; Jung, Yoon Sun; Ko, Jung-In; Shin, So Mi

2018-01-31

We conducted this study to investigate whether ESI combined with qSOFA score (ESI+qSOFA) predicts hospital outcome better than ESI alone in the emergency department (ED). This was a retrospective study for patients aged over 15years who visited an ED of a tertiary referral hospital from January 1st, 2015 to December 31st, 2015. We calculated and compared predictive performances of ESI alone and ESI+qSOFA for prespecified outcomes. The primary outcome was hospital mortality, and the secondary outcome was composite outcome of in-hospital mortality and ICU admission. We calculated in-hospital mortality rates by positive qSOFA in each subgroup divided according to ESI levels (1, 2, 3, 4+5). 43,748 patients were enrolled. The area under receiver-operating characteristics curves were higher in ESI+qSOFA than in ESI alone for both mortality and composite outcome (0.786 vs. 0.777, P<.001 for mortality; 0.778 vs. 0.774, P<.001 for composite outcome). In each subgroup divided by ESI levels, patients with positive qSOFA had significantly higher in-hospital mortality rate compared to those with negative qSOFA (20.4% vs. 14.7%, P=.117 in ESI level 1 subgroup; 11.3% vs. 2.7%, P=.001 in ESI level 2 subgroup; 2.3% vs. 0.4%, P<.001 in ESI level 3 subgroup; 0.0% vs. 0.0% in ESI level 4 or 5 subgroup). The prognostic performance of ESI+qSOFA for in-hospital mortality was significantly higher than that of ESI alone. Within each subgroup, patients with positive qSOFA had higher in-hospital mortality compared to those with negative qSOFA. Copyright © 2018 Elsevier Inc. All rights reserved.

Catechin concentrates of garden tea leaves (Camellia sinensis L.): extraction/isolation and evaluation of chemical composition.

PubMed

Gadkari, Pravin Vasantrao; Kadimi, Udaya Sankar; Balaraman, Manohar

2014-11-01

Solid-liquid (SLE) and liquid-liquid (LLE) extraction techniques were applied to extract catechins and caffeine from quick mechanically expelled tea leaf juice (QMETLJ) and freeze-dried (FD)-QMETLJ of Camellia sinensis L. The concentrates obtained were analyzed for total polyphenol content and antioxidant activity (DPPH(•) inhibition, FRAP and phosphomolybdenum assay). Catechins were identified and quantified using HPLC. Overall, 95% (v/v) ethanol was the best solvent system for extracting total polyphenols (355.26 ± 23.68 to 457.89 ± 28.94 g GAE kg(-1) extractable solid yield (ESY)) and antioxidants (DPPH(•) inhibition, 16.97 ± 0.52 to 20.83 ± 3.11%; FRAP, 4.15 ± 0.32 to 6.38 ± 0.57 mmol TE g(-1) ESY; Mo(V) reduction, 2.47 ± 0.19 to 3.84 ± 0.39 mmol AAE g(-1) ESY) from FD-QMETLJ. Similarly, in LLE, ethyl acetate showed the best results for recovering polyphenols (960.52 ± 7.89 g GAE kg(-1) ESY) and antioxidants (DPPH(•) inhibition, 42.39 ± 0.91%; FRAP, 11.39 ± 0.83 mmol TE g(-1) ESY; Mo(V) reduction, 6.71 ± 1.14 mmol AAE g(-1) ESY) from QMETLJ. It was found that 95% ethanol can be used to increase the total polyphenols and antioxidants in extracts from FD-QMETLJ, while ethyl acetate can be effectively employed for concentrating catechins from QMETLJ. © 2014 Society of Chemical Industry.

A comprehensive high-resolution mass spectrometry approach for characterization of metabolites by combination of ambient ionization, chromatography and imaging methods.

PubMed

Berisha, Arton; Dold, Sebastian; Guenther, Sabine; Desbenoit, Nicolas; Takats, Zoltan; Spengler, Bernhard; Römpp, Andreas

2014-08-30

An ideal method for bioanalytical applications would deliver spatially resolved quantitative information in real time and without sample preparation. In reality these requirements can typically not be met by a single analytical technique. Therefore, we combine different mass spectrometry approaches: chromatographic separation, ambient ionization and imaging techniques, in order to obtain comprehensive information about metabolites in complex biological samples. Samples were analyzed by laser desorption followed by electrospray ionization (LD-ESI) as an ambient ionization technique, by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging for spatial distribution analysis and by high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS) for quantitation and validation of compound identification. All MS data were acquired with high mass resolution and accurate mass (using orbital trapping and ion cyclotron resonance mass spectrometers). Grape berries were analyzed and evaluated in detail, whereas wheat seeds and mouse brain tissue were analyzed in proof-of-concept experiments. In situ measurements by LD-ESI without any sample preparation allowed for fast screening of plant metabolites on the grape surface. MALDI imaging of grape cross sections at 20 µm pixel size revealed the detailed distribution of metabolites which were in accordance with their biological function. HPLC/ESI-MS was used to quantify 13 anthocyanin species as well as to separate and identify isomeric compounds. A total of 41 metabolites (amino acids, carbohydrates, anthocyanins) were identified with all three approaches. Mass accuracy for all MS measurements was better than 2 ppm (root mean square error). The combined approach provides fast screening capabilities, spatial distribution information and the possibility to quantify metabolites. Accurate mass measurements proved to be critical in order to reliably combine data from different MS techniques. Initial results on the mycotoxin deoxynivalenol (DON) in wheat seed and phospholipids in mouse brain as a model for mammalian tissue indicate a broad applicability of the presented workflow. Copyright © 2014 John Wiley & Sons, Ltd.

Regio- and stereoselective synthesis of benzothiazolo-pyrimidinones via an NHC-catalyzed Mannich/lactamization domino reaction† †Electronic supplementary information (ESI) available. CCDC 1029497. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc08594a

PubMed Central

Ni, Qijian; Song, Xiaoxiao; Xiong, Jiawen; Raabe, Gerhard

2015-01-01

An NHC-catalyzed regio- and stereoselective Mannich/lactamization domino reaction of N-(benzothiazolyl)imines with α-chloroaldehydes has been developed. This new protocol provides a facile approach for the asymmetric synthesis of benzothiazolo-pyrimidinones and a pyrrolo[1,2-a]indolone in moderate to good yields (34–78%) and excellent stereoselectivities (87–99% ee, up to >20 : 1 d.r.). PMID:25476422

A Comparison of Alternating Current and Direct Current Electrospray Ionization for Mass Spectrometry

PubMed Central

Sarver, Scott A.; Gartner, Carlos A.; Chetwani, Nishant; Go, David B.; Dovichi, Norman J.

2014-01-01

A series of studies comparing the performance of alternating current electrospray ionization (AC ESI) mass spectrometry (MS) and direct current electrospray ionization (DC ESI) MS has been conducted, exploring the absolute signal intensity and signal-to-background ratios produced by both methods using caffeine and a model peptide as targets. Because the high-voltage AC signal was more susceptible to generating gas discharges, the operating voltage range of AC ESI was significantly smaller than that for DC ESI, such that the absolute signal intensities produced by DC ESI at peak voltages were 1 - 2 orders of magnitude greater than those for AC ESI. Using an electronegative nebulizing gas, sulfur hexafluoride (SF6), instead of nitrogen (N2) increased the operating range of AC ESI by ~50%, but did not appreciably improve signal intensities. While DC ESI generated far greater signal intensities, both ionization methods produced comparable signal-to-background noise, with AC ESI spectra appearing qualitatively cleaner. A quantitative calibration analysis was performed for two analytes, caffeine and the peptide MRFA. AC ESI utilizing SF6 outperforms all other techniques for the detection of MRFA, producing chromatographic limits of detection nearly one order of magnitude lower than that of DC ESI utilizing N2, and one half that of DC ESI utilizing SF6. However, DC ESI outperforms AC ESI for the analysis of caffeine, indicating improvements in spectral quality may benefit certain compounds, or classes of compounds, on an individual basis. PMID:24464359

Quantitative analysis of serotonin secreted by human embryonic stem cells-derived serotonergic neurons via pH-mediated online stacking-CE-ESI-MRM.

PubMed

Zhong, Xuefei; Hao, Ling; Lu, Jianfeng; Ye, Hui; Zhang, Su-Chun; Li, Lingjun

2016-04-01

A CE-ESI-MRM-based assay was developed for targeted analysis of serotonin released by human embryonic stem cells-derived serotonergic neurons in a chemically defined environment. A discontinuous electrolyte system was optimized for pH-mediated online stacking of serotonin. Combining with a liquid-liquid extraction procedure, LOD of serotonin in the Krebs'-Ringer's solution by CE-ESI-MS/MS on a 3D ion trap MS was0.15 ng/mL. The quantitative results confirmed the serotonergic identity of the in vitro developed neurons and the capacity of these neurons to release serotonin in response to stimulus. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the role of ionic liquids to tune the polymorphic outcome of organic compounds† †Electronic supplementary information (ESI) available: CCDC 1577981. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04353h

PubMed Central

Zeng, Qingying; Mukherjee, Arijit; Müller, Peter; Rogers, Robin D.

2017-01-01

While molecular solvents are commonly used in the screening of polymorphs, the choices are often restricted. Ionic liquids (ILs) – also referred as designer solvents – have immense possibility in this regard because of their wide flexibility of tunability. More importantly, the interactions among the IL components are completely unique compared to those present in the molecular solvents. In this context, we have chosen tetrolic acid (TA) and isonicotinamide (INA), which showed solution-structure link in molecular solvents in the past, as probes to investigate the role of imidazolium based ionic liquids in the polymorphism of these two systems and whether the different solute–solvent interactions in ILs affect the polymorphic outcome. It is observed that the selected imidazolium-based ILs, with varying anion basicity have influenced the crystallization outcome by the interaction between ILs and model compounds. Later, we have utilized the concept of double salt ionic liquids (DSIL) for INA, a penta-morphic system, to investigate the variation in the polymorphic outcome. This approach helped to obtain the forms that were otherwise inaccessible in ILs. PMID:29675194

Estimated historical distribution of grassland communities of the Southern Great Plains

USGS Publications Warehouse

Reese, Gordon C.; Manier, Daniel J.; Carr, Natasha B.; Callan, Ramana; Leinwand, Ian I.F.; Assal, Timothy J.; Burris, Lucy; Ignizio, Drew A.

2016-12-07

The purpose of this project was to map the estimated distribution of grassland communities of the Southern Great Plains prior to Euro-American settlement. The Southern Great Plains Rapid Ecoregional Assessment (REA), under the direction of the Bureau of Land Management and the Great Plains Landscape Conservation Cooperative, includes four ecoregions: the High Plains, Central Great Plains, Southwestern Tablelands, and the Nebraska Sand Hills. The REA advisors and stakeholders determined that the mapping accuracy of available national land-cover maps was insufficient in many areas to adequately address management questions for the REA. Based on the recommendation of the REA stakeholders, we estimated the potential historical distribution of 10 grassland communities within the Southern Great Plains project area using data on soils, climate, and vegetation from the Natural Resources Conservation Service (NRCS) including the Soil Survey Geographic Database (SSURGO) and Ecological Site Information System (ESIS). The dominant grassland communities of the Southern Great Plains addressed as conservation elements for the REA area are shortgrass, mixed-grass, and sand prairies. We also mapped tall-grass, mid-grass, northwest mixed-grass, and cool season bunchgrass prairies, saline and foothill grasslands, and semi-desert grassland and steppe. Grassland communities were primarily defined using the annual productivity of dominant species in the ESIS data. The historical grassland community classification was linked to the SSURGO data using vegetation types associated with the predominant component of mapped soil units as defined in the ESIS data. We augmented NRCS data with Landscape Fire and Resource Management Planning Tools (LANDFIRE) Biophysical Settings classifications 1) where NRCS data were unavailable and 2) where fifth-level watersheds intersected the boundary of the High Plains ecoregion in Wyoming. Spatial data representing the estimated historical distribution of grassland communities of the Southern Great Plains are provided as a 30 x 30-meter gridded surface (raster dataset). This information will help to address the priority management questions for grassland communities for the Southern Great Plains REA and can be used to inform other regional-level land management decisions.

Reforming the reform: the Greek National Health System in transition.

PubMed

Tountas, Yannis; Karnaki, Panagiota; Pavi, Elpida

2002-10-01

The National Health System (ESY) in Greece, which was established in 1983, is in a state of continuous crisis. This situation is caused mainly by the system's problematic administration, low productivity and inadequate Primary Health Care. These have led the re-elected PASOK government to introduce by the end of 2000 a radical reform of the health system. The 200 reform measures announced by the new Minister of Health and Welfare include changes aiming at: the decentralization of the ESY, the creation of a unified financing system for the social insurance funds, a new management structure in public hospitals, the organization of a Primary Health System in urban areas, and the strengthening of Public Health and Health Promotion. These changes are presented and discussed in this paper.

An enhanced droplet-based liquid microjunction surface sampling system coupled with HPLC-ESI-MS/MS for spatially resolved analysis

DOE PAGES

Van Berkel, Gary J.; Weiskittel, Taylor M.; Kertesz, Vilmos

2014-11-07

Droplet-based liquid microjunction surface sampling coupled with high-performance liquid chromatography (HPLC)-electrospray ionization (ESI)-tandem mass spectrometry (MS/MS) for spatially resolved analysis provides the possibility of effective analysis of complex matrix samples and can provide a greater degree of chemical information from a single spot sample than is typically possible with a direct analysis of an extract. Described here is the setup and enhanced capabilities of a discrete droplet liquid microjunction surface sampling system employing a commercially available CTC PAL autosampler. The system enhancements include incorporation of a laser distance sensor enabling unattended analysis of samples and sample locations of dramatically disparatemore » height as well as reliably dispensing just 0.5 μL of extraction solvent to make the liquid junction to the surface, wherein the extraction spot size was confined to an area about 0.7 mm in diameter; software modifications improving the spatial resolution of sampling spot selection from 1.0 to 0.1 mm; use of an open bed tray system to accommodate samples as large as whole-body rat thin tissue sections; and custom sample/solvent holders that shorten sampling time to approximately 1 min per sample. Lastly, the merit of these new features was demonstrated by spatially resolved sampling, HPLC separation, and mass spectral detection of pharmaceuticals and metabolites from whole-body rat thin tissue sections and razor blade (“crude”) cut mouse tissue.« less

An enhanced droplet-based liquid microjunction surface sampling system coupled with HPLC-ESI-MS/MS for spatially resolved analysis

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

Van Berkel, Gary J.; Weiskittel, Taylor M.; Kertesz, Vilmos

Droplet-based liquid microjunction surface sampling coupled with high-performance liquid chromatography (HPLC)-electrospray ionization (ESI)-tandem mass spectrometry (MS/MS) for spatially resolved analysis provides the possibility of effective analysis of complex matrix samples and can provide a greater degree of chemical information from a single spot sample than is typically possible with a direct analysis of an extract. Described here is the setup and enhanced capabilities of a discrete droplet liquid microjunction surface sampling system employing a commercially available CTC PAL autosampler. The system enhancements include incorporation of a laser distance sensor enabling unattended analysis of samples and sample locations of dramatically disparatemore » height as well as reliably dispensing just 0.5 μL of extraction solvent to make the liquid junction to the surface, wherein the extraction spot size was confined to an area about 0.7 mm in diameter; software modifications improving the spatial resolution of sampling spot selection from 1.0 to 0.1 mm; use of an open bed tray system to accommodate samples as large as whole-body rat thin tissue sections; and custom sample/solvent holders that shorten sampling time to approximately 1 min per sample. Lastly, the merit of these new features was demonstrated by spatially resolved sampling, HPLC separation, and mass spectral detection of pharmaceuticals and metabolites from whole-body rat thin tissue sections and razor blade (“crude”) cut mouse tissue.« less

Progress in a selective method for the determination of the acetaldehyde-derived DNA adducts by using HILIC-ESI-MS/MS.

PubMed

Murakami, Hiroya; Horiba, Ruri; Iwata, Tomoko; Miki, Yuta; Uno, Bunji; Sakai, Tadao; Kaneko, Kazuhiro; Ishihama, Yasushi; Teshima, Norio; Esaka, Yukihiro

2018-01-15

Acetaldehyde (AA), which is present in tobacco smoke, automobile exhaust gases and alcohol beverage, is a mutagen and carcinogen. AA reacts with 2'-deoxyguanosine (dG) in DNA to form N 2 -ethyl-dG (EtdG) and cyclic, 1, N 2 -propano-dG (CPrdG), which are considered to have a critical role in carcinogenesis induced by AA. In this study, we have developed a highly sensitive method for the quantitation of the two AA-derived DNA adducts by using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) in which hydrophilic interaction chromatography (HILIC) employing mobile phases of high organic solvent concentration was selected to improve the ionization efficiency in the ESI process. Fourteen times and 11 times larger peak areas for EtdG and CPrdG, respectively, in HILIC-ESI-MS/MS were obtained compared with those in reversed phase (RP)-LC-ESI-MS/MS. Furthermore, 6.9 times (for EtdG) and 2.4 times (for CPrdG) larger peak areas were also obtained as additional enhancement by varying additive compounds in the HILIC mobile phases from ammonium acetate to ammonium bicarbonate. In total, the enhancements in detected MS signal intensities by exchanging from the RP-LC system to the HILIC system are 97 times for EtdG and 26 times for CPrdG, respectively. Three commercially available HILIC columns with different polar functional groups were examined and sufficient separation between normal 2'-deoxynucleosides and the AA-derived DNA adducts was achieved by a carbamoyl-bonded HILIC column. Finally, we applied the established method to quantify EtdG and CPrdG in the damaged calf thymus DNA. Copyright © 2017 Elsevier B.V. All rights reserved.

Release of Native-like Gaseous Proteins from Electrospray Droplets via the Charged Residue Mechanism: Insights from Molecular Dynamics Simulations.

PubMed

McAllister, Robert G; Metwally, Haidy; Sun, Yu; Konermann, Lars

2015-10-07

The mechanism whereby gaseous protein ions are released from charged solvent droplets during electrospray ionization (ESI) remains a matter of debate. Also, it is unclear to what extent electrosprayed proteins retain their solution structure. Molecular dynamics (MD) simulations offer insights into the temporal evolution of protein systems. Surprisingly, there have been no all-atom simulations of the protein ESI process to date. The current work closes this gap by investigating the behavior of protein-containing aqueous nanodroplets that carry excess positive charge. We focus on "native ESI", where proteins initially adopt their biologically active solution structures. ESI proceeds while the protein remains entrapped within the droplet. Protein release into the gas phase occurs upon solvent evaporation to dryness. Droplet shrinkage is accompanied by ejection of charge carriers (Na(+) for the conditions chosen here), keeping the droplet at ∼85% of the Rayleigh limit throughout its life cycle. Any remaining charge carriers bind to the protein as the final solvent molecules evaporate. The outcome of these events is largely independent of the initial protein charge and the mode of charge carrier binding. ESI charge states and collision cross sections of the MD structures agree with experimental data. Our results confirm the Rayleigh/charged residue model (CRM). Field emission of excess Na(+) plays an ancillary role by governing the net charge of the shrinking droplet. Models that envision protein ejection from the droplet are not supported. Most nascent CRM ions retain native-like conformations. For unfolded proteins ESI likely proceeds along routes that are different from the native state mechanism explored here.

Improved Sensitivity for Molecular Detection of Bacterial and Candida Infections in Blood

PubMed Central

Bacconi, Andrea; Richmond, Gregory S.; Baroldi, Michelle A.; Laffler, Thomas G.; Blyn, Lawrence B.; Carolan, Heather E.; Frinder, Mark R.; Toleno, Donna M.; Metzgar, David; Gutierrez, Jose R.; Massire, Christian; Rounds, Megan; Kennel, Natalie J.; Rothman, Richard E.; Peterson, Stephen; Carroll, Karen C.; Wakefield, Teresa; Ecker, David J.

2014-01-01

The rapid identification of bacteria and fungi directly from the blood of patients with suspected bloodstream infections aids in diagnosis and guides treatment decisions. The development of an automated, rapid, and sensitive molecular technology capable of detecting the diverse agents of such infections at low titers has been challenging, due in part to the high background of genomic DNA in blood. PCR followed by electrospray ionization mass spectrometry (PCR/ESI-MS) allows for the rapid and accurate identification of microorganisms but with a sensitivity of about 50% compared to that of culture when using 1-ml whole-blood specimens. Here, we describe a new integrated specimen preparation technology that substantially improves the sensitivity of PCR/ESI-MS analysis. An efficient lysis method and automated DNA purification system were designed for processing 5 ml of whole blood. In addition, PCR amplification formulations were optimized to tolerate high levels of human DNA. An analysis of 331 specimens collected from patients with suspected bloodstream infections resulted in 35 PCR/ESI-MS-positive specimens (10.6%) compared to 18 positive by culture (5.4%). PCR/ESI-MS was 83% sensitive and 94% specific compared to culture. Replicate PCR/ESI-MS testing from a second aliquot of the PCR/ESI-MS-positive/culture-negative specimens corroborated the initial findings in most cases, resulting in increased sensitivity (91%) and specificity (99%) when confirmed detections were considered true positives. The integrated solution described here has the potential to provide rapid detection and identification of organisms responsible for bloodstream infections. PMID:24951806

Improved amplification results following episodes of failure to amplify at the Amelogenin Locus using PowerPlex® ESI 16 Fast System.

PubMed

Berlyne, Sigal; Oz, Carla; Einot, Naftaly; Avraham, Shlomit; Ram, Tanya; Goldberg, Miri D; Gafny, Ron

2017-07-01

In 2012 the Israel Police DNA Casework laboratory adopted the 16 STR PowerPlex ® ESI kit for routine use. The Promega Company updated this kit and developed the PowerPlex ® ESI 16 Fast System in which all autosomal primer pairs remained identical to the original set, except at the amelogenin site. The master mix was improved and optimized which allowed for direct, faster and more robust amplification. Prior to implementing the PowerPlex ® ESI 16 Fast System in our lab, we conducted a preliminary assay where 213 casework samples were amplified using the new kit. These samples had previously been extracted by one of two extraction kits employed by our lab. (the PrepFiler ExpressTM and PrepFiler BTATM Forensic DNA Extraction Kits). The amplification results from these samples were compared to samples amplified using the original PowerPlex ® ESI 16 kit. Multiple incidents of failure to amplify at the amelogenin locus were noted using the new system with the recommended protocol at a rate of 13% (28 of 213 samples). Experiments were performed to understand whether these amplification failures could be a result of primer binding site mutations, extraction method reagents and/or inhibitors. The conclusions reached following these experiments, in conjunction with consultation with the manufacturer, led to the trial of a modified amplification protocol where the suggested annealing temperature was reduced by 2 degrees. To evaluate the efficiency of this altered protocol, a comparison study was undertaken where 88 additional casework samples were chosen and amplified using both the modified 58°C and the recommended 60°C annealing temperatures. We concluded that the most effective method in our laboratory for achieving a consistent and balanced amplification at the amelogenin locus was to reduce the annealing temperature from the manufacturer's recommended 60°C to 58°C. This modification resulted in a reduction of the failure to amplify at the amelogenin locus from 13% (28/213) to 1.1% (1/88) without any observed changes to the autosomal STR amplification results. Copyright © 2017 Elsevier B.V. All rights reserved.

Stem cell secretome-rich nanoclay hydrogel: a dual action therapy for cardiovascular regeneration

NASA Astrophysics Data System (ADS)

Waters, Renae; Pacelli, Settimio; Maloney, Ryan; Medhi, Indrani; Ahmed, Rafeeq P. H.; Paul, Arghya

2016-03-01

A nanocomposite hydrogel with photocrosslinkable micro-porous networks and a nanoclay component was successfully prepared to control the release of growth factor-rich stem cell secretome. The proven pro-angiogenic and cardioprotective potential of this new bioactive system provides a valuable therapeutic platform for cardiac tissue repair and regeneration.A nanocomposite hydrogel with photocrosslinkable micro-porous networks and a nanoclay component was successfully prepared to control the release of growth factor-rich stem cell secretome. The proven pro-angiogenic and cardioprotective potential of this new bioactive system provides a valuable therapeutic platform for cardiac tissue repair and regeneration. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07806g

Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

PubMed Central

Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

2011-01-01

Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry.

PubMed

Souda, Puneet; Ryan, Christopher M; Cramer, William A; Whitelegge, Julian

2011-12-01

Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein's native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electron-capture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. Copyright © 2011 Elsevier Inc. All rights reserved.

Reversible solvatomagnetic switching in a single-ion magnet from an entatic state† †Electronic supplementary information (ESI) available: Preparation methods and physical characterization data. Crystallographic refinement and computational details. Additional figures (Fig. S1–S12) and tables (Tables S1–S5). CCDC 952077 and 938463. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05188j Click here for additional data file. Click here for additional data file.

PubMed Central

Vallejo, J.; Viciano-Chumillas, M.; Castro, I.; Amorós, P.; Déniz, M.; Ruiz-Pérez, C.; Yuste-Vivas, C.; Krzystek, J.; Julve, M.; Lloret, F.

2017-01-01

A vast impact on molecular nanoscience can be achieved using simple transition metal complexes as dynamic chemical systems to perform specific and selective tasks under the control of an external stimulus that switches “ON” and “OFF” their electronic properties. While the interest in single-ion magnets (SIMs) lies in their potential applications in information storage and quantum computing, the switching of their slow magnetic relaxation associated with host–guest processes is insufficiently explored. Herein, we report a unique example of a mononuclear cobalt(ii) complex in which geometrical constraints are the cause of easy and reversible water coordination and its release. As a result, a reversible and selective colour and SIM behaviour switch occurs between a “slow-relaxing” deep red anhydrous material (compound 1) and its “fast-relaxing” orange hydrated form (compound 2). The combination of this optical and magnetic switching in this new class of vapochromic and thermochromic SIMs offers fascinating possibilities for designing multifunctional molecular materials. PMID:28580105

A Pilot Test of the Everyday Stressors Index-Spanish Version in a Sample of Hispanic Women Attending Prenatal Care.

PubMed

Gómez, María L; Ashford, Kristin; Linares, Ana M; Hall, Lynne A

2015-01-01

Prenatal and postpartum psychosocial stress are associated with adverse pregnancy outcomes. Hispanic women experience higher levels of stress during pregnancy. This pilot study assessed the psychometric characteristics of the Everyday Stressors Index-Spanish (ESI-S) version. Secondary analysis in a convenience sample, n = 51 women. The ESI-S showed adequate internal consistency (Cronbach's alpha = .86). Two factors accounted for 40% of the item variance. The greatest sources of stress were "having too many responsibilities" and "not enough money for basics". Higher levels of stressors were associated with older age, living without a partner, and working part or full time. The ESI-S was positively correlated with measures of perinatal depression. Findings support the reliability and validity of the newly translated ESI-S.

Profiling LC-DAD-ESI-TOF MS method for the determination of phenolic metabolites from avocado (Persea americana).

PubMed

Hurtado-Fernández, Elena; Carrasco-Pancorbo, Alegría; Fernández-Gutiérrez, Alberto

2011-03-23

A powerful HPLC-DAD-ESI-TOF MS method was established for the efficient identification of the chemical constituents in the methanolic extracts of avocado (Persea americana). Separation and detection conditions were optimized by using a standard mix containing 39 compounds belonging to phenolic acids and different categories of flavonoids, analytes that could be potentially present in the avocado extracts. Optimum LC separation was achieved on a Zorbax Eclipse Plus C18 analytical column (4.6×150 mm, 1.8 μm particle size) by gradient elution with water+acetic acid (0.5%) and acetonitrile as mobile phases, at a flow rate of 1.6 mL/min. The detection was carried out by ultraviolet-visible absorption and ESI-TOF MS. The developed method was applied to the study of 3 different varieties of avocado, and 17 compounds were unequivocally identified with standards. Moreover, around 25 analytes were tentatively identified by taking into account the accuracy and isotopic information provided by TOF MS.

Unambiguous Metabolite Identification in High-Throughput Metabolomics by Hybrid 1H-NMR/ESI-MS1 Approach

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

The invention improves accuracy of metabolite identification by combining direct infusion ESI-MS with one-dimensional 1H-NMR spectroscopy. First, we apply a standard 1H-NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in a metabolomics reference libraries. This generates a list of candidate metabolites. The list contains both false positive and ambiguous identifications. The software tool (the invention) takes the list of candidate metabolites, generated from NMRbased metabolite identification, and then calculates, for each of the candidate metabolites, the monoisotopic mass-tocharge (m/z) ratios for each commonly observedmore » ion, fragment and adduct feature. These are then used to assign m/z ratios in experimental ESI-MS spectra of the same sample. Detection of the signals of a given metabolite in both NMR and MS spectra resolves the ambiguities, and therefore, significantly improves the confidence of the identification.« less

Proanthocyanidin screening by LC-ESI-MS of Portuguese red wines made with teinturier grapes.

PubMed

Teixeira, Natércia; Azevedo, Joana; Mateus, Nuno; de Freitas, Victor

2016-01-01

Proanthocyanidins (PAs) are one of the most important polyphenolic compounds in wine. Among PAs, prodelphinidin (PD) dimers and trimers have not been widely detected in wines due to the lack of available commercial standards and the difficulty to detect and isolate them from natural sources. LC-ESI-MS (liquid chromatography-electrospray ionization-mass spectrometry) with the right chromatographic conditions has proven to be a powerful tool for PAs detection and identification in complex samples. This technique has been applied to an exhaustive study of PA composition of two Portuguese red wines made with teinturier grapes, especially for the identification of PD dimers and trimers. Tandem mass spectrometry (MS/MS) with ion trap provided additional information about the structures of these compounds through the fragmentation patterns of the pseudomolecular ions. A LC-ESI-MS method was optimized and 41 different compounds were found. Among them are included 8 PD dimers and 13 PD trimers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Pulsed Direct Current Electrospray: Enabling Systematic Analysis of Small Volume Sample by Boosting Sample Economy.

PubMed

Wei, Zhenwei; Xiong, Xingchuang; Guo, Chengan; Si, Xingyu; Zhao, Yaoyao; He, Muyi; Yang, Chengdui; Xu, Wei; Tang, Fei; Fang, Xiang; Zhang, Sichun; Zhang, Xinrong

2015-11-17

We had developed pulsed direct current electrospray ionization mass spectrometry (pulsed-dc-ESI-MS) for systematically profiling and determining components in small volume sample. Pulsed-dc-ESI utilized constant high voltage to induce the generation of single polarity pulsed electrospray remotely. This method had significantly boosted the sample economy, so as to obtain several minutes MS signal duration from merely picoliter volume sample. The elongated MS signal duration enable us to collect abundant MS(2) information on interested components in a small volume sample for systematical analysis. This method had been successfully applied for single cell metabolomics analysis. We had obtained 2-D profile of metabolites (including exact mass and MS(2) data) from single plant and mammalian cell, concerning 1034 components and 656 components for Allium cepa and HeLa cells, respectively. Further identification had found 162 compounds and 28 different modification groups of 141 saccharides in a single Allium cepa cell, indicating pulsed-dc-ESI a powerful tool for small volume sample systematical analysis.

A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

PubMed

Stinson, Craig A; Xia, Yu

2016-06-21

Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

Isodeoxyelephantopin induces protective autophagy in lung cancer cells via Nrf2-p62-keap1 feedback loop

PubMed Central

Wang, Yang; Zhang, Jing; Huang, Zhi-Hao; Huang, Xiao-Hui; Zheng, Wei-Bin; Yin, Xing-Feng; Li, Yao-Lan; Li, Bin; He, Qing-Yu

2017-01-01

Isodeoxyelephantopin (ESI), isolated from Elephantopus scaber L. has been reported to exert anticancer effects. In this study, we aimed to investigate whether and how cancer cells exert protective responses against ESI treatment. Confocal fluorescence microscopy showed that ESI significantly induced autophagy flux in the lung cancer cells expressing mCherry-EGFP-LC3 reporter. Treatment of the cells with ESI increased the expression levels of the autophagy markers including LC3-II, ATG3 and Beclin1 in a dose-dependent manner. Pretreatment with autophagy inhibitor 3-methyladenine (3-MA) not only attenuated the effects of ESI on autophagy, but also enhanced the effects of ESI on cell viability and apoptosis. Mechanistically, the SILAC quantitative proteomics coupled with bioinformatics analysis revealed that the ESI-regulated proteins were mainly involved in Nrf2-mediated oxidative stress response. We found that ESI induced the nuclear translocation of Nrf2 for activating the downstream target genes including HO-1 and p62 (SQSTM1). More importantly, ESI-induced p62 could competitively bind with Keap1, and releases Nrf2 to activate downstream target gene p62 as a positive feedback loop, therefore promoting autophagy. Furthermore, knockdown of Nrf2 or p62 could abrogate the ESI-induced autophagy and significantly enhanced the anticancer effect of ESI. Taken together, we demonstrated that ESI can sustain cell survival by activating protective autophagy through Nrf2-p62-keap1 feedback loop, whereas targeting this regulatory axis combined with ESI treatment may be a promising strategy for anticancer therapy. PMID:28617433

Isodeoxyelephantopin induces protective autophagy in lung cancer cells via Nrf2-p62-keap1 feedback loop.

PubMed

Wang, Yang; Zhang, Jing; Huang, Zhi-Hao; Huang, Xiao-Hui; Zheng, Wei-Bin; Yin, Xing-Feng; Li, Yao-Lan; Li, Bin; He, Qing-Yu

2017-06-15

Isodeoxyelephantopin (ESI), isolated from Elephantopus scaber L. has been reported to exert anticancer effects. In this study, we aimed to investigate whether and how cancer cells exert protective responses against ESI treatment. Confocal fluorescence microscopy showed that ESI significantly induced autophagy flux in the lung cancer cells expressing mCherry-EGFP-LC3 reporter. Treatment of the cells with ESI increased the expression levels of the autophagy markers including LC3-II, ATG3 and Beclin1 in a dose-dependent manner. Pretreatment with autophagy inhibitor 3-methyladenine (3-MA) not only attenuated the effects of ESI on autophagy, but also enhanced the effects of ESI on cell viability and apoptosis. Mechanistically, the SILAC quantitative proteomics coupled with bioinformatics analysis revealed that the ESI-regulated proteins were mainly involved in Nrf2-mediated oxidative stress response. We found that ESI induced the nuclear translocation of Nrf2 for activating the downstream target genes including HO-1 and p62 (SQSTM1). More importantly, ESI-induced p62 could competitively bind with Keap1, and releases Nrf2 to activate downstream target gene p62 as a positive feedback loop, therefore promoting autophagy. Furthermore, knockdown of Nrf2 or p62 could abrogate the ESI-induced autophagy and significantly enhanced the anticancer effect of ESI. Taken together, we demonstrated that ESI can sustain cell survival by activating protective autophagy through Nrf2-p62-keap1 feedback loop, whereas targeting this regulatory axis combined with ESI treatment may be a promising strategy for anticancer therapy.

Using a set of strategic indicator systems as a decision-making support implement for establishing a recycling-oriented society. A Taiwanese case study.

PubMed

Chang, I-Cheng; Lu, Li-Teh; Lin, Shiann-Shan

2005-01-01

BACKGROUND, SCOPE AND AIMS: To realize the vision of sustainable development (SD) originating from the 'only one earth' philosophy, and to integrate the conceptions of ecology and sustainability into the planning and decision-making criteria of urban growth management, the establishment of a recycling-oriented society (ROS) is essential. However, before the above intention can be achieved, it is indispensable to develop a system of strategic indicators for supporting a radical reformation of the urban development plan. Therefore, this study, based on the conception of the new urban development pattern ROS, attempted to carefully choose a sample city in Taiwan for launching a preliminary case study, and furthermore designed and proposed a concise and strategy-oriented assessment indicator system termed ROSAIS. ROSAIS, on the one hand, can act as a compass for understanding resource using efficiency and recycling status during city development and, on the other hand, can serve as an implement supporting decision-making for ROS construction. According to the definition and spirit of ROS, the structure of ROSAIS should clearly represent the relationship between resources and environment in human activities. The eco-efficiency indicator system (EEIS) and environmental symbiosis indicator system (ESIS) can be considered two key subindicator systems, and are the necessary components of ROSAIS. EEIS chooses the dominant production sectors in urban economic activities to calculate their eco-efficiency (EE). Separately, for obtaining a consensus regarding the framework of ESIS, the questionnaire approaches and expert consultation, together with the research experience and foundation of current relevant studies and indicator systems, are applied when crucial resource and environmental issues and respective indicators are selected. The calculation results of EEIS in this case study indicated that among the three dominant production activities (agricultural, fishery, and animal husbandry sector) the fishery sector has the highest EE, which indicates that the fishery activities and resources significantly influence the sustainability of the economic-environmental system of the sample city. Furthermore, according to a consensus achieved in ESIS, local green spaces, resource recovery, energy consumption pattern change, freshwater conservation and greenhouse effect abatement were considered as the five crucial issues influencing how the case study city can develop into an ES-city. The rate of local green spaces, resource recycling, freshwater conservation and the rate of reduction of nonrenewable energy use as well as carbon dioxide (CO2) emissions were used to evaluate the above five issues. This case study is unparalleled in Taiwan. Even in Japan, where ROS legislation has been implemented, this kind of study remains in the preliminary stages. Furthermore, when communicating the indicator results, it is essential to provide the context and countermeasures of the crucial issues that are faced. The two sub-indicator systems proposed in this case study could comply completely with the above-mentioned requirements. For example, the EEIS provides information for achieving a balance between environmental burden and economic benefits among dominant production sectors; the ESIS provides information for setting strategies for overcoming the crucial issues faced. This study recommends that urban planers should consider the construction of the corresponding strategic indicator system to be indispensable, and makes further use of the indicator results related to the environmental education of residents for identifying and promoting participation with ROS, and turning them into implements for supporting urban SD decision-making. Furthermore, a successful indicator system depends on data availability and quality. This study recommends that urban planers should pay considerable attention to constructing relevant data collection channels, databases and the data quality.

Chlorogenic acid-arabinose hybrid domains in coffee melanoidins: Evidences from a model system.

PubMed

Moreira, Ana S P; Coimbra, Manuel A; Nunes, Fernando M; Passos, Cláudia P; Santos, Sónia A O; Silvestre, Armando J D; Silva, André M N; Rangel, Maria; Domingues, M Rosário M

2015-10-15

Arabinose from arabinogalactan side chains was hypothesized as a possible binding site for chlorogenic acids in coffee melanoidins. To investigate this hypothesis, a mixture of 5-O-caffeoylquinic acid (5-CQA), the most abundant chlorogenic acid in green coffee beans, and (α1 → 5)-L-arabinotriose, structurally related to arabinogalactan side chains, was submitted to dry thermal treatments. The compounds formed during thermal processing were identified by electrospray ionization mass spectrometry (ESI-MS) and characterized by tandem MS (ESI-MS(n)). Compounds composed by one or two CQAs covalently linked with pentose (Pent) residues (1-12) were identified, along with compounds bearing a sugar moiety but composed exclusively by the quinic or caffeic acid moiety of CQAs. The presence of isomers was demonstrated by liquid chromatography online coupled to ESI-MS and ESI-MS(n). Pent1-2CQA were identified in coffee samples. These results give evidence for a diversity of chlorogenic acid-arabinose hybrids formed during roasting, opening new perspectives for their identification in melanoidin structures. Copyright © 2015 Elsevier Ltd. All rights reserved.

The crystalline sponge method: MOF terminal ligand effects† †Electronic supplementary information (ESI) available: Experimental and crystallographic procedures, and data tables. CCDC 1063685 and 1063686. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cc03840e Click here for additional data file. Click here for additional data file.

PubMed Central

Ramadhar, Timothy R.; Zheng, Shao-Liang; Chen, Yu-Sheng

2015-01-01

Bromide and chloride analogs of the commonly used zinc iodide-based metal organic framework for the crystalline sponge method were synthesized and evaluated. Inclusion of (1R)-(–)-menthyl acetate into these MOFs was analysed using third-generation synchrotron radiation, and the effects and potential benefits of varying the MOF terminal ligand are discussed. PMID:26081991

A self-powered kinesin-microtubule system for smart cargo delivery

NASA Astrophysics Data System (ADS)

Jia, Yi; Dong, Weiguang; Feng, Xiyun; Li, Jieling; Li, Junbai

2014-11-01

A smart self-powered cargo delivery system that is composed of creatine phosphate kinase (CPK) microspheres, kinesins and microtubules is demonstrated. The CPK microsphere not only acts as an ATP generation and buffering system, but also as a carrier for cargo transport, thus realizing the easy loading and self-powered delivery of cargos at the same time.A smart self-powered cargo delivery system that is composed of creatine phosphate kinase (CPK) microspheres, kinesins and microtubules is demonstrated. The CPK microsphere not only acts as an ATP generation and buffering system, but also as a carrier for cargo transport, thus realizing the easy loading and self-powered delivery of cargos at the same time. Electronic supplementary information (ESI) available: Experimental details, Fig. S1-S4, and Mov. S1-S6. See DOI: 10.1039/c4nr04454a

12 CFR 1080.6 - Civil investigative demands.

Code of Federal Regulations, 2012 CFR

2012-01-01

...) Manner and form of production of ESI. When a civil investigative demand requires the production of ESI... and form of production. Absent any instructions as to the form for producing ESI, ESI must be produced...

The IRIDICA PCR/Electrospray Ionization-Mass Spectrometry Assay on Bronchoalveolar Lavage for Bacterial Etiology in Mechanically Ventilated Patients with Suspected Pneumonia.

PubMed

Strålin, Kristoffer; Ehn, Fredrik; Giske, Christian G; Ullberg, Måns; Hedlund, Jonas; Petersson, Johan; Spindler, Carl; Özenci, Volkan

2016-01-01

We studied the diagnostic performance of the IRIDICA PCR/electrospray ionization-mass spectrometry (PCR/ESI-MS) assay applied on bronchoalveolar lavage (BAL) samples, from 51 mechanically ventilated patients with suspected pneumonia, in a prospective study. In 32 patients with X-ray verified pneumonia, PCR/ESI-MS was positive in 66% and BAL culture was positive in 38% (p = 0.045), and either of the methods was positive in 69%. The following BAL result combinations were noted: PCR/ESI-MS+/culture+, 34%; PCR/ESI-MS+/culture-, 31%; PCR/ESI-MS-/culture+, 3.1%; PCR/ESI-MS-/culture-, 31%; kappa 0.36 (95% confidence interval (CI), 0.10-0.63). In pneumonia patients without prior antibiotic treatment, optimal agreement was noted with 88% PCR/ESI-MS+/culture+ and 12% PCR/ESI-MS-/culture- (kappa 1.0). However, in patients with prior antibiotic treatment, the test agreement was poor (kappa 0.16; 95% CI, -0.10-0.44), as 10 patients were PCR/ESI-MS+/culture-. In 8/10 patients the pathogens detected by PCR/ESI-MS could be detected by other conventional tests or PCR tests on BAL. Compared with BAL culture, PCR/ESI-MS showed specificities and negative predictive values of ≥87% for all individual pathogens, an overall sensitivity of 77% and positive predictive value (PPV) of 42%. When other conventional tests and PCR tests were added to the reference standard, the overall PPV increased to 87%. The PCR/ESI-MS semi-quantitative level tended to be higher for PCR/ESI-MS positive cases with pneumonia compared with cases without pneumonia (p = 0.074). In conclusion, PCR/ESI-MS applied on BAL showed a promising performance and has potential to be clinically useful in mechanically ventilated patients with suspected pneumonia. The usefulness of the method for establishment of pneumonia etiology and selection of antibiotic therapy should be further studied.

The IRIDICA PCR/Electrospray Ionization–Mass Spectrometry Assay on Bronchoalveolar Lavage for Bacterial Etiology in Mechanically Ventilated Patients with Suspected Pneumonia

PubMed Central

Ehn, Fredrik; Giske, Christian G.; Ullberg, Måns; Hedlund, Jonas; Petersson, Johan; Spindler, Carl; Özenci, Volkan

2016-01-01

We studied the diagnostic performance of the IRIDICA PCR/electrospray ionization–mass spectrometry (PCR/ESI-MS) assay applied on bronchoalveolar lavage (BAL) samples, from 51 mechanically ventilated patients with suspected pneumonia, in a prospective study. In 32 patients with X-ray verified pneumonia, PCR/ESI-MS was positive in 66% and BAL culture was positive in 38% (p = 0.045), and either of the methods was positive in 69%. The following BAL result combinations were noted: PCR/ESI-MS+/culture+, 34%; PCR/ESI-MS+/culture-, 31%; PCR/ESI-MS-/culture+, 3.1%; PCR/ESI-MS-/culture-, 31%; kappa 0.36 (95% confidence interval (CI), 0.10–0.63). In pneumonia patients without prior antibiotic treatment, optimal agreement was noted with 88% PCR/ESI-MS+/culture+ and 12% PCR/ESI-MS-/culture- (kappa 1.0). However, in patients with prior antibiotic treatment, the test agreement was poor (kappa 0.16; 95% CI, -0.10–0.44), as 10 patients were PCR/ESI-MS+/culture-. In 8/10 patients the pathogens detected by PCR/ESI-MS could be detected by other conventional tests or PCR tests on BAL. Compared with BAL culture, PCR/ESI-MS showed specificities and negative predictive values of ≥87% for all individual pathogens, an overall sensitivity of 77% and positive predictive value (PPV) of 42%. When other conventional tests and PCR tests were added to the reference standard, the overall PPV increased to 87%. The PCR/ESI-MS semi-quantitative level tended to be higher for PCR/ESI-MS positive cases with pneumonia compared with cases without pneumonia (p = 0.074). In conclusion, PCR/ESI-MS applied on BAL showed a promising performance and has potential to be clinically useful in mechanically ventilated patients with suspected pneumonia. The usefulness of the method for establishment of pneumonia etiology and selection of antibiotic therapy should be further studied. PMID:27463099

A Pilot Test of the Everyday Stressors Index–Spanish Version in a Sample of Hispanic Women Attending Prenatal Care

PubMed Central

Gómez, María L.; Ashford, Kristin; Linares, Ana M.; Hall, Lynne A.

2016-01-01

Background and Purpose Prenatal and postpartum psychosocial stress are associated with adverse pregnancy outcomes. Hispanic women experience higher levels of stress during pregnancy. This pilot study assessed the psychometric characteristics of the Everyday Stressors Index-Spanish (ESI-S) version. Methods Secondary analysis in a convenience sample, n = 51 women. Results The ESI-S showed adequate internal consistency (Cronbach’s alpha = .86). Two factors accounted for 40% of the item variance. The greatest sources of stress were “having too many responsibilities” and “not enough money for basics”. Higher levels of stressors were associated with older age, living without a partner, and working part or full time. The ESI-S was positively correlated with measures of perinatal depression. Conclusions Findings support the reliability and validity of the newly translated ESI-S. PMID:26673774

Exit site and tunnel infections in children on chronic peritoneal dialysis: findings from the Standardizing Care to Improve Outcomes in Pediatric End Stage Renal Disease (SCOPE) Collaborative.

PubMed

Swartz, Sarah J; Neu, Alicia; Skversky Mason, Amy; Richardson, Troy; Rodean, Jonathan; Lawlor, John; Warady, Bradley; Somers, Michael J G

2018-06-01

The Standardizing Care to Improve Outcomes in Pediatric End Stage Renal Disease (SCOPE) Collaborative is a quality improvement initiative to reduce dialysis-associated infections. The frequency of peritoneal dialysis (PD) catheter exit site infection (ESI) and variables influencing its development and end result are unclear. We sought to determine ESI rates, to elucidate the epidemiology, risk factors, and outcomes for ESI, and to assess for association between provider compliance with care bundles and ESI risk. We reviewed demographic, dialysis and ESI data, and care bundle adherence and outcomes for SCOPE enrollees from October 2011 to September 2014. ESI involved only the exit site, only the subcutaneous catheter tunnel, or both. A total of 857 catheter insertions occurred in 734 children over 10,110 cumulative months of PD provided to these children. During this period 207 ESIs arose in 124 children or 0.25 ESIs per dialysis year. Median time to ESI was 392 days, with 69% of ESIs involving exit site only, 23% involving the tunnel only, and 8% involving both sites. Peritonitis developed in 6%. ESI incidence was associated with age (p = 0.003), being the lowest in children aged < 2 years and highest in those aged 6-12 years, and with no documented review of site care or an exit site score  of > 0 at prior month's visit (p < 0.001). Gender, race, end stage renal disease etiology, exit site orientation, catheter cuff number or mobilization, and presence of G-tube, stoma, or vesicostomy were unassociated with ESI incidence. Of the ESIs reported, 71% resolved with treatment, 24% required hospitalization, and 9% required catheter removal, generally secondary to tunnel infection. Exit site infections occur at an annualized rate of 0.25, typically well into the dialysis course. Younger patient age and documented review of site care are associated with lower ESI rates. Although most ESIs resolve, hospitalization is frequent, and tunnel involvement/catheter loss complicate outcomes.

The Evolution of Electrospray Generated Droplets is Not Affected by Ionization Mode

NASA Astrophysics Data System (ADS)

Liigand, Piia; Heering (Suu), Agnes; Kaupmees, Karl; Leito, Ivo; Girod, Marion; Antoine, Rodolphe; Kruve, Anneli

2017-10-01

Ionization efficiency and mechanism in ESI is strongly affected by the properties of mobile phase. The use of mobile-phase properties to accurately describe droplets in ESI source is convenient but may be inadequate as the composition of the droplets is changing in the plume due to electrochemical reactions occurring in the needle tip as well as continuous drying and fission of droplets. Presently, there is paucity of research on the effect of the polarity of the ESI mode on mobile phase composition in the droplets. In this paper, the change in the organic solvent content, pH, and droplet size are studied in the ESI plume in both ESI+ and ESI- ionization mode. We introduce a rigorous way - the absolute pH (pHabs H 2 O) - to describe pH change in the plume that takes into account organic solvent content in the mobile phase. pHabs H 2 O enables comparing acidities of ESI droplets with different organic solvent contents. The results are surprisingly similar for both ionization modes, indicating that the dynamics of the change of mobile-phase properties is independent from the ESI mode used. This allows us to conclude that the evolution of ESI droplets first of all proceeds via the evaporation of the organic modifier and to a lesser extent via fission of smaller droplets from parent droplets. Secondly, our study shows that qualitative findings related to the ESI process obtained on the ESI+ mode can almost directly be applied also in the ESI- mode. [Figure not available: see fulltext.

Forensic validation of the PowerPlex® ESI 16 STR Multiplex and comparison of performance with AmpFlSTR® SGM Plus®.

PubMed

Tucker, Valerie C; Kirkham, Amanda J; Hopwood, Andrew J

2012-05-01

We describe the forensic validation of Promega's PowerPlex® European Standard Investigator 16 (ESI 16) multiplex kit and compare results generated with the AmpFlSTR® SGM Plus® (SGM+) multiplex. ESI 16 combines the loci contained within the SGM+ multiplex with five additional loci: D2S441, D10S1248, D22S1045, D1S1656, and D12S391. A relative reduction in amplicon size of the SGM+ loci facilitates an increased robustness and amplification success of these amplicons with degraded DNA samples. Tests performed herein supplement ESI 16 data published previously with sensitivity, profile quality, mock casework, inhibitor and mixture study data collected in our laboratories in alignment with our internal technical and quality guidelines and those issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM), the DNA Advisory Board (DAB) and the DNA working group (DNAWG) of the European Network of Forensic Science Institutes (ENFSI). Full profiles were routinely generated from a fully heterozygous single source DNA template using 62.5 pg for ESI 16 and 500 pg for SGM+. This increase in sensitivity has a consequent effect on mixture analyses and the detection of minor mixture components. The improved PCR chemistry confers enhanced tolerance to high levels of laboratory prepared inhibitors compared with SGM+ results. In summary, our results demonstrate that the ESI 16 multiplex kit is more robust and sensitive compared with SGM+ and will be a suitable replacement system for the analysis of forensic DNA samples providing compliance with the European standard set of STR loci.

Underivatized oxysterols and nanoLC-ESI-MS: A mismatch.

PubMed

Roberg-Larsen, Hanne; Vesterdal, Caroline; Wilson, Steven Ray; Lundanes, Elsa

2015-07-01

Due to their non-charged character, liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) measurements of oxysterols are often performed after derivatization with e.g. charged Girard reagents. However, derivatization reactions are time-consuming and may require numerous steps to remove excess reagent. In addition, extensive sample handling can be associated with cholesterol autoxidation, resulting in analyte artifacts and hence false positives. Nano scale liquid chromatography in combination with electrospray-mass spectrometry (nanoLC-ESI-MS) is a powerful tool for analyzing limited samples, due to substantially increased sensitivity compared to conventional LC-ESI-MS. The signal enhancement may compensate for the poor ionization of the oxysterols; hence we have explored the possibility to quantify oxysterols without derivatization using nanoLC-ESI-MS. Non-derivatized oxysterols and nanoLC were however not compatible, due to persistent and large carry-over. This was attributed to the extended contribution of surface to volume ratio in such miniaturized systems and interactions with the materials of the nanoLC instrumentation (e.g. adsorption to the fused silica tubing). Two contemporary MS instruments (Q-Exactive™ hybrid quadrupole-Orbitrap and TSQ Quantiva™ triple quadrupole) were used. However, both the MS and MS/MS spectra of non-derivatized oxysterols were ambiguous and/or unrepeatable for both of the instruments employed. Derivatizing oxysterols is more cumbersome, but provides more selective and reliable results, and Girard derivatization+nanoLC-ESI-MS continues to be our recommended choice for measuring oxysterols in very limited samples. These investigations also indicate that extra care should be taken to remove lipids prior to nanoLC of other analytes, as adsorbed oxysterols, etc. can compromise analysis. Copyright © 2015 Elsevier Inc. All rights reserved.

Electrical stimulation of the insular cortex as a novel target for the relief of refractory pain: An experimental approach in rodents.

PubMed

Dimov, Luiz Fabio; Toniolo, Elaine Flamia; Alonso-Matielo, Heloísa; de Andrade, Daniel Ciampi; Garcia-Larrea, Luis; Ballester, Gerson; Teixeira, Manoel Jacobsen; Dale, Camila Squarzoni

2018-07-02

Cortical electrical stimulation (CES) has shown to be an effective therapeutic alternative for neuropathic pain refractory to pharmacological treatment. The primary motor cortex(M1) was the main cortical target used in the vast majority of both invasive and non-invasive studies. Despite positive results M1-based approaches still fail to relieve pain in a significant proportion of individuals. It has been advocated that the direct stimulation of cortical areas directly implicated in the central integration of pain could increase the efficacy of analgesic brain stimulation. Here, we evaluated the behavioral effects of electrical stimulation of the insular cortex (ESI) on pain sensitivity in an experimental rat model of peripheral neuropathy, and have described the pathways involved. Animals underwent chronic constriction of the sciatic nerve in the right hind limb and had concentric electrodes implanted in the posterior dysranular insular cortex. Mechanical nociception responses were evaluated before and at the end of a 15-min session of ESI (60Hz, 210μs, 1V). ESI reversed mechanical hypersensitivity in the paw contralateral to the brain hemisphere stimulated, without inducing motor impairment in the open-field test. Pharmacological blockade of μ-opioid (MOR) or type 1-cannabinoid receptors (CB1R) abolished ESI-induced antinociceptive effects. Evaluation of CB1R and MOR spatial expression demonstrated differential modulation of CB1R and MOR in the periaqueductal gray matter (PAG) of ESI-treated rats in sub-areas involved in pain processing/modulation. These results indicate that ESI induces antinociception by functionally modulating opioid and cannabinoid systems in the PAG pain circuitry in rats with experimentally induced neuropathic pain. Copyright © 2017 Elsevier B.V. All rights reserved.

Studying the reducing potencies of antioxidants with the electrochemistry inherently present in electrospray ionization-mass spectrometry.

PubMed

Plattner, Sabine; Erb, Robert; Chervet, Jean-Pierre; Oberacher, Herbert

2014-01-01

In this proof-of-principle study, the applicability of electrospray ionization-mass spectrometry (ESI-MS) to characterize the reducing potencies of natural antioxidants is demonstrated. The ESI source represents a controlled-current electrochemical cell. The interfacial potential at the emitter electrode will be at or near the electrochemical potential of those reactions that sufficiently supply all the required current for the ESI circuit. Indicator molecules prone to oxidation in ESI such as amodiaquine were used to visualize the impact of reducing compounds on the interfacial potential. The extent of inhibition of the oxidation of the indicator molecule was found to be dependent on the kind and amount of antioxidant added. Concentration-inhibition curves were constructed and used to compare reducing potencies and to rank antioxidants. This ranking was found to be dependent on the electrode material-indicator molecule combination applied. For fast and automated characterization of the reducing potencies of electrochemically active molecules, a flow-injection system was combined with ESI-MS. Liquid chromatography was used to process complex biological samples, such as red and white wine. Due to their high content of different polyphenols, red wine fractions were found to exhibit higher reducing potencies than the corresponding white wine fractions. Furthermore, for 14 important natural antioxidants, the results obtained with the controlled-current EC-ESI-MS assay were compared to those obtained with chemical antioxidant assays. Irrespectively of the kind of assay used to test the reducing potency, gallic acid, quercetin, and epicatechin were found to be potent reductants. Other antioxidants performed well in one particular assay only. This observation suggests that different kinds of redox and antioxidant chemistry were assessed with each of the assays applied. Therefore, several assays should be used to comprehensively study antioxidants and their reducing potencies.

Assessing the evolution of soil moisture and vegetation conditions during the 2012 United States flash drought

USGS Publications Warehouse

Otkin, Jason A.; Anderson, Martha C.; Hain, Christopher; Svoboda, Mark; Johnson, David; Mueller, Richard; Tadesse, Tsegaye; Wardlow, Brian D.; Brown, Jesslyn

2016-01-01

This study examines the evolution of several model-based and satellite-derived drought metrics sensitive to soil moisture and vegetation conditions during the extreme flash drought event that impacted major agricultural areas across the central U.S. during 2012. Standardized anomalies from the remote sensing based Evaporative Stress Index (ESI) and Vegetation Drought Response Index (VegDRI) and soil moisture anomalies from the North American Land Data Assimilation System (NLDAS) are compared to the United States Drought Monitor (USDM), surface meteorological conditions, and crop and soil moisture data compiled by the National Agricultural Statistics Service (NASS).Overall, the results show that rapid decreases in the ESI and NLDAS anomalies often preceded drought intensification in the USDM by up to 6 wk depending on the region. Decreases in the ESI tended to occur up to several weeks before deteriorations were observed in the crop condition datasets. The NLDAS soil moisture anomalies were similar to those depicted in the NASS soil moisture datasets; however, some differences were noted in how each model responded to the changing drought conditions. The VegDRI anomalies tracked the evolution of the USDM drought depiction in regions with slow drought development, but lagged the USDM and other drought indicators when conditions were changing rapidly. Comparison to the crop condition datasets revealed that soybean conditions were most similar to ESI anomalies computed over short time periods (2–4 wk), whereas corn conditions were more closely related to longer-range (8–12 wk) ESI anomalies. Crop yield departures were consistent with the drought severity depicted by the ESI and to a lesser extent by the NLDAS and VegDRI datasets.

Analysis of antioxidants in insulation cladding of copper wire: a comparison of different mass spectrometric techniques (ESI-IT, MALDI-RTOF and RTOF-SIMS).

PubMed

Schnöller, Johannes; Pittenauer, Ernst; Hutter, Herbert; Allmaier, Günter

2009-12-01

Commercial copper wire and its polymer insulation cladding was investigated for the presence of three synthetic antioxidants (ADK STAB AO412S, Irganox 1010 and Irganox MD 1024) by three different mass spectrometric techniques including electrospray ionization-ion trap-mass spectrometry (ESI-IT-MS), matrix-assisted laser desorption/ionization reflectron time-of-flight (TOF) mass spectrometry (MALDI-RTOF-MS) and reflectron TOF secondary ion mass spectrometry (RTOF-SIMS). The samples were analyzed either directly without any treatment (RTOF-SIMS) or after a simple liquid/liquid extraction step (ESI-IT-MS, MALDI-RTOF-MS and RTOF-SIMS). Direct analysis of the copper wire itself or of the insulation cladding by RTOF-SIMS allowed the detection of at least two of the three antioxidants but at rather low sensitivity as molecular radical cations and with fairly strong fragmentation (due to the highly energetic ion beam of the primary ion gun). ESI-IT- and MALDI-RTOF-MS-generated abundant protonated and/or cationized molecules (ammoniated or sodiated) from the liquid/liquid extract. Only ESI-IT-MS allowed simultaneous detection of all three analytes in the extract of insulation claddings. The latter two so-called 'soft' desorption/ionization techniques exhibited intense fragmentation only by applying low-energy collision-induced dissociation (CID) tandem MS on a multistage ion trap-instrument and high-energy CID on a tandem TOF-instrument (TOF/RTOF), respectively. Strong differences in the fragmentation behavior of the three analytes could be observed between the different CID spectra obtained from either the IT-instrument (collision energy in the very low eV range) or the TOF/RTOF-instrument (collision energy 20 keV), but both delivered important structural information. Copyright 2009 John Wiley & Sons, Ltd.

Isotope-coded ESI-enhancing derivatization reagents for differential analysis, quantification and profiling of metabolites in biological samples by LC/MS: A review.

PubMed

Higashi, Tatsuya; Ogawa, Shoujiro

2016-10-25

The analysis of the qualitative and quantitative changes of metabolites in body fluids and tissues yields valuable information for the diagnosis, pathological analysis and treatment of many diseases. Recently, liquid chromatography/electrospray ionization-(tandem) mass spectrometry [LC/ESI-MS(/MS)] has been widely used for these purposes due to the high separation capability of LC, broad coverage of ESI for various compounds and high specificity of MS(/MS). However, there are still two major problems to be solved regarding the biological sample analysis; lack of sensitivity and limited availability of stable isotope-labeled analogues (internal standards, ISs) for most metabolites. Stable isotope-coded derivatization (ICD) can be the answer for these problems. By the ICD, different isotope-coded moieties are introduced to the metabolites and one of the resulting derivatives can serve as the IS, which minimize the matrix effects. Furthermore, the derivatization can improve the ESI efficiency, fragmentation property in the MS/MS and chromatographic behavior of the metabolites, which lead to a high sensitivity and specificity in the various detection modes. Based on this background, this article reviews the recently-reported isotope-coded ESI-enhancing derivatization (ICEED) reagents, which are key components for the ICD-based LC/MS(/MS) studies, and their applications to the detection, identification, quantification and profiling of metabolites in human and animal samples. The LC/MS(/MS) using the ICEED reagents is the powerful method especially for the differential analysis (relative quantification) of metabolites in two comparative samples, simultaneous quantification of multiple metabolites whose stable isotope-labeled ISs are not available, and submetabolome profiling. Copyright © 2016 Elsevier B.V. All rights reserved.

Concordance and population studies along with stutter and peak height ratio analysis for the PowerPlex ® ESX 17 and ESI 17 Systems.

PubMed

Hill, Carolyn R; Duewer, David L; Kline, Margaret C; Sprecher, Cynthia J; McLaren, Robert S; Rabbach, Dawn R; Krenke, Benjamin E; Ensenberger, Martin G; Fulmer, Patricia M; Storts, Douglas R; Butler, John M

2011-08-01

The PowerPlex(®) ESX 17 and ESI 17 Systems for short tandem repeat (STR) amplification were developed by the Promega Corporation to meet the European Network of Forensic Science Institutes (ENFSI) and the European DNA Profiling (EDNAP) Group recommendations for increasing the number of STR loci included in the European Standard Set (ESS). The PowerPlex ESX 17 and ESI 17 Systems utilize different PCR primer combinations to co-amplify the following 17 loci: D1S1656, D2S441, D2S1338, D3S1358, D8S1179, D10S1248, D12S391, D16S539, D18S51, D19S433, D21S11, D22S1045, FGA, TH01, vWA, SE33, and the sex-typing locus amelogenin. A total of 1443 U.S. population samples were evaluated with pre-commercialization versions of both kits. Stutter and heterozygote peak height ratios have been used to characterize kit performance. Typing results have been used to estimate the match probabilities provided by the chosen loci as well as in concordance studies. Full concordance between the typing results for the two kits was observed in 99.994% (49,055 out of 49,062) STR allele calls compared. All genotyping discrepancies were confirmed by DNA sequence analysis. As a result of these comparisons, a second forward primer for the D22S1045 locus has been added to the PowerPlex ESX 17 System to address a primer binding site mutation and the D1S1656 locus reverse primer in the PowerPlex ESI 17 System was modified to eliminate an amplification-efficiency reducing primer dimer. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Formation of oligomeric alkenylperoxides during the oxidation of unsaturated fatty acids: an electrospray ionization tandem mass spectrometry study.

PubMed

Villaverde, Juan José; Santos, Sónia A O; Maciel, Elisabete; Simões, Mário M Q; Pascoal Neto, Carlos; Domingues, M Rosário M; Silvestre, Armando J D

2012-02-01

This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS(2)), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe(2+)/H(2)O(2)) and Fe(2+)/O(2) systems. The reactions were followed by ferrous oxidation-xylenol orange method together with GC-MS and GC-FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH(·) radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI-MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra. Copyright © 2012 John Wiley & Sons, Ltd.

Binding of anions in triply interlocked coordination catenanes and dynamic allostery for dehalogenation reactions† †Electronic supplementary information (ESI) available: Characterization data and additional tables and figures. CCDC 1515722 and 1515723. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04070a

PubMed Central

Yang, Linlin; Jing, Xu; An, Bowen; Yang, Yang

2017-01-01

By synergistic combination of multicomponent self-assembly and template-directed approaches, triply interlocked metal organic catenanes that consist of two isolated chirally identical tetrahedrons were constructed and stabilized as thermodynamic minima. In the presence of suitable template anions, the structural conversion from the isolated tetrahedral conformers into locked catenanes occurred via the cleavage of an intrinsically reversible coordination bond in each of the tetrahedrons, followed by the reengineering and interlocking of two fragments with the regeneration of the broken coordination bonds. The presence of several kinds of individual pocket that were attributed to the triply interlocked patterns enabled the possibility of encapsulating different anions, allowing the dynamic allostery between the unlocked/locked conformers to promote the dehalogenation reaction of 3-bromo-cyclohexene efficiently, as with the use of dehalogenase enzymes. The interlocked structures could be unlocked into two individual tetrahedrons through removal of the well-matched anion templates. The stability and reversibility of the locked/unlocked structures were further confirmed by the catching/releasing process that accompanied emission switching, providing opportunities for the system to be a dynamic molecular logic system. PMID:29675152

First use of a divalent lanthanide for visible-light-promoted photoredox catalysis† †Electronic supplementary information (ESI) available. CCDC 1539923. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02479g

PubMed Central

Jenks, Tyler C.; Bailey, Matthew D.; Hovey, Jessica L.; Fernando, Shanilke; Basnayake, Gihan; Cross, Michael E.; Li, Wen

2017-01-01

We report the first catalytic use of a divalent lanthanide in visible-light-promoted bond-forming reactions. Our new precatalyst uses europium in the +2 oxidation state and is active in the presence of blue light from light-emitting diodes. The use of low-energy visible light reduces the occurrence of potential side reactions that might be induced by higher-energy UV light. The system described here uses zinc metal as a sacrificial reductant and is tolerant to wet, protic solvents. The catalyst can be made in situ from relatively inexpensive and air-stable EuCl3·6H2O, and the ligand can be synthesized in large quantities in two steps. With 0.5% loading of precatalyst, an average of 120 turnovers was observed in six hours for reductive coupling of benzyl chloride. We expect that the results will initiate the study of visible-light-promoted photoredox catalysis using divalent europium in a variety of reactions. PMID:29675173

Profiling of adrenocorticotropic hormone and arginine vasopressin in human pituitary gland and tumor thin tissue sections using droplet-based liquid-microjunction surface-sampling-HPLC–ESI-MS–MS

DOE PAGES

Kertesz, Vilmos; Calligaris, David; Feldman, Daniel R.; ...

2015-06-18

Described here are the results from the profiling of the proteins arginine vasopressin (AVP) and adrenocorticotropic hormone (ACTH) from normal human pituitary gland and pituitary adenoma tissue sections using a fully automated droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system for spatially resolved sampling, HPLC separation, and mass spectral detection. Excellent correlation was found between the protein distribution data obtained with this droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system and those data obtained with matrix assisted laser desorption ionization (MALDI) chemical imaging analyses of serial sections of the same tissue. The protein distributions correlated with the visible anatomic pattern of the pituitary gland.more » AVP was most abundant in the posterior pituitary gland region (neurohypophysis) and ATCH was dominant in the anterior pituitary gland region (adenohypophysis). The relative amounts of AVP and ACTH sampled from a series of ACTH secreting and non-secreting pituitary adenomas correlated with histopathological evaluation. ACTH was readily detected at significantly higher levels in regions of ACTH secreting adenomas and in normal anterior adenohypophysis compared to non-secreting adenoma and neurohypophysis. AVP was mostly detected in normal neurohypophysis as anticipated. This work demonstrates that a fully automated droplet-based liquid microjunction surface sampling system coupled to HPLC-ESI-MS/MS can be readily used for spatially resolved sampling, separation, detection, and semi-quantitation of physiologically-relevant peptide and protein hormones, such as AVP and ACTH, directly from human tissue. In addition, the relative simplicity, rapidity and specificity of the current methodology support the potential of this basic technology with further advancement for assisting surgical decision-making.« less

Profiling of adrenocorticotropic hormone and arginine vasopressin in human pituitary gland and tumor thin tissue sections using droplet-based liquid-microjunction surface-sampling-HPLC–ESI-MS–MS

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

Kertesz, Vilmos; Calligaris, David; Feldman, Daniel R.

Described here are the results from the profiling of the proteins arginine vasopressin (AVP) and adrenocorticotropic hormone (ACTH) from normal human pituitary gland and pituitary adenoma tissue sections using a fully automated droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system for spatially resolved sampling, HPLC separation, and mass spectral detection. Excellent correlation was found between the protein distribution data obtained with this droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system and those data obtained with matrix assisted laser desorption ionization (MALDI) chemical imaging analyses of serial sections of the same tissue. The protein distributions correlated with the visible anatomic pattern of the pituitary gland.more » AVP was most abundant in the posterior pituitary gland region (neurohypophysis) and ATCH was dominant in the anterior pituitary gland region (adenohypophysis). The relative amounts of AVP and ACTH sampled from a series of ACTH secreting and non-secreting pituitary adenomas correlated with histopathological evaluation. ACTH was readily detected at significantly higher levels in regions of ACTH secreting adenomas and in normal anterior adenohypophysis compared to non-secreting adenoma and neurohypophysis. AVP was mostly detected in normal neurohypophysis as anticipated. This work demonstrates that a fully automated droplet-based liquid microjunction surface sampling system coupled to HPLC-ESI-MS/MS can be readily used for spatially resolved sampling, separation, detection, and semi-quantitation of physiologically-relevant peptide and protein hormones, such as AVP and ACTH, directly from human tissue. In addition, the relative simplicity, rapidity and specificity of the current methodology support the potential of this basic technology with further advancement for assisting surgical decision-making.« less

New methodology for capillary electrophoresis with ESI-MS detection: Electrophoretic focusing on inverse electromigration dispersion gradient. High-sensitivity analysis of sulfonamides in waters.

PubMed

Malá, Zdena; Gebauer, Petr; Boček, Petr

2016-09-07

This article describes for the first time the combination of electrophoretic focusing on inverse electromigration dispersion (EMD) gradient, a new separation principle described in 2010, with electrospray-ionization (ESI) mass spectrometric detection. The separation of analytes along the electromigrating EMD profile proceeds so that each analyte is focused and concentrated within the profile at a particular position given by its pKa and ionic mobility. The proposed methodology combines this principle with the transport of the focused zones to the capillary end by superimposed electromigration, electroosmotic flow and ESI suction, and their detection by the MS detector. The designed electrolyte system based on maleic acid and 2,6-lutidine is suitable to create an inverse EMD gradient of required properties and its components are volatile enough to be compatible with the ESI interface. The characteristic properties of the proposed electrolyte system and of the formed inverse gradient are discussed in detail using calculated diagrams and computer simulations. It is shown that the system is surprisingly robust and allows sensitive analyses of trace amounts of weak acids in the pKa range between approx. 6 and 9. As a first practical application of electrophoretic focusing on inverse EMD gradient, the analysis of several sulfonamides in waters is reported. It demonstrates the potential of the developed methodology for fast and high-sensitivity analyses of ionic trace analytes, with reached LODs around 3 × 10(-9) M (0.8 ng mL(-1)) of sulfonamides in spiked drinking water without any sample pretreatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Time-Resolved Molecular Characterization of Limonene/Ozone Aerosol using High-Resolution Electrospray Ionization Mass Spectrometry

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

Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia

2009-09-09

Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100,000 (m/Δm). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O:C ratios, double bond equivalency (DBE) factors, and aromaticity indexes (AI) in hundreds of identified individual SOA species.

Rhodium(i)-catalyzed asymmetric [4 + 2] cycloaddition reactions of 2-alkylenecyclobutanols with cyclic enones through C–C bond cleavage: efficient access to trans-bicyclic compounds† †Electronic supplementary information (ESI) available. CCDC 1575240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04784c

PubMed Central

Zheng, Xinxin; Guo, Rui

2018-01-01

We report a rhodium-catalyzed asymmetric formal intermolecular [4 + 2] cycloaddition reaction of 2-alkylenecyclobutanols with α,β-unsaturated cyclic ketones leading to synthetically useful trans-bicyclic molecules. Three consecutive stereogenic centers are formed in a highly enantio- and diastereoselective manner. Stepwise C–C bond cleavage and annulation are likely involved in the reaction pathway. Here, iPr-Duphos is the viable chiral ligand that promotes excellent enantio-control. PMID:29675233

Does the thermal evolution of molecular structures critically affect the magnetic anisotropy?† †Electronic supplementary information (ESI) available. CCDC 1045631–1045633. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01245g

PubMed Central

Qian, Kang; Baldoví, José J.; Zhang, Yi-Quan; Overgaard, Jacob; Wang, Bing-Wu

2015-01-01

A dysprosium based single-ion magnet is synthesized and characterized by the angular dependence of the single-crystal magnetic susceptibility. Ab initio and effective electrostatic analyses are performed using the molecular structures determined from single crystal X-ray diffraction at 20 K, 100 K and 300 K. Contrary to the common assumption, the results reveal that the structural thermal effects that may affect the energy level scheme and magnetic anisotropy below 100 K are negligible. PMID:29568416

Rapid access to diverse, trifluoromethyl-substituted alkenes using complementary strategies† †Electronic supplementary information (ESI) available. CCDC 1811877, 1817386–1817390. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc05420c

PubMed Central

Phelan, James P.; Wiles, Rebecca J.; Lang, Simon B.; Kelly, Christopher B.

2018-01-01

Two synergistic approaches to the facile assembly of complex α-trifluoromethyl alkenes are described. Using α-trifluoromethyl-β-silyl alcohols as masked trifluoromethyl alkenes, cross-coupling or related functionalization processes at distal electrophilic sites can be executed without inducing Peterson elimination. Subsequent Lewis acidic activation affords functionalized α-trifluoromethyl alkenes. Likewise, the development of a novel α-trifluoromethylvinyl trifluoroborate reagent complements this approach and allows a one-step cross-coupling of (hetero)aryl halides to access a broad array of complex α-trifluoromethyl alkenes. PMID:29732105

[Eppendorf Schizophrenia Inventory (ESI) vs. Frankfurt Complaint Questionnaire (FCQ). Direct comparison in a clinical trial].

PubMed

Mass, R

2005-09-01

This study is the first to directly compare two clinical questionnaires which are both aimed at self-experienced cognitive dysfunctions of schizophrenia: Eppendorf Schizophrenia Inventory (ESI) and Frankfurt Complaint Questionnaire (FCQ). Evaluated were (a) diagnostic validity, (b) psychometric properties, (c) scale intercorrelations, and (d) factor analytic stability. Ad (a): schizophrenic subjects (n=36) show highly significant increases in the ESI scales and sum score when compared to other clinical groups (patients with depression, alcohol dependence, or obsessive-compulsive disorder, n>30, respectively); on the other hand, the FCQ yields no systematic group differences. Ad (b): mean of reliability coefficients (Cronbach alpha) of the ESI scales is r(tt)=0.86, mean of reliability coefficients of the FCQ scales is significantly lower. Ad (c): the mean intercorrelation between ESI and FCQ scales amounts to r(xy)=0.56 (minimum 0.29, maximum 0.73), corresponding to an average shared variance of about 31%. Ad (d): factor analysis yielded an ESI factor and a FBF factor; one-way ANOVA with the factor scores confirms the diagnostic validity of the ESI. ESI and FCQ measure essentially different aspects of schizophrenic psychopathology. Regarding reliability and diagnostic validity, the ESI is superior to the FCQ.

Comparisons of social interaction and activities of daily living between long-term care facility and community-dwelling stroke patients.

PubMed

Yoon, Jeong-Ae; Park, Se-Gwan; Roh, Hyo-Lyun

2015-10-01

[Purpose] This study was conducted to compare the correlation between social interaction and activities of daily living (ADL) between community-dwelling and long-term care facility stroke patients. [Subjects and Methods] The Subjects were 65 chronic stroke patients (32 facility-residing, 33 community-dwelling). The Evaluation Social Interaction (ESI) tool was used to evaluate social interaction and the Assessment of Motor and Process Skills (AMPS) measure was used to evaluate ADL. [Results] Both social interaction and ADL were higher in community-dwelling than facility-residing stroke patients. There was a correlation between ESI and ADL for both motor and process skills among facility-residing patients, while only ADL process skills and ESI correlated among community-dwelling patients. In a partial correlation analysis using ADL motor and process skills as control variables, only process skills correlated with ESI. [Conclusion] For rehabilitation of stroke patients, an extended treatment process that combines ADL and social activities is likely to be required. Furthermore, treatment programs and institutional systems that can improve social interaction and promote health maintenance for community-dwelling and facility-residing chronic stroke patients are needed throughout the rehabilitation process.

Screening anti-allergic components of Astragali Radix using LAD2 cell membrane chromatography coupled online with UHPLC-ESI-MS/MS method.

PubMed

Lv, Yanni; Sun, Yueming; Fu, Jia; Kong, Liyun; Han, Shengli

2017-02-01

Huangqi (Astragali Radix), a traditional Chinese herb, is widely used in clinical therapy in China. In addition, an anti-allergic effect of constituents in Huangqi has been reported in the scientific literature. In the present study, cell membrane chromatography coupled online with UHPLC-ESI-MS/MS method was developed to screen, analyze and identify the anti-allergic components of Huangqi. The Laboratory of Allergic Disease 2 (LAD2) cell was used to establish cell membrane chromatography, which was combined with UHPLC-ESI-MS/MS. The coupled system was then used to screen anti-allergic components from Huangqi. Effects of active components were verified by histamine release assay. A component retained on the LAD2 cell membrane chromatography was identified as formononetin. Bioactivity of formononetin was investigated by histamine release assay in LAD2 cells, and it was found that formononetin could inhibit histamine release in a dose-dependent manner from 1 to 100 μm. The LAD2 cell membrane chromatography online with UHPLC-ESI-MS/MS method is an effective technique for screening the anti-allergic components of Huangqi. Copyright © 2016 John Wiley & Sons, Ltd.

Identification of a Panax ginseng fruit fingerprint by HPLC-ESI-MS.

PubMed

Zhao, H F; Xu, F F; Guo, Y T; Mi, H

2016-03-11

Over many years, parts of Panax ginseng (root and rhizome) have been identified and applied for medical purposes as traditional Chinese herbal medicine. Recently, research has indicated that ginseng fruit also contains similar compounds and is as rich as the other parts of the ginseng. This discovery may dramatically improve the efficient of outputs derived from ginseng products. Here, a new technique combining high-performance liquid chromatography (HPLC) with electrospray ionization tandem mass spectrometry (ESI-MS) was employed to identify the fingerprint of P. ginseng fruit. Using HPLC, compounds that are important for medical purposes were extracted and purified. Combined with ESI-MS, the characteristic peaks (nine common peaks) of those compounds were identified, and the accuracy was confirmed by analysis using the Chromatographic Fingerprint Similarity Evaluation System (2004A edition). Overall, 15 batches of ginseng fruit had a similarity of more than 0.80, 13 batches of samples had a similarity between 0.97 and 0.99, and two batches had a similarity less than 0.90. The test solution and mobile phase selection was discussed. The HPLC-ESI-MS method can produce repeatable and reliable results and can be applied in the quality control of P. ginseng fruit.

A porous graphitized carbon LC-ESI/MS method for the quantitation of metronidazole and fluconazole in breast milk and human plasma.

PubMed

Geballa-Koukoula, Ariadni; Panderi, Irene; Zervas, Konstantinos; Geballa-Koukoulas, Khalil; Kavvalou, Eirini; Panteri-Petratou, Eirini; Vourna, Panagiota; Gennimata, Dimitra

2018-05-01

Information on drug transfer into the breast milk is essential to protect the infant from undesirable adverse effects of maternal consumption of drugs and to allow effective pharmacological treatment of breastfeeding mothers. Metronidazole and fluconazole are two drugs frequently used in nursing women to treat various infections, thus questioning infant's safety due to drug exposure through breast milk. In this article a porous graphitized carbon LC/ESI-MS assay was developed for the quantitation of metronidazole and fluconazole in breast milk and human plasma. The assay was based on the use of 150 μL of biological samples, following acetonitrile precipitation of proteins and filtration that enabled injection into the LC/ESI-MS system. All analytes and the internal standard, ropinirole, were separated by using a porous graphitized carbon analytical column (150 × 2.1 mm i.d., particle size 5 μm) with isocratic elution. The mobile phase consists of 55% acetonitrile in water acidified with 0.1% concentrated formic acid and pumped at a flow rate of 0.25 mL min -1 . The assay was linear over a concentration range of 0.1 to 15 μg mL -1 for all analytes in both biological samples. Intermediate precision was found to be <8.4% over the tested concentration ranges. A run time of <5 min for each sample made it possible to analyze a large number of biological samples per day. The method is the first reported application for the analysis of metronidazole and fluconazole in both breast milk and human plasma and it can be used to support a wide range of clinical studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Characterization and quantification of flavonoids and saponins in adzuki bean (Vigna angularis L.) by HPLC-DAD-ESI-MSn analysis.

PubMed

Liu, Rui; Cai, Zongwei; Xu, Baojun

2017-09-22

Bioactive activities of adzuki bean have been widely reported, however, the phytochemical information of adzuki bean is incomplete. The aim of this study was to characterize and quantify flavonoids and saponins in adzuki bean. High performance liquid chromatography with diode array detection and electro spray ionization-tandem multi-stage mass spectrometry (HPLC-DAD-ESI-MS n ) were applied to do qualitative and quantitative analyses. A total of 15 compounds from adzuki bean were identified by HPLC-DAD-ESI-MS n . Among 15 compounds identified, four flavonoids (catechin, vitexin-4″-O-glucoside, quercetin-3-O-glucoside, and quercetin-3-O-rutinoside) and six saponins (azukisaponin I, II, III, IV, V, and VI) in adzuki bean were further quantified by external calibration method using HPLC-MS with the program of time segment and extract ion chromatogram (EIC) analysis. Current qualitative and quantitative method based on HPLC and MS technique provides a scientific basis for in vitro and in vivo pharmacological study in the future. Graphical abstract Isolation and characterization of flavonoids and saponins from adzuki bean.

[Identification of chemical constituents in Sinopodophylli Fructus by HPLC-DAD-ESI-IT-TOF-MSn].

PubMed

Wang, Ai-Hua; Ma, Li-Man; Fan, Shan-Shan; Liu, Guang-Xue; Xu, Feng; Shang, Ming-Ying; Cai, Shao-Qing

2018-01-01

This experiment was performed to analyze and identify the chemical constituents of Sinopodophylli Fructus by HPLC-DAD-ESI-IT-TOF-MSn. The analysis was performed on an Agilent Zorbax SB-C₁₈ (4.6 mm×250 mm, 5 μm) column.The mobile phase consisted of 0.1% formic acid was used for gradient at a flow rate of 1.0 mL·min⁻¹. Electrospray ionization ion trap time-of-flight multistage mass spectrometry was applied for qualitative analysis under positive and negative ion modes. The results indicated that 54 compounds consisted of 18 lignans and 36 flavonoids from Xiaoyelian had been detected by their HRMS data, the information of literature and reference substance. Among them, 27 compounds were reported in Sinopodophylli Fructus for the first time. In conclusion, an HPLC-DAD-ESI-IT-TOF-MSn method was established to qualitative analysis of Xiaoyelian in this study, which will provide the evidence for evaluating the quality of Xiaoyelian herbs, clarifying the mechanism, and guiding the development of pharmacological active ingredients. Copyright© by the Chinese Pharmaceutical Association.

Liquid Chromatography Electrospray Ionization Mass Spectrometric (LC-ESI-MS) and Desorption Electrospray Ionization Mass Spectrometric (DESI-MS) Identification of Chemical Warfare Agents in Consumer Products

DTIC Science & Technology

2007-06-01

T ACanadaY Approved for PublicR Distribution Uln& Liquid Chromatography Electrospray Ionization Mass Spectrometric ( LC -ESI- MS) and Desorption...consumer products with chemical warfare agents or other toxic chemicals. Liquid chromatography electrospray ionization mass spectrometry ( LC -ESI-MS) and...house LC -ESI-MS and LC -ESI-MS/MS methods were evaluated for the determination of chemical warfare agents in spiked bottled water samples. The

Monolithic Integration of Two-Dimensional Liquid Chromatography-Capillary Electrophoresis and Electrospray Ionization on a Microfluidic Device

PubMed Central

Chambers, Andrew G.; Mellors, J. Scott; Henley, W. Hampton; Ramsey, J. Michael

2011-01-01

A microfluidic device capable of two-dimensional reversed-phase liquid chromatography-capillary electrophoresis with integrated electrospray ionization (LC-CE-ESI) for mass spectrometry (MS)-based proteomic applications is described. Traditional instrumentation was used for the LC sample injection and delivery of the LC mobile phase. The glass microfabricated device incorporated a sample-trapping region and an LC channel packed with reversed-phase particles. Rapid electrokinetic injections of the LC effluent into the CE dimension were performed at a cross channel intersection. The CE separation channel terminated at a corner of the square device, which functioned as an integrated electrospray tip. In addition to LC-CE-ESI, this device was used for LC-ESI without any instrumental modifications. To evaluate the system, LC-MS and LC-CE-MS analysis of protein digests were performed and compared. PMID:21214194

Energy Systems Integration News | Energy Systems Integration Facility |

Science.gov Websites

NREL News Energy Systems Integration News A monthly recap of the latest happenings at the Energy Systems Integration Facility and developments in energy systems integration (ESI) research at NREL ; said Vahan Gevorgian, chief engineer with NREL's Power Systems Engineering Center. "Results of

Characterization of dicarboxylic naphthenic acid fraction compounds utilizing amide derivatization: Proof of concept.

PubMed

Kovalchik, Kevin A; MacLennan, Matthew S; Peru, Kerry M; Ajaero, Chukwuemeka; McMartin, Dena W; Headley, John V; Chen, David D Y

2017-12-30

The characterization of naphthenic acid fraction compounds (NAFCs) in oil sands process affected water (OSPW) is of interest for both toxicology studies and regulatory reasons. Previous studies utilizing authentic standards have identified dicarboxylic naphthenic acids using two-dimensional gas chromatography hyphenated to time-of-flight mass spectrometry (GC × GC/TOFMS). The selective derivatization of hydroxyl groups has also recently aided in the characterization of oxy-NAFCs, and indirectly the characterization of dicarboxylic NAFCs. However, there has been no previous report of derivatization being used to directly aid in the standard-free characterization of NAFCs with multiple carboxylic acid functional groups. Herein we present proof-of-concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization. Carboxylic acid groups in OSPW extract and in a dicarboxylic acidstandard were derivatized to amides using a previously described method. The derivatized extract and derivatized standard were analyzed by direct-injection positive-mode electrospray ionization ((+)ESI) high-resolution mass spectrometry (HRMS), and the underivatized extract was analyzed by (-)ESI MS. Tandem mass spectrometry (MS/MS) was carried out on selected ions of the derivatized standard and derivatized OSPW. Data analysis was carried out using the Python programming language. The distribution of monocarboxylic NAFCs observed in the amide-derivatized OSPW sample by (+)ESI-MS was generally similar to that seen in underivatized OSPW by (-)ESI-MS. The dicarboxylic acid standard shows evidence of being doubly derivatized, although the second derivatization appears to be inefficient. Furthermore, a spectrum of potential diacid NAFCs is presented, identified by both charge state and derivatization mass. Interference due to the presence of multiple derivatization products is noted, but can be eliminated using on-line separation or an isotopically labelled derivatization reagent. Proof of concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization is demonstrated. Furthermore, (+)ESI-HRMS of the derivatized monocarboxylic NAFCS yields similar information to (-)ESI-MS analysis of underivatized NAFCs, with the benefit of added selectivity for carboxylic acid species and the characterization of diacids. Copyright © 2017 John Wiley & Sons, Ltd.

Influence of Sulfolane on ESI-MS Measurements of Protein-Ligand Affinities

NASA Astrophysics Data System (ADS)

Yao, Yuyu; Richards, Michele R.; Kitova, Elena N.; Klassen, John S.

2016-03-01

The results of an investigation into the influence of sulfolane, a commonly used supercharging agent, on electrospray ionization mass spectrometry (ESI-MS) measurements of protein-ligand affinities are described. Binding measurements carried out on four protein-carbohydrate complexes, lysozyme with β- d-GlcNAc-(1→4)-β- d-GlcNAc-(1→4)-β- d-GlcNAc-(1→4)- d-GlcNAc, a single chain variable fragment and α- d-Gal-(1→2)-[α- d-Abe-(1→3)]-α- d-Man-OCH3, cholera toxin B subunit homopentamer with β- d-Gal-(1→3)-β- d-GalNAc-(1→4)[α- d-Neu5Ac-(2→3)]-β- d-Gal-(1→4)-β- d-Glc, and a fragment of galectin 3 and α- l-Fuc-(1→2)-β- d-Gal-(1→3)-β- d-GlcNAc-(1→3)-β- d-Gal-(1→4)-β- d-Glc, revealed that sulfolane generally reduces the apparent (as measured by ESI-MS) protein-ligand affinities. To establish the origin of this effect, a detailed study was undertaken using the lysozyme-tetrasaccharide interaction as a model system. Measurements carried out using isothermal titration calorimetry (ITC), circular dichroism, and nuclear magnetic resonance spectroscopies reveal that sulfolane reduces the binding affinity in solution but does not cause any significant change in the higher order structure of lysozyme or to the intermolecular interactions. These observations confirm that changes to the structure of lysozyme in bulk solution are not responsible for the supercharging effect induced by sulfolane. Moreover, the agreement between the ESI-MS and ITC-derived affinities indicates that there is no dissociation of the complex during ESI or in the gas phase (i.e., in-source dissociation). This finding suggests that supercharging of lysozyme by sulfolane is not related to protein unfolding during the ESI process. Binding measurements performed using liquid sample desorption ESI-MS revealed that protein supercharging with sulfolane can be achieved without a reduction in affinity.

Influence of Sulfolane on ESI-MS Measurements of Protein-Ligand Affinities.

PubMed

Yao, Yuyu; Richards, Michele R; Kitova, Elena N; Klassen, John S

2016-03-01

The results of an investigation into the influence of sulfolane, a commonly used supercharging agent, on electrospray ionization mass spectrometry (ESI-MS) measurements of protein-ligand affinities are described. Binding measurements carried out on four protein-carbohydrate complexes, lysozyme with β-D-GlcNAc-(1→4)-β-D-GlcNAc-(1→4)-β-D-GlcNAc-(1→4)-D-GlcNAc, a single chain variable fragment and α-D-Gal-(1→2)-[α-D-Abe-(1→3)]-α-D-Man-OCH3, cholera toxin B subunit homopentamer with β-D-Gal-(1→3)-β-D-GalNAc-(1→4)[α-D-Neu5Ac-(2→3)]-β-D-Gal-(1→4)-β-D-Glc, and a fragment of galectin 3 and α-L-Fuc-(1→2)-β-D-Gal-(1→3)-β-D-GlcNAc-(1→3)-β-D-Gal-(1→4)-β-D-Glc, revealed that sulfolane generally reduces the apparent (as measured by ESI-MS) protein-ligand affinities. To establish the origin of this effect, a detailed study was undertaken using the lysozyme-tetrasaccharide interaction as a model system. Measurements carried out using isothermal titration calorimetry (ITC), circular dichroism, and nuclear magnetic resonance spectroscopies reveal that sulfolane reduces the binding affinity in solution but does not cause any significant change in the higher order structure of lysozyme or to the intermolecular interactions. These observations confirm that changes to the structure of lysozyme in bulk solution are not responsible for the supercharging effect induced by sulfolane. Moreover, the agreement between the ESI-MS and ITC-derived affinities indicates that there is no dissociation of the complex during ESI or in the gas phase (i.e., in-source dissociation). This finding suggests that supercharging of lysozyme by sulfolane is not related to protein unfolding during the ESI process. Binding measurements performed using liquid sample desorption ESI-MS revealed that protein supercharging with sulfolane can be achieved without a reduction in affinity.

Efficiently measuring dimensions of the externalizing spectrum model: Development of the Externalizing Spectrum Inventory-Computerized Adaptive Test (ESI-CAT).

PubMed

Sunderland, Matthew; Slade, Tim; Krueger, Robert F; Markon, Kristian E; Patrick, Christopher J; Kramer, Mark D

2017-07-01

The development of the Externalizing Spectrum Inventory (ESI) was motivated by the need to comprehensively assess the interrelated nature of externalizing psychopathology and personality using an empirically driven framework. The ESI measures 23 theoretically distinct yet related unidimensional facets of externalizing, which are structured under 3 superordinate factors representing general externalizing, callous aggression, and substance abuse. One limitation of the ESI is its length at 415 items. To facilitate the use of the ESI in busy clinical and research settings, the current study sought to examine the efficiency and accuracy of a computerized adaptive version of the ESI. Data were collected over 3 waves and totaled 1,787 participants recruited from undergraduate psychology courses as well as male and female state prisons. A series of 6 algorithms with different termination rules were simulated to determine the efficiency and accuracy of each test under 3 different assumed distributions. Scores generated using an optimal adaptive algorithm evidenced high correlations (r > .9) with scores generated using the full ESI, brief ESI item-based factor scales, and the 23 facet scales. The adaptive algorithms for each facet administered a combined average of 115 items, a 72% decrease in comparison to the full ESI. Similarly, scores on the item-based factor scales of the ESI-brief form (57 items) were generated using on average of 17 items, a 70% decrease. The current study successfully demonstrates that an adaptive algorithm can generate similar scores for the ESI and the 3 item-based factor scales using a fraction of the total item pool. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

A systematic review to assess comparative effectiveness studies in epidural steroid injections for lumbar spinal stenosis and to estimate reimbursement amounts.

PubMed

Bresnahan, Brian W; Rundell, Sean D; Dagadakis, Marissa C; Sullivan, Sean D; Jarvik, Jeffrey G; Nguyen, Hiep; Friedly, Janna L

2013-08-01

To systematically appraise published comparative effectiveness evidence (clinical and economic) of epidural steroid injections (ESI) for lumbar spinal stenosis and to estimate Medicare reimbursement amounts for ESI procedures. TYPE: Systematic review. PubMed, Embase, and CINAHL were searched through August 2012 for key words that pertain to low back pain, spinal stenosis or sciatica, and epidural steroid injection. We used institutional and Medicare reimbursement amounts for our cost estimation. Articles published in English that assessed ESIs for adults with lumbar spinal stenosis versus a comparison intervention were included. Our search identified 146 unique articles, and 138 were excluded due to noncomparative study design, not having a study population with lumbar spinal stenosis, not having an appropriate outcome, or not being in English. We fully summarized 6 randomized controlled trials and 2 large observational studies. Randomized controlled trial articles were reviewed, and the study population, sample size, treatment groups, ESI dosage, ESI approaches, concomitant interventions, outcomes, and follow-up time were reported. Descriptive resource use estimates for ESIs were calculated with use of data from our institution during 2010 and Medicare-based reimbursement amounts. ESIs or anesthetic injections alone resulted in better short-term improvement in walking distance compared with control injections. However, there were no longer-term differences. No differences between ESIs versus anesthetic in self-reported improvement in pain were reported. Transforaminal approaches had better improvement in pain scores (≤4 months) compared with interlaminar injections. Two observational studies indicated increased rates of lumbar ESI in Medicare beneficiaries. Our sample included 279 patients who received at least 1 ESI during 2010, with an estimated mean total outpatient reimbursement for one ESI procedure "event" to be $637, based on 2010 Medicare reimbursement amounts ($505 technical and $132 professional payments). This systematic review of ESI for treating lumbar spinal stenosis found a limited amount of data that suggest that ESI is effective in some patients for improving select short-term outcomes, but results differed depending on study design, outcome measures used, and comparison groups evaluated. Overall, there are relatively few comparative clinical or economic studies for ESI procedures for lumbar spinal stenosis in adults, which indicated a need for additional evidence. Copyright © 2013. Published by Elsevier Inc.

Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

PubMed

Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

2016-09-01

The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

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

Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu

2015-07-28

Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent developmentmore » in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.« less

Practical implications of some recent studies in electrospray ionization fundamentals.

PubMed

Cech, N B; Enke, C G

2001-01-01

In accomplishing successful electrospray ionization analyses, it is imperative to have an understanding of the effects of variables such as analyte structure, instrumental parameters, and solution composition. Here, we review some fundamental studies of the ESI process that are relevant to these issues. We discuss how analyte chargeability and surface activity are related to ESI response, and how accessible parameters such as nonpolar surface area and reversed phase HPLC retention time can be used to predict relative ESI response. Also presented is a description of how derivitizing agents can be used to maximize or enable ESI response by improving the chargeability or hydrophobicity of ESI analytes. Limiting factors in the ESI calibration curve are discussed. At high concentrations, these factors include droplet surface area and excess charge concentration, whereas at low concentrations ion transmission becomes an issue, and chemical interference can also be limiting. Stable and reproducible non-pneumatic ESI operation depends on the ability to balance a number of parameters, including applied voltage and solution surface tension, flow rate, and conductivity. We discuss how changing these parameters can shift the mode of ESI operation from stable to unstable, and how current-voltage curves can be used to characterize the mode of ESI operation. Finally, the characteristics of the ideal ESI solvent, including surface tension and conductivity requirements, are discussed. Analysis in the positive ion mode can be accomplished with acidified methanol/water solutions, but negative ion mode analysis necessitates special constituents that suppress corona discharge and facilitate the production of stable negative ions. Copyright 2002 Wiley Periodicals, Inc.

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

PubMed

Rodrigues, Maria A A; Mendes, Débora C; Ramamurthy, Vaidhyanathan; Da Silva, José P

2017-11-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br - , Cl - , F - ) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

Programmed serial stereochemical relay and its application in the synthesis of morphinans† †Electronic supplementary information (ESI) available. CCDC 1526432. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03189k Click here for additional data file. Click here for additional data file.

PubMed Central

Ho (Kenny) Park, Kun; Chen, Rui

2017-01-01

Herein we report a rationally designed, serial point-to-axial and axial-to-point stereoinduction and its integration into multi-step and target-oriented organic synthesis. In this proof-of-concept study, the configurational stability of several carefully designed atropisomeric intermediates and the fidelity of their unconventional stereoinductions were systematically investigated. The highly functionalized prepared synthetic intermediate was further applied in a novel chemical method to access the morphinans and it is potentially applicable to other structurally related alkaloids. PMID:29147530

End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS).

PubMed

Jackson, Anthony T; Slade, Susan E; Thalassinos, Konstantinos; Scrivens, James H

2008-10-01

The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis).

Unified approach to prenylated indole alkaloids: total syntheses of (–)-17-hydroxy-citrinalin B, (+)-stephacidin A, and (+)-notoamide I† †Electronic supplementary information (ESI) available. CCDC 1400755 and 1400756. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01977j

PubMed Central

Mercado-Marin, Eduardo V.

2015-01-01

A unified strategy for the synthesis of congeners of the prenylated indole alkaloids is presented. This strategy has yielded the first synthesis of the natural product (–)-17-hydroxy-citrinalin B as well as syntheses of (+)-stephacidin A and (+)-notoamide I. An enolate addition to an in situ generated isocyanate was utilized in forging a key bicyclo[2.2.2]diazaoctane moiety, and in this way connected the two structural classes of the prenylated indole alkaloids through synthesis. PMID:26417428

Biochemical and Pharmacological Characterizations of ESI-09 Based EPAC Inhibitors: Defining the ESI-09 “Therapeutic Window”

PubMed Central

Zhu, Yingmin; Chen, Haijun; Boulton, Stephen; Mei, Fang; Ye, Na; Melacini, Giuseppe; Zhou, Jia; Cheng, Xiaodong

2015-01-01

The cAMP signaling cascade is one of the most frequently targeted pathways for the development of pharmaceutics. A plethora of recent genetic and pharmacological studies suggest that exchange proteins directly activated by cAMP (EPACs) are implicated in multiple pathologies. Selective EPAC inhibitors have been recently developed. One specific inhibitor, ESI-09, has been shown to block EPAC activity and functions, as well as to recapitulate genetic phenotypes of EPAC knockout mice when applied in vivo. However, a recent study raised concern that ESI-09 might act as a non-specific protein denaturant. Herein, we present a detailed biochemical and pharmacological characterization, as well as a structure-activity relationship (SAR) analysis of ESI-09. Our studies show that ESI-09 dose-dependently inhibits activity of both EPAC1 and EPAC2 with apparent IC50 values well below the concentrations shown to induce “protein denaturation”. Moreover, the ESI-09's action towards EPAC proteins is highly sensitive to minor modifications of the 3-chlorophenyl moiety. Taken together, these results demonstrate that ESI-09 indeed acts as an EPAC specific antagonist and does not significantly destabilize/denature proteins at pharmacological effective concentrations. This conclusion is further supported by NMR data showing that ESI-09 induces residue-dependent chemical shift changes at low concentrations, while preserving well dispersed peaks. PMID:25791905

Biochemical and pharmacological characterizations of ESI-09 based EPAC inhibitors: defining the ESI-09 "therapeutic window".

PubMed

Zhu, Yingmin; Chen, Haijun; Boulton, Stephen; Mei, Fang; Ye, Na; Melacini, Giuseppe; Zhou, Jia; Cheng, Xiaodong

2015-03-20

The cAMP signaling cascade is one of the most frequently targeted pathways for the development of pharmaceutics. A plethora of recent genetic and pharmacological studies suggest that exchange proteins directly activated by cAMP (EPACs) are implicated in multiple pathologies. Selective EPAC inhibitors have been recently developed. One specific inhibitor, ESI-09, has been shown to block EPAC activity and functions, as well as to recapitulate genetic phenotypes of EPAC knockout mice when applied in vivo. However, a recent study raised concern that ESI-09 might act as a non-specific protein denaturant. Herein, we present a detailed biochemical and pharmacological characterization, as well as a structure-activity relationship (SAR) analysis of ESI-09. Our studies show that ESI-09 dose-dependently inhibits activity of both EPAC1 and EPAC2 with apparent IC50 values well below the concentrations shown to induce "protein denaturation". Moreover, the ESI-09's action towards EPAC proteins is highly sensitive to minor modifications of the 3-chlorophenyl moiety. Taken together, these results demonstrate that ESI-09 indeed acts as an EPAC specific antagonist and does not significantly destabilize/denature proteins at pharmacological effective concentrations. This conclusion is further supported by NMR data showing that ESI-09 induces residue-dependent chemical shift changes at low concentrations, while preserving well dispersed peaks.

Insight into Signal Response of Protein Ions in Native ESI-MS from the Analysis of Model Mixtures of Covalently Linked Protein Oligomers.

PubMed

Root, Katharina; Wittwer, Yves; Barylyuk, Konstantin; Anders, Ulrike; Zenobi, Renato

2017-09-01

Native ESI-MS is increasingly used for quantitative analysis of biomolecular interactions. In such analyses, peak intensity ratios measured in mass spectra are treated as abundance ratios of the respective molecules in solution. While signal intensities of similar-size analytes, such as a protein and its complex with a small molecule, can be directly compared, significant distortions of the peak ratio due to unequal signal response of analytes impede the application of this approach for large oligomeric biomolecular complexes. We use a model system based on concatenated maltose binding protein units (MBPn, n = 1, 2, 3) to systematically study the behavior of protein mixtures in ESI-MS. The MBP concatamers differ from each other only by their mass while the chemical composition and other properties remain identical. We used native ESI-MS to analyze model mixtures of MBP oligomers, including equimolar mixtures of two proteins, as well as binary mixtures containing different fractions of the individual components. Pronounced deviation from a linear dependence of the signal intensity with concentration was observed for all binary mixtures investigated. While equimolar mixtures showed linear signal dependence at low concentrations, distinct ion suppression was observed above 20 μM. We systematically studied factors that are most often used in the literature to explain the origin of suppression effects. Implications of this effect for quantifying protein-protein binding affinity by native ESI-MS are discussed in general and demonstrated for an example of an anti-MBP antibody with its ligand, MBP. Graphical Abstract ᅟ.

High-resolution liquid chromatography/electrospray ionization time-of-flight mass spectrometry combined with liquid chromatography/electrospray ionization tandem mass spectrometry to identify polyphenols from grape antioxidant dietary fiber.

PubMed

Touriño, Sonia; Fuguet, Elisabet; Jáuregui, Olga; Saura-Calixto, Fulgencio; Cascante, Marta; Torres, Josep Lluís

2008-11-01

Grape antioxidant dietary fiber (GADF) is a dietary supplement that combines the benefits of both fiber and antioxidants that help prevent cancer and cardiovascular diseases. The antioxidant polyphenolic components in GADF probably help prevent cancer in the digestive tract, where they are bioavailable. Mass spectrometry coupled to liquid chromatography is a powerful tool for the analysis of complex plant derivatives such as GADF. We use a combination of MS techniques, namely liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF-MS) and liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) on a triple quadrupole, for the identification of the polyphenolic constituents of the soluble fraction of GADF. First, we separated the mixture into four fractions which were tested for phenolic constituents using the TOF system in the full scan mode. The high sensitivity and resolution of the TOF detector over the triple quadrupole facilitate the preliminary characterization of the fractions. Then we used LC/ESI-MS/MS to identify the individual phenols through MS/MS experiments (product ion scan, neutral loss scan, precursor ion scan). Finally, most of the identities were unequivocally confirmed by accurate mass measurements on the TOF spectrometer. LC/ESI-TOF-MS combined with MS/MS correctly identifies the bioactive polyphenolic components from the soluble fraction of GADF. High-resolution TOF-MS is particularly useful for identifying the structure of compounds with the same LC/ESI-MS/MS fragmentation patterns.

Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary

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

Gary S. Groenewold; Jean-Jacques Gaumet

2011-12-01

Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were supplied via a target capillary orthogonally situated with respect to the electrospray. Comparison with direct electrospray (ESI) showed that the same coordination complexes were produced in each experiment, and could be described by the general formula [Ce(NO3)m=0-2(TBP)n](3-m)+. This result indicates that DESI has utility for measuring metal speciation for metal ligand solutions where the gas-phase complexes generated by ESI have been correlated with solution speciation. Such an application wouldmore » be useful for analyses where it is desirable to limit the total amount of metal being handled, or that have solvent systems that are not readily amenable to ESI. Both the direct ESI and DESI mass spectra showed similar trends with respect to the TBP:Ce ratio, viz. high values tend to favor formation of a larger fraction of the 1+ species, and the 2+ and 3+ species become relatively more important as the ratio is decreased. Within individual charge state ion envelopes, lower TBP:Ce ratios produce coordination complexes with fewer ligands, a trend also seen using both approaches. These trends again point toward strong similarity between the direct ESI and DESI analyses of the metal-ligand solutions. The DESI experiments were less sensitive for measuring the coordination complexes compared to the direct ESI experiments, by a factor of 10 - 100 depending on whether minimum detectable concentration or absolute ion abundances were considered. Nevertheless, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.« less

On the Ionization and Ion Transmission Efficiencies of Different ESI-MS Interfaces

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

Cox, Jonathan T.; Marginean, Ioan; Smith, Richard D.

2014-09-30

It is well known that the achievable sensitivity of electrospray ionization mass spectrometry (ESI-MS) is largely determined by the ionization efficiency in the ESI source and ion transmission efficiency through the ESI-MS interface. In this report we systematically study the ion transmission and ionization efficiencies in different ESI-MS interface configurations. The configurations under investigation include a single emitter/single inlet capillary, single emitter/multi-inlet capillary, and a subambient pressure ionization with nanoelectrospray (SPIN) MS interfaces with a single emitter and an emitter array, respectively. We present an effective method to evaluate the overall ion utilization efficiency of an ESI-MS interface by measuringmore » the total gas phase ion current transmitted through the interface and correlating it to the observed ion abundance measured in the corresponding mass spectrum. Our experimental results suggest that the overall ion utilization efficiency in the SPIN-MS interface configurations is better than that in the inlet capillary based ESI-MS interface configurations.« less

An analytical approach based on ESI-MS, LC-MS and PCA for the quali-quantitative analysis of cycloartane derivatives in Astragalus spp.

PubMed

Napolitano, Assunta; Akay, Seref; Mari, Angela; Bedir, Erdal; Pizza, Cosimo; Piacente, Sonia

2013-11-01

Astragalus species are widely used as health foods and dietary supplements, as well as drugs in traditional medicine. To rapidly evaluate metabolite similarities and differences among the EtOH extracts of the roots of eight commercial Astragalus spp., an approach based on direct analyses by ESI-MS followed by PCA of ESI-MS data, was carried out. Successively, quali-quantitative analyses of cycloartane derivatives in the eight Astragalus spp. by LC-ESI-MS(n) and PCA of LC-ESI-MS data were performed. This approach allowed to promptly highlighting metabolite similarities and differences among the various Astragalus spp. PCA results from LC-ESI-MS data of Astragalus samples were in reasonable agreement with both PCA results of ESI-MS data and quantitative results. This study affords an analytical method for the quali-quantitative determination of cycloartane derivatives in herbal preparations used as health and food supplements. Copyright © 2013 Elsevier B.V. All rights reserved.

Newly Branded Energy Systems Integration Group Joins International

Science.gov Websites

research fellow at NREL. Likewise, UVIG sees opportunity in partnering with iiESI. The international Group Joins International Institute for Energy Systems Integration Newly Branded Energy Systems Integration Group Joins International Institute for Energy Systems Integration March 22, 2018 The world of

Novel multistep BRET-FRET energy transfer using nanoconjugates of firefly proteins, quantum dots, and red fluorescent proteins

NASA Astrophysics Data System (ADS)

Alam, Rabeka; Zylstra, Joshua; Fontaine, Danielle M.; Branchini, Bruce R.; Maye, Mathew M.

2013-05-01

Sequential bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET) from firefly luciferase to red fluorescent proteins using quantum dot or rod acceptor/donor linkers is described. The effect of morphology and tuned optical properties on the efficiency of this unique BRET-FRET system was evaluated.Sequential bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET) from firefly luciferase to red fluorescent proteins using quantum dot or rod acceptor/donor linkers is described. The effect of morphology and tuned optical properties on the efficiency of this unique BRET-FRET system was evaluated. Electronic supplementary information (ESI) available: Experimental details, Fig. S1 and Table S1-S4. See DOI: 10.1039/c3nr01842c

Intra- versus intermolecular electron transfer in radical nucleophilic aromatic substitution of dihalo(hetero)arenes – a tool for estimating π-conjugation in aromatic systems† †Electronic supplementary information (ESI) available: Experimental details and procedures, 1H and 13C NMR data, GC traces and mass spectra. CCDC 1526301 and 1526302. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00100b Click here for additional data file. Click here for additional data file.

PubMed Central

Janhsen, B.; Daniliuc, C. G.

2017-01-01

In this paper, the application of the double radical nucleophilic aromatic substitution (SRN1) in various dihalogenated, mostly diiodinated, π-conjugated systems as a tool for qualitatively estimating their π-conjugation is described. This approach uses electron delocalisation as a measure of π-conjugation. Electron injection into the π-system is achieved via reaction of an intermediate aryl radical, itself generated from a dihalogenated π-system via SET-reduction of the C–I bond and subsequent reaction with a thiolate anion. The generated arene radical anion can then further react with the second aryl-halogen moiety within the π-system via an intramolecular electron transfer process. The efficiency of this intramolecular electron transfer is related to the π-conjugation of the radical anion. If the π-conjugation within the aromatic unit is weak, the arene radical anion reacts via an intermolecular ET with the starting dihalide. The intramolecular ET process delivers a product of a double SRN1 substitution whereas the intermolecular ET pathway provides a product of a mono- SRN1 substitution. By simple product analysis of mono- versus double substitution, π-conjugation can be qualitatively evaluated. This mechanistic tool is applied to various dihalogenated π-conjugated systems and the results are discussed within the context of π-conjugation. The conjugation mode within the π-system and the length of the aromatic system are varied, and the effect of relative positioning of the two halides within small π-systems is also addressed. PMID:28580099

Sensitivity improvement in hydrophilic interaction chromatography negative mode electrospray ionization mass spectrometry using 2-(2-methoxyethoxy)ethanol as a post-column modifier for non-targeted metabolomics.

PubMed

Koch, Wendelin; Forcisi, Sara; Lehmann, Rainer; Schmitt-Kopplin, Philippe

2014-09-26

The application of ammonia acetate buffered liquid chromatography (LC) eluents is known to concomitantly lead to ion suppression when electrospray ionization mass spectrometry (ESI-MS) detection is used. In negative ESI mode, post column infusion of 2-(2-methoxyethoxy)ethanol (2-MEE) was shown in the literature to help to compensate this adverse effect occurring in reversed phase liquid chromatography mass spectrometry (RP-LC-MS) analyses. Here a setup of direct infusion and hydrophilic interaction chromatography (HILIC) post-column infusion experiments was established in order to investigate systematically the beneficial effects of 2-MEE. We demonstrate that, 2-MEE can help to improve ESI-MS sensitivity in HILIC too and reveal analyte structure specific behaviors. Our study indicates that 2-MEE especially improves ESI response for small and polar molecules. The ESI response of stable isotope labeled amino acids spiked into biological matrices increases up to 50-fold (i.e. D5-l-glutamic acid) when post column infusion of 2-MEE is applied. A non-targeted analysis of a pooled urine sample via HILIC-ESI-QTOF-MS supports this hypothesis. In direct infusion, the combined application of an ammonia acetate buffered solution together with 2-MEE results in an improved ESI response compared to a non-buffered solution. We observed up to 60-fold increased ESI response of l-lysine. We propose this effect is putatively caused by the formation of smaller ESI droplets and stripping of positive charge from ESI droplets due to evaporation of acetic acid anions. In summary, post-column infusion of 2-MEE especially enhances ESI response of small and polar molecules. Therefore it can be regarded as a valuable add-on in targeted or non-targeted metabolomic HILIC-MS studies since this method sets a focus on this molecule category. Copyright © 2014 Elsevier B.V. All rights reserved.

What Is Energy Systems Integration? | Energy Systems Integration Facility |

Science.gov Websites

NREL What Is Energy Systems Integration? What Is Energy Systems Integration? Energy systems integration (ESI) is an approach to solving big energy challenges that explores ways for energy systems to Research Community NREL is a founding member of the International Institute for Energy Systems Integration

The Association between Exit Site Infection and Subsequent Peritonitis among Peritoneal Dialysis Patients

PubMed Central

van Diepen, Anouk T.N.; Tomlinson, George A.

2012-01-01

Summary Background and objectives Peritonitis is the most common infectious complication seen in peritoneal dialysis (PD). Traditionally, exit site infection (ESI) has been thought to predispose PD patients to peritonitis, although the risks have not been quantified. This study aimed to quantify the risk of PD peritonitis after ESI. Design, setting, participants, & measurements Data from 203 clinically stable PD patients >18 years of age who were followed as part of a randomized controlled trial over 18 months were used to estimate the risk of developing peritonitis within 30 days of an ESI compared with individuals who did not have a recent ESI. Sensitivity analyses were performed at 15, 45, and 60 days. Results Patients were mostly male (64.5%) and Caucasian, with a mean age of 60.5±14.4 years. There were 44 ESIs and 87 peritonitis episodes during the 18-month study. Seven patients had an ESI followed by peritonitis within 30 days. Using a frailty model, patients who had an ESI had a significantly higher risk of developing peritonitis within 30 days, even if the ESI was appropriately treated. This risk was maximal early on and diminished with time, with hazard ratios (95% confidence interval) of 11.1 at 15 days (HR=11.1, 95% CI=4.9–25.1), 5.3 at 45 days (2.5–11.3), and 4.9 at 60 days (2.4–9.9). In 2.3% of patients, subsequent peritonitis was caused by the same organism as the previous ESI. Conclusions A strong association between a treated ESI and subsequent PD peritonitis was present up to 60 days after initial diagnosis. PMID:22745277

Comparison of piracetam measured with HPLC-DAD, HPLC-ESI-MS, DIP-APCI-MS, and a newly developed and optimized DIP-ESI-MS.

PubMed

Lenzen, Claudia; Winterfeld, Gottfried A; Schmitz, Oliver J

2016-06-01

The direct inlet probe-electrospray ionization (DIP-ESI) presented here was based on the direct inlet probe-atmospheric pressure chemical ionization (DIP-APCI) developed by our group. It was coupled to an ion trap mass spectrometer (MS) for the detection of more polar compounds such as degradation products from pharmaceuticals. First, the position of the ESI tip, the gas and solvent flow rates, as well as the gas temperature were optimized with the help of the statistic program Minitab® 17 and a caffeine standard. The ability to perform quantitative analyses was also tested by using different concentrations of caffeine and camphor. Calibration curves with a quadratic calibration regression of R (2) = 0.9997 and 0.9998 for caffeine and camphor, respectively, were obtained. The limit of detection of 2.5 and 1.7 ng per injection for caffeine and camphor were determined, respectively. Furthermore, a solution of piracetam was used to compare established analytical methods for this drug and its impurities such as HPLC-diode array detector (DAD) and HPLC-ESI-MS with the DIP-APCI and the developed DIP-ESI. With HPLC-DAD and 10 μg piracetam on column, no impurity could be detected. With HPLC-ESI-MS, two impurities (A and B) were identified with only 4.6 μg piracetam on column, while with DIP-ESI, an amount of 1.6 μg piracetam was sufficient. In the case of the DIP-ESI measurements, all detected impurities could be identified by MS/MS studies. Graphical Abstract Scheme of the DIP-ESI principle.

A Magnetic Bead-Integrated Chip for the Large Scale Manufacture of Normalized esiRNAs

PubMed Central

Wang, Zhao; Huang, Huang; Zhang, Hanshuo; Sun, Changhong; Hao, Yang; Yang, Junyu; Fan, Yu; Xi, Jianzhong Jeff

2012-01-01

The chemically-synthesized siRNA duplex has become a powerful and widely used tool for RNAi loss-of-function studies, but suffers from a high off-target effect problem. Recently, endoribonulease-prepared siRNA (esiRNA) has been shown to be an attractive alternative due to its lower off-target effect and cost effectiveness. However, the current manufacturing method for esiRNA is complicated, mainly in regards to purification and normalization on a large-scale level. In this study, we present a magnetic bead-integrated chip that can immobilize amplification or transcription products on beads and accomplish transcription, digestion, normalization and purification in a robust and convenient manner. This chip is equipped to manufacture ready-to-use esiRNAs on a large-scale level. Silencing specificity and efficiency of these esiRNAs were validated at the transcriptional, translational and functional levels. Manufacture of several normalized esiRNAs in a single well, including those silencing PARP1 and BRCA1, was successfully achieved, and the esiRNAs were subsequently utilized to effectively investigate their synergistic effect on cell viability. A small esiRNA library targeting 68 tyrosine kinase genes was constructed for a loss-of-function study, and four genes were identified in regulating the migration capability of Hela cells. We believe that this approach provides a more robust and cost-effective choice for manufacturing esiRNAs than current approaches, and therefore these heterogeneous RNA strands may have utility in most intensive and extensive applications. PMID:22761791

Contraception and hormonal management in the perimenopause.

PubMed

Long, Margaret E; Faubion, Stephanie S; MacLaughlin, Kathy L; Pruthi, Sandhya; Casey, Petra M

2015-01-01

This literature review focuses on contraception in perimenopausal women. As women age, their fecundity decreases but does not disappear until menopause. After age 40, 75% of pregnancies are unplanned and may result in profound physical and emotional impact. Clinical evaluation must be relied on to diagnose menopause, since hormonal levels fluctuate widely. Until menopause is confirmed, some potential for pregnancy remains; at age 45, women's sterility rate is 55%. Older gravidas experience higher rates of diabetes, hypertension, and death. Many safe and effective contraceptive options are available to perimenopausal women. In addition to preventing an unplanned and higher-risk pregnancy, perimenopausal contraception may improve abnormal uterine bleeding, hot flashes, and menstrual migraines. Long-acting reversible contraceptives, including the levonorgestrel intrauterine system (LNG-IUS), the etonogestrel subdermal implant (ESI), and the copper intrauterine device (Cu-IUD), provide high efficacy without estrogen. LNG-IUS markedly decreases menorrhagia commonly seen in perimenopause. Both ESI and LNG-IUS provide endometrial protection for women using estrogen for vasomotor symptoms. Women without cardiovascular risk factors can safely use combined hormonal contraception. The CDC's Medical Eligibility Criteria for Contraceptive Use informs choices for women with comorbidities. No medical contraindications exist for levonorgestrel emergency-contraceptive pills, though obesity does decrease efficacy. In contrast, the Cu-IUD provides reliable emergency and ongoing contraception regardless of body mass index (BMI).

An assessment of emergy, energy, and cost-benefits of grain production over 6 years following a biochar amendment in a rice paddy from China.

PubMed

Wang, Lei; Li, Lianqing; Cheng, Kun; Ji, Chunying; Yue, Qian; Bian, Rongjun; Pan, Genxing

2018-04-01

Biochar soil amendment had been increasingly advocated for improving crop productivity and reducing carbon footprint in agriculture worldwide. However, the long-term benefits of biochar application with farming systems had not been thoroughly understood. This study quantified and assessed emergy, energy, and economic benefits of rice and wheat production throughout 6 rotation years following a single biochar amendment in a rice paddy from Southeastern China. Using the data from farm inventory, the quantified emergy indices included grain outputs, unit emergy value, and relative percentage of free renewable resources, environmental loading ratio, emergy yield ratio, and emergy sustainability index (ESI). The results indicated contrasting differences in these emergy values between biochar-amended and unamended production systems over the 6 years. The overall emergy efficiency of rice and wheat productions in biochar-amended system were higher by 11-28 and 15-47%, respectively, than that of unamended one of which the production being highly resource intensive. Moreover, ESI on average was 0.46 for rice and 0.63 for wheat in amended system, compared to 0.35 for rice and 0.39 for wheat in unamended one. Furthermore, over the 6 years following a single application, the ESI values showed considerable variation in the unamended system but consistently increasing in the amended system. Again, the biochar-amended system exerted significantly higher energy and economic return than the unamended one. Nonetheless, there was a tradeoff between rice and wheat in grain yield and net economic gain. Overall, biochar amendment could be a viable measure to improve the resilience of grain production while to reduce resource intensity and environment impacts in paddy soil from China.

Final expanded site inspection, ammunition storage area, Anniston Army Depot, Anniston, Alabama. Final report, September 1992-November 1994

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

Suomela, K.D.; Highsmith, R.L.; Rapuano, K.F.

1994-11-15

An Expanded Site Inspection (ESI) was conducted at the Anniston Army Depot (ANAD) Ammunition Storage Area (ASA). The objective of this ESI was to gather the information and data necessary to determine whether there is sufficient evidence of any release of contamination that would require additional investigation. The ASA contains 1,300 ammunition storage magazines and an ammunition maintenance workshop complex which includes buildings for maintenance, demilitarization, and inspection of all types of ammunition and their components. Fifteen Solid Waste Management Units (SWMUs) were the focus of the ESI, of which 11 were recommend for further investigation. The work included amore » review of historical records, field investigations, laboratory analyses, data interpretation, and report preparation. Contamination from volatile organic compounds and semi volatile organic compounds is not a major problem at the ASA. Arsenic, beryllium, cadmium, chromium, lead, mercury, nickel, silver, vanadium, zinc, explosives, and total petroleum hydrocarbons were detected above control screening values levels in one or more of the media sampled. Nitrate/nitrite and total organic carbon were also detected above control screening values in samples of groundwater, soil, and sediment from a number of SWMUs.« less

Understanding co-polymerization in amyloid formation by direct observation of mixed oligomers† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00620a Click here for additional data file.

PubMed Central

Young, Lydia M.; Tu, Ling-Hsien; Raleigh, Daniel P.; Ashcroft, Alison E.

2017-01-01

Although amyloid assembly in vitro is commonly investigated using single protein sequences, fibril formation in vivo can be more heterogeneous, involving co-assembly of proteins of different length, sequence and/or post-translational modifications. Emerging evidence suggests that co-polymerization can alter the rate and/or mechanism of aggregation and can contribute to pathogenicity. Electrospray ionization-ion mobility spectrometry-mass spectrometry (ESI-IMS-MS) is uniquely suited to the study of these heterogeneous ensembles. Here, ESI-IMS-MS combined with analysis of fibrillation rates using thioflavin T (ThT) fluorescence, is used to track the course of aggregation of variants of islet-amyloid polypeptide (IAPP) in isolation and in pairwise mixtures. We identify a sub-population of extended monomers as the key precursors of amyloid assembly, and reveal that the fastest aggregating sequence in peptide mixtures determines the lag time of fibrillation, despite being unable to cross-seed polymerization. The results demonstrate that co-polymerization of IAPP sequences radically alters the rate of amyloid assembly by altering the conformational properties of the mixed oligomers that form. PMID:28970890

Blue emitting undecaplatinum clusters

NASA Astrophysics Data System (ADS)

Chakraborty, Indranath; Bhuin, Radha Gobinda; Bhat, Shridevi; Pradeep, T.

2014-07-01

A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents.A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents. Electronic supplementary information (ESI) available: Details of experimental procedures, instrumentation, chromatogram of the crude cluster; SEM/EDAX, DLS, PXRD, TEM, FT-IR, and XPS of the isolated Pt11 cluster; UV/Vis, MALDI MS and SEM/EDAX of isolated 2 and 3; and 195Pt NMR of the K2PtCl6 standard. See DOI: 10.1039/c4nr02778g

Chemical characterisation of non-defective and defective green arabica and robusta coffees by electrospray ionization-mass spectrometry (ESI-MS).

PubMed

Mendonça, Juliana C F; Franca, Adriana S; Oliveira, Leandro S; Nunes, Marcella

2008-11-15

The coffee roasted in Brazil is considered to be of low quality, due to the presence of defective coffee beans that depreciate the beverage quality. These beans, although being separated from the non-defective ones prior to roasting, are still commercialized in the coffee trading market. Thus, it was the aim of this work to verify the feasibility of employing ESI-MS to identify chemical characteristics that will allow the discrimination of Arabica and Robusta species and also of defective and non-defective coffees. Aqueous extracts of green (raw) defective and non-defective coffee beans were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS) and this technique provided characteristic fingerprinting mass spectra that not only allowed for discrimination of species but also between defective and non-defective coffee beans. ESI-MS profiles in the positive mode (ESI(+)-MS) provided separation between defective and non-defective coffees within a given species, whereas ESI-MS profiles in the negative mode (ESI(-)-MS) provided separation between Arabica and Robusta coffees. Copyright © 2008 Elsevier Ltd. All rights reserved.

A Corona Discharge Initiated Electrochemical Electrospray Ionization Technique

PubMed Central

Lloyd, John R.; Hess, Sonja

2009-01-01

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity and selectivity of ESI experiments. Synopsis Using a standard ESI source a corona discharge initiated electrochemical ionization technique was established resulting from the electrochemistry occurring at the CD electrode surface. PMID:19747843

On the Ionization and Ion Transmission Efficiencies of Different ESI-MS Interfaces

PubMed Central

Cox, Jonathan T.; Marginean, Ioan; Smith, Richard D.; Tang, Keqi

2014-01-01

The achievable sensitivity of electrospray ionization mass spectrometry (ESI-MS) is largely determined by the ionization efficiency in the ESI source and ion transmission efficiency through the ESI-MS interface. These performance characteristics are difficult to evaluate and compare across multiple platforms as it is difficult to correlate electrical current measurements to actual analyte ions reaching the detector of a mass spectrometer. We present an effective method to evaluate the overall ion utilization efficiency of an ESI-MS interface by measuring the total gas phase ion current transmitted through the interface and correlating it to the observed ion abundance measured in the corresponding mass spectrum. Using this method we systematically studied the ion transmission and ionization efficiencies of different ESI-MS interface configurations, including a single emitter/single inlet capillary, single emitter/multi-inlet capillary, and a subambient pressure ionization with nanoelectrospray (SPIN) MS interface with a single emitter and an emitter array, respectively. Our experimental results indicate that the overall ion utilization efficiency of SPIN-MS interface configurations exceeds that of the inlet capillary-based ESI-MS interface configurations. PMID:25267087

On the ionization and ion transmission efficiencies of different ESI-MS interfaces.

PubMed

Cox, Jonathan T; Marginean, Ioan; Smith, Richard D; Tang, Keqi

2015-01-01

The achievable sensitivity of electrospray ionization mass spectrometry (ESI-MS) is largely determined by the ionization efficiency in the ESI source and ion transmission efficiency through the ESI-MS interface. These performance characteristics are difficult to evaluate and compare across multiple platforms as it is difficult to correlate electrical current measurements to actual analyte ions reaching the detector of a mass spectrometer. We present an effective method to evaluate the overall ion utilization efficiency of an ESI-MS interface by measuring the total gas-phase ion current transmitted through the interface and correlating it to the observed ion abundance measured in the corresponding mass spectrum. Using this method, we systematically studied the ion transmission and ionization efficiencies of different ESI-MS interface configurations, including a single emitter/single inlet capillary, single emitter/multi-inlet capillary, and a subambient pressure ionization with nanoelectrospray (SPIN) MS interface with a single emitter and an emitter array, respectively. Our experimental results indicate that the overall ion utilization efficiency of SPIN-MS interface configurations exceeds that of the inlet capillary-based ESI-MS interface configurations.

Characterization of nucleosides and nucleobases in natural Cordyceps by HILIC-ESI/TOF/MS and HILIC-ESI/MS.

PubMed

Zhao, Heng-Qiang; Wang, Xiao; Li, Hong-Mei; Yang, Bin; Yang, Hong-Jun; Huang, Luqi

2013-08-15

A method combining hydrophilic interaction chromatography (HILIC) and electrospray ionization mass spectrometry (ESI-MS) was developed for the characterization and determination of natural Cordyceps. Separation was achieved on a Waters Xbridge Amide column with gradient elution. Identification of 15 target nucleosides and nucleobases was based on retention time, UV spectra and mass measurements of the protonated molecules ([M+H]⁺) and main fragment ions (ESI-TOF/MS). Eight non-target compounds were tentatively identified by ESI-TOF/MS. The 15 target compounds were quantified by HILIC-ESI-MS/MS using time-programmed selective ion monitoring or multiple reaction monitoring in positive-ion mode under optimized mass conditions. This technique showed good linearity, repeatability and recovery. This approach was also successfully implemented in the analysis of nucleosides and nucleobases in 12 batches of natural Cordyceps samples that were collected from different regions in China. The developed HILIC-ESI-MS method exhibited clear advantages in identifying and determining highly polar bioactive components in Cordyceps, as well as their quality control.

Risk of Osteoporotic Fracture After Steroid Injections in Patients With Medicare.

PubMed

Carreon, Leah Y; Ong, Kevin L; Lau, Edmund; Kurtz, Steven M; Glassman, Steven D

To further evaluate the relationship between steroid injections and osteoporotic fracture risk, we analyzed Medicare administrative claims data on both large-joint steroid injections (LJSIs) into knee and hip and transforaminal steroid injections (TSIs), as well as osteoporotic hip and wrist fractures. Our hypothesis was that a systemic effect of steroid injections would increase fracture risk in all skeletal locations regardless of injection site, whereas a local effect would produce a disproportionate increased risk of spine fracture with spine injection. Patients treated with an LJSI, a TSI, or an epidural steroid injection (ESI) were identified from 5% Medicare claims data. Patients under age 65 years and patients with prior osteoporotic fracture were excluded. Analyses were performed to determine fracture risk (adjusted hazard ratio) for each type of injection. Analysis of the Medicare data revealed that ESIs were associated with decreased osteoporotic spine fracture risk, but the effect was small and might not be clinically relevant. ESIs did not influence osteoporotic hip or wrist fracture risk, but LJSIs reduced the risk.

Dual parallel mass apectrometry (LC1/MS2 and LC2/MS2) for lipid and vitamin D analysis

USDA-ARS?s Scientific Manuscript database

Atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and electrospray ionization (ESI) MS are complementary techniques that provide different types of information for lipids such as triacylglycerols, phospholipids, and fat-soluble vitamins. Since no one technique is by itself idea...

Dual Parallel Mass Spectrometry (LC1/MS2 and LC2/MS2) for Lipid and Vitamin D Analysis

USDA-ARS?s Scientific Manuscript database

Atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and electrospray ionization (ESI) MS are complementary techniques that provide different types of information for lipids such as triacylglycerols (TAGs), phospholipids, and fat-soluble vitamins. Since no one technique is by itsel...

LC-ESI-QTOF-MS based screening and identification of isomeric jujubogenin and pseudojujubogenin aglycones in Bacopa monnieri extract.

PubMed

Nuengchamnong, Nitra; Sookying, Sontaya; Ingkaninan, Kornkanok

2016-09-10

Bacopa monnieri (L.) Wettst. (Scrophulariaceae) is an Ayurvedic medicinal plant used as a memory enhancer. Its major chemical constituents are Bacopa saponins consisting of jujubogenin and pseudojujubogenin glycosides. These two aglycones are isomers different at the positions of prenyl substitution i.e., at C-23 for jujubogenin and at C-22 for pseudojujubogenin. In this study, we demonstrate the rapid and comprehensive characterization of saponin glycosides in B. monnieri using liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometer (LC-ESI-QTOF-MS). This shows that ESI-QTOF-MS in positive-ion mode, jujubogenin and pseudojujubogenin glycosides could be discriminated by the peak abundance ratio of m/z 455 [Aglycone+H-H2O](+) to m/z of 473 [Aglycone+H](+). Furthermore, the sequence of sugar moieties can be observed. In a similar manner, the isomeric saponins; deoxyjujubogenin and deoxypseudojujubogenin glycosides can be distinguished using the m/z 437[Aglycone+H-H2O](+) and m/z 455[Aglycone+H](+) peak ratio. Use of the negative-ion mode with MS/MS fragmentation can provide information about the type of sugar linked to the aglycone i.e., at m/z 633 (aglycone+glucose) or at m/z 603 (aglycone+arabinose). With our method, 62 chemical constituents in B. monnieri including saponin glycosides, flavonoids, and alkaloids were identified. This is the first systematic study in structural characterization on isomeric saponins and other metabolites in B. monnieri using ESI-QTOF-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

An analytical strategy to investigate Semen Strychni nephrotoxicity based on simultaneous HILIC-ESI-MS/MS detection of Semen Strychni alkaloids, tyrosine and tyramine in HEK 293t cell lysates.

PubMed

Gu, Liqiang; Hou, Pengyi; Zhang, Ruowen; Liu, Ziying; Bi, Kaishun; Chen, Xiaohui

2016-10-15

A Previous metabolomics study has demonstrated that tyrosine metabolism might be disrupted by treating with Semen Strychni on the cell nephrotoxicity model. To investigate the relationship between Semen Strychni alkaloids (SAs) and endogenous tyrosine, tyramine under the nephrotoxicity condition, an HILIC-ESI-MS/MS based analytical strategy was applied in this study. Based on the established Semen Strychni nephrotoxicity cell model, strychnine and brucine were identified and screened as the main SAs by an HPLC-Q Exactive hybrid quadrupole Orbitrap mass system. Then, a sensitive HILIC-ESI-MS/MS method was developed to simultaneously monitor strychnine, brucine, tyrosine and tyramine in cell lysate. The analytes were separated by a Shiseido CAPCELL CORE PC (150mm×2.1mm, 2.7μm) HILIC column in an acetonitrile/0.1% formic acid gradient system. All the calibration curves were linear with regression coefficients above 0.9924. The absolute recoveries were more than 80.5% and the matrix effects were between 91.6%-107.0%. With the developed method, analytes were successfully determined in cell lysates. Decreased levels of tyrosine and tyramine were observed only in combination with increased levels of SAs, indicating that the disturbance of tyrosine metabolism might be induced by the accumulation of SAs in kidney cell after exposure of Semen Strychni. The HILIC-ESI-MS/MS based analytical strategy is a useful tool to reveal the relationships between the toxic herb components and the endogenous metabolite profiling in the toxicity investigation of herb medicines. Copyright © 2016 Elsevier B.V. All rights reserved.

Persistent four-coordinate iron-centered radical stabilized by π-donation† †Electronic supplementary information (ESI) available: Experimental, crystallographic, computational details, and crystal data for 2, 4, 5 and 8. CCDC 1057111–1057113 and 1425703. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02601f Click here for additional data file. Click here for additional data file.

PubMed Central

Ishida, Shintaro; Hirakawa, Fumiya; Shiota, Yoshihito; Yoshizawa, Kazunari; Kanegawa, Shinji; Sato, Osamu; Nagashima, Hideo

2016-01-01

Dinuclear iron carbonyl complex 2, which contains an elongated unsupported Fe–Fe bond, was synthesized by the reaction between Fe2(CO)9 and phosphinyl radical 1. Thermal Fe–Fe bond homolysis led to the generation of a four-coordinate carbonyl-based iron-centered radical, 3, which is stabilized by π-donation. Complex 3 exhibited high reactivity toward organic radicals to form diamagnetic five-coordinate Fe(ii) complexes. PMID:28758000

Redox-promoted associative assembly of metal–organic materials† †Electronic supplementary information (ESI) available: Experimental procedures, compound characterization data, and X-ray crystallographic data for compounds 3–7 and 9–11. CCDC 1405641–1405645, 1429643, 1405647 and 1405648. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02214b Click here for additional data file. Click here for additional data file.

PubMed Central

Glavinović, Martin; Qi, Feng; Katsenis, Athanassios D.

2016-01-01

We develop an associative synthesis of metal–organic materials that combines solid-state metal oxidation and coordination-driven self-assembly into a one-step, waste-free transformation. The methodology hinges on the unique reactivity of ortho-quinones, which we introduce as versatile oxidants for mechanochemical synthesis. Our strategy opens a previously unexplored route to paramagnetic metal–organic materials from elementary metals. PMID:28791114

Organocatalytic, enantioselective synthesis of benzoxaboroles via Wittig/oxa-Michael reaction Cascade of α-formyl boronic acids† †Electronic supplementary information (ESI) available. CCDC 1487136. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc04522g Click here for additional data file. Click here for additional data file.

PubMed Central

Hazra, Gurupada; Maity, Sanjay; Bhowmick, Sudipto

2017-01-01

An unprecedented enantioselective synthesis of 3-substituted benzoxaboroles has been developed. An in situ generated ortho-boronic acid containing chalcone provides the chiral benzoxaboroles via an asymmetric oxa-Michael addition of hydroxyl group attached to the boronic acid triggered by the cinchona alkaloid based chiral amino-squaramide catalysts. In general, good yields with good to excellent enantioselectivities (up to 99%) were obtained. The resulting benzoxaboroles were converted to the corresponding chiral β-hydroxy ketones without affecting the enantioselectivity. PMID:28451370

Modular chiral gold(i) phosphite complexes†Electronic supplementary information (ESI) available: Experimental results and NMR data. CCDC 933751 (L11(AuCl)), 933752 (L12(AuCl)a), 933753 (L9(AuCl)), 933754 (L10(AuCl)), 933756 (L8(AuCl)), 933757 (L12(AuCl)e). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3cy00250kClick here for additional data file.Click here for additional data file.

PubMed

Delpont, Nicolas; Escofet, Imma; Pérez-Galán, Patricia; Spiegl, Dirk; Raducan, Mihai; Bour, Christophe; Sinisi, Riccardo; Echavarren, Antonio M

2013-10-07

Chiral gold(i) phosphite complexes are readily prepared modularly from 3,3'-bis(triphenylsilyl)-1,1'-bi-2-naphthol. These chiral gold(i) phosphite complexes are very reactive precatalysts for the [4+2] cycloaddition of aryl-substituted 1,6-enynes with enantiomeric ratios ranging from 86 : 14 up to 94 : 6.

Hydrogen gas storage in fluorinated ultramicroporous tunnel crystal

NASA Astrophysics Data System (ADS)

Kataoka, Keisuke; Katagiri, Toshimasa

2012-07-01

We report hydrogen storage at an ordinary pressure due to a bottle-neck effect of an ultramicroporous crystal. Stored hydrogen was kept at an ordinary pressure below -110 °C. The amounts of stored hydrogen gas linearly correlated with the initial pressures. These phenomena suggested the ultramicroporous tunnels worked as a molecular gas cylinder.We report hydrogen storage at an ordinary pressure due to a bottle-neck effect of an ultramicroporous crystal. Stored hydrogen was kept at an ordinary pressure below -110 °C. The amounts of stored hydrogen gas linearly correlated with the initial pressures. These phenomena suggested the ultramicroporous tunnels worked as a molecular gas cylinder. Electronic supplementary information (ESI) available. CCDC 246922. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30940h

ESI-MS, ESI-MS/MS fingerprint and LC-ESI-MS analysis of proathocyanidins from Bursera simaruba Sarg bark.

PubMed

Maldini, Mariateresa; Montoro, Paola; Piacente, Sonia; Pizza, Cosimo

2009-12-01

Direct flow injection/electrospray ionization/ion trap tandem mass spectrometry was used to investigate the presence of proanthocyanidins (PAs) in the methanolic extract of B. simaruba bark. Additionally, an LC-ESI-MS qualitative study was performed by using a monolithic stationary phase. The fragmentation pattern obtained evidenced the presence in B. simaruba bark of PAs belonging to the series of polymers of epicatechin, along with their glycosilated derivatives.

Characterization of a PEGylated protein therapeutic by ion exchange chromatography with on-line detection by native ESI MS and MS/MS.

PubMed

Muneeruddin, K; Bobst, C E; Frenkel, R; Houde, D; Turyan, I; Sosic, Z; Kaltashov, I A

2017-01-16

Detailed profiling of both enzymatic (e.g., glycosylation) and non-enzymatic (e.g., oxidation and deamidation) post-translational modifications (PTMs) is frequently required for the quality assessment of protein-based drugs. Challenging as it is, this task is further complicated for the so-called second-generation biopharmaceuticals, which also contain "designer PTMs" introduced to either enhance their pharmacokinetic profiles (e.g., PEGylated proteins) or endow them with therapeutic activity (e.g., protein-drug conjugates). Such modifications of protein covalent structure can dramatically increase structural heterogeneity, making the very notion of "molecular mass" meaningless, as ions representing different glycoforms of a PEGylated protein may have nearly identical distributions of ionic current as a function of m/z, making their contributions to the mass spectrum impossible to distinguish. In this work we demonstrate that a combination of ion exchange chromatography (IXC) with on-line detection by electrospray ionization mass spectrometry (ESI MS) and methods of ion manipulation in the gas phase (limited charge reduction and collision-induced dissociation) allows meaningful structural information to be obtained on a structurally heterogeneous sample of PEGylated interferon β-1a. IXC profiling of the protein sample gives rise to a convoluted chromatogram with several partially resolved peaks which can represent both deamidation and different glycosylation patterns within the protein, as well as varying extent of PEGylation. Thus, profiling the protein with on-line IXC/ESI/MS/MS allows it to be characterized by providing information on three different types of PTMs (designer, enzymatic and non-enzymatic) within a single protein therapeutic.

Informing Antibiotic Treatment Decisions: Evaluating Rapid Molecular Diagnostics To Identify Susceptibility and Resistance to Carbapenems against Acinetobacter spp. in PRIMERS III.

PubMed

Evans, Scott R; Hujer, Andrea M; Jiang, Hongyu; Hill, Carol B; Hujer, Kristine M; Mediavilla, Jose R; Manca, Claudia; Tran, Thuy Tien T; Domitrovic, T Nicholas; Higgins, Paul G; Seifert, Harald; Kreiswirth, Barry N; Patel, Robin; Jacobs, Michael R; Chen, Liang; Sampath, Rangarajan; Hall, Thomas; Marzan, Christine; Fowler, Vance G; Chambers, Henry F; Bonomo, Robert A

2017-01-01

The widespread dissemination of carbapenem-resistant Acinetobacter spp. has created significant therapeutic challenges. At present, rapid molecular diagnostics (RMDs) that can identify this phenotype are not commercially available. Two RMD platforms, PCR combined with electrospray ionization mass spectrometry (PCR/ESI-MS) and molecular beacons (MB), for detecting genes conferring resistance/susceptibility to carbapenems in Acinetobacter spp. were evaluated. An archived collection of 200 clinical Acinetobacter sp. isolates was tested. Predictive values for susceptibility and resistance were estimated as a function of susceptibility prevalence and were based on the absence or presence of beta-lactamase (bla) NDM, VIM, IMP, KPC, and OXA carbapenemase genes (e.g., bla OXA-23 , bla OXA-24/40 , and bla OXA-58 found in this study) against the reference standard of MIC determinations. According to the interpretation of MICs, 49% (n = 98) of the isolates were carbapenem resistant (as defined by either resistance or intermediate resistance to imipenem). The susceptibility sensitivities (95% confidence interval [CI]) for imipenem were 82% (74%, 89%) and 92% (85%, 97%) for PCR/ESI-MS and MB, respectively. Resistance sensitivities (95% CI) for imipenem were 95% (88%, 98%) and 88% (80%, 94%) for PCR/ESI-MS and MB, respectively. PRIMERS III establishes that RMDs can discriminate between carbapenem resistance and susceptibility in Acinetobacter spp. In the context of a known prevalence of resistance, SPVs and RPVs can inform clinicians regarding the best choice for empiric antimicrobial therapy against this multidrug-resistant pathogen. Copyright © 2016 American Society for Microbiology.

Quantification of γ-Aminobutyric Acid in Cerebrospinal Fluid Using Liquid Chromatography-Electrospray Tandem Mass Spectrometry.

PubMed

Arning, Erland; Bottiglieri, Teodoro

2016-01-01

We describe a simple stable isotope dilution method for accurate and precise measurement of γ-aminobutyric acid (GABA), a major inhibitory neurotransmitter in human cerebrospinal fluid (CSF) as a clinical diagnostic test. Determination of GABA in CSF (50 μL) was performed utilizing high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analysis of free and total GABA requires two individual sample preparations and mass spectrometry analyses. Free GABA in CSF is determined by a 1:2 dilution with internal standard (GABA-D2) and injected directly onto the HPLC-ESI-MS/MS system. Determination of total GABA in CSF requires additional sample preparation in order to hydrolyze all the bound GABA in the sample to the free form. This requires hydrolyzing the sample by boiling in acidic conditions (hydrochloric acid) for 4 h. The sample is then further diluted 1:10 with a 90 % acetonitrile/0.1 % formic acid solution and injected into the HPLC-ESI-MS/MS system. Each assay is quantified using a five-point standard curve and is linear from 6 nM to 1000 nM and 0.63 μM to 80 μM for free and total GABA, respectively.

Combined electroencephalography-functional magnetic resonance imaging and electrical source imaging improves localization of pediatric focal epilepsy.

PubMed

Centeno, Maria; Tierney, Tim M; Perani, Suejen; Shamshiri, Elhum A; St Pier, Kelly; Wilkinson, Charlotte; Konn, Daniel; Vulliemoz, Serge; Grouiller, Frédéric; Lemieux, Louis; Pressler, Ronit M; Clark, Christopher A; Cross, J Helen; Carmichael, David W

2017-08-01

Surgical treatment in epilepsy is effective if the epileptogenic zone (EZ) can be correctly localized and characterized. Here we use simultaneous electroencephalography-functional magnetic resonance imaging (EEG-fMRI) data to derive EEG-fMRI and electrical source imaging (ESI) maps. Their yield and their individual and combined ability to (1) localize the EZ and (2) predict seizure outcome were then evaluated. Fifty-three children with drug-resistant epilepsy underwent EEG-fMRI. Interictal discharges were mapped using both EEG-fMRI hemodynamic responses and ESI. A single localization was derived from each individual test (EEG-fMRI global maxima [GM]/ESI maximum) and from the combination of both maps (EEG-fMRI/ESI spatial intersection). To determine the localization accuracy and its predictive performance, the individual and combined test localizations were compared to the presumed EZ and to the postsurgical outcome. Fifty-two of 53 patients had significant maps: 47 of 53 for EEG-fMRI, 44 of 53 for ESI, and 34 of 53 for both. The EZ was well characterized in 29 patients; 26 had an EEG-fMRI GM localization that was correct in 11, 22 patients had ESI localization that was correct in 17, and 12 patients had combined EEG-fMRI and ESI that was correct in 11. Seizure outcome following resection was correctly predicted by EEG-fMRI GM in 8 of 20 patients, and by the ESI maximum in 13 of 16. The combined EEG-fMRI/ESI region entirely predicted outcome in 9 of 9 patients, including 3 with no lesion visible on MRI. EEG-fMRI combined with ESI provides a simple unbiased localization that may predict surgery better than each individual test, including in MRI-negative patients. Ann Neurol 2017;82:278-287. © 2017 American Neurological Association.

National and state-specific health insurance disparities for adults in same-sex relationships.

PubMed

Gonzales, Gilbert; Blewett, Lynn A

2014-02-01

We examined national and state-specific disparities in health insurance coverage, specifically employer-sponsored insurance (ESI) coverage, for adults in same-sex relationships. We used data from the American Community Survey to identify adults (aged 25-64 years) in same-sex relationships (n = 31,947), married opposite-sex relationships (n = 3,060,711), and unmarried opposite-sex relationships (n = 259,147). We estimated multinomial logistic regression models and state-specific relative differences in ESI coverage with predictive margins. Men and women in same-sex relationships were less likely to have ESI than were their married counterparts in opposite-sex relationships. We found ESI disparities among adults in same-sex relationships in every region, but we found the largest ESI gaps for men in the South and for women in the Midwest. ESI disparities were narrower in states that had extended legal same-sex marriage, civil unions, and broad domestic partnerships. Men and women in same-sex relationships experience disparities in health insurance coverage across the country, but residing in a state that recognizes legal same-sex marriage, civil unions, or broad domestic partnerships may improve access to ESI for same-sex spouses and domestic partners.

A new class of boron nitride fibers with tunable properties by combining an electrospinning process and the polymer-derived ceramics route

NASA Astrophysics Data System (ADS)

Salles, Vincent; Bernard, Samuel; Brioude, Arnaud; Cornu, David; Miele, Philippe

2010-02-01

Novel boron nitride (BN) fibers have been developed with diameters ranging from the nano- to microscale by thermal conversion of as-electrospun fibers from polyacrylonitrile and poly[B-(methylamino)borazine] blend solutions. Such a new class of ceramic fibers is seen as potential candidate for thermal management applications and filtration systems in harsh environments.Novel boron nitride (BN) fibers have been developed with diameters ranging from the nano- to microscale by thermal conversion of as-electrospun fibers from polyacrylonitrile and poly[B-(methylamino)borazine] blend solutions. Such a new class of ceramic fibers is seen as potential candidate for thermal management applications and filtration systems in harsh environments. Electronic supplementary information (ESI) available: Experimental details and EDX results. See DOI: 10.1039/b9nr00185a

Development and use of an instrument to measure scientific inquiry and related factors

NASA Astrophysics Data System (ADS)

Dunbar, Terry Frank

The use of the scientific inquiry method of teaching science was investigated in one district's elementary schools. The study generated data directly from Albuquerque Public Schools fourth- and fifth-grade teachers through a mail-out survey and through observation. Two forms of an inquiry evaluation research instrument (Elementary Science Inquiry Survey - ESIS) were created. The ESIS-A is a classroom observation tool. The ESIS-B is a survey questionnaire designed to collect information from teachers. The study was designed first to establish reliability and validity for both forms of the instrument. The study made use of multiple regression and exploratory factor analysis. Sources used to establish the instruments' reliability and validity included: (1) Input from an international panel (qualitative analysis of comments sent by raters and quantitative analysis of numerical ratings sent by raters); (2) Cronbach's alpha; (3) Results of factor analysis; (4) Survey respondents' comments (qualitative analysis); (5) Teacher observation data. Cronbach's alpha for the data set was .8955. Inquiry practices were reported to occur between twice per week and three times per week. Teachers' comments regarding inquiry were reported. The ESIS was used to collect inquiry self-report data and teacher background data. The teacher background data included teacher science knowledge and information about their standards awareness and implementation. The following teacher knowledge factors were positively correlated with inquiry use: semesters of college science, science workshops taken, conducted scientific research, and SIMSE (NSF institute) participation. The following standards awareness and implementation factors were positively correlated with inquiry use: familiarity with the National Science Education Standards, familiarity with New Mexico science standards, state or national standards as a curriculum selection factor, student interest as a curriculum selection factor, and "no limits" indicated as an inquiry-limiting factor. The following eight variables (all inquiry-limiting factors) were negatively correlated with inquiry use: available instructional materials, student prior knowledge/reading level, lack of experience with inquiry, not enough time, unsuccessful previous attempts, doubts about students' capability, insufficient time and support, and insufficient background in science.

Online Simultaneous Hydrogen/Deuterium Exchange of Multitarget Gas-Phase Molecules by Electrospray Ionization Mass Spectrometry Coupled with Gas Chromatography.

PubMed

Jeong, Eun Sook; Cha, Eunju; Cha, Sangwon; Kim, Sunghwan; Oh, Han Bin; Kwon, Oh-Seung; Lee, Jaeick

2017-11-21

In this study, a hydrogen/deuterium (H/D) exchange method using gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) was first investigated as a novel tool for online H/D exchange of multitarget analytes. The GC and ESI source were combined with a homemade heated column transfer line. GC-ESI/MS-based H/D exchange occurs in an atmospheric pressure ion source as a result of reacting the gas-phase analyte eluted from GC with charged droplets of deuterium oxide infused as the ESI spray solvent. The consumption of the deuterated solvent at a flow rate of 2 μL min -1 was more economical than that in online H/D exchange methods reported to date. In-ESI-source H/D exchange by GC-ESI/MS was applied to 11 stimulants with secondary amino or hydroxyl groups. After H/D exchange, the spectra of the stimulants showed unexchanged, partially exchanged, and fully exchanged ions showing various degrees of exchange. The relative abundances corrected for naturally occurring isotopes of the fully exchanged ions of stimulants, except for etamivan, were in the range 24.3-85.5%. Methylephedrine and cyclazodone showed low H/D exchange efficiency under acidic, neutral, and basic spray solvent conditions and nonexchange for etamivan with an acidic phenolic OH group. The in-ESI-source H/D exchange efficiency by GC-ESI/MS was sufficient to determine the number of hydrogen by elucidation of fragmentation from the spectrum. Therefore, this online H/D exchange technique using GC-ESI/MS has potential as an alternative method for simultaneous H/D exchange of multitarget analytes.

Endometrial scratch injury before intrauterine insemination: is it time to re-evaluate its value? Evidence from a systematic review and meta-analysis of randomized controlled trials.

PubMed

Vitagliano, Amerigo; Noventa, Marco; Saccone, Gabriele; Gizzo, Salvatore; Vitale, Salvatore Giovannni; Laganà, Antonio Simone; Litta, Pietro Salvatore; Saccardi, Carlo; Nardelli, Giovanni Battista; Di Spiezio Sardo, Attilio

2018-01-01

To assess the impact of endometrial scratch injury (ESI) on the outcomes of intrauterine insemination (IUI) stimulated cycles. Systematic review and meta-analysis. Not applicable. Infertile women undergoing one or more IUI stimulated cycles. Randomized controlled trials (RCTs) were identified by searching electronic databases. We included RCTs comparing ESI (i.e., intervention group) during the course of IUI stimulated cycle (C-ESI) or during the menstrual cycle preceding IUI treatment (P-ESI) with controls (no endometrial scratch). The summary measures were reported as odds ratio (OR) with 95% confidence-interval (CI). Clinical pregnancy rate, ongoing pregnancy rate, multiple pregnancy rate, ectopic pregnancy rate, miscarriage rate. Eight trials were included in the meta-analysis, comprising a total of 1,871 IUI cycles. Endometrial scratch injury was associated with a higher clinical pregnancy rate (OR 2.27) and ongoing pregnancy rate (OR 2.04) in comparison with the controls. No higher risk of multiple pregnancy (OR 1.09), miscarriage (OR 0.80), or ectopic pregnancy (OR 0.82) was observed in patients receiving ESI. Subgroup analysis based on ESI timing showed higher clinical pregnancy rate (OR 2.57) and ongoing pregnancy rate (OR 2.27) in patients receiving C-ESI and no advantage in patients receiving P-ESI. Available data suggest that ESI performed once, preferably during the follicular phase of the same cycle of IUI with flexible aspiration catheters, may improve clinical pregnancy and ongoing pregnancy rates in IUI cycles. Endometrial scratch injury does not appear to increase the risk of multiple pregnancy, miscarriage, or ectopic pregnancy. Copyright © 2017 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

Broad-Range PCR Coupled with Electrospray Ionization Time of Flight Mass Spectrometry for Detection of Bacteremia and Fungemia in Patients with Neutropenic Fever

PubMed Central

Maertens, J.; Bueselinck, K.; Lagrou, K.

2016-01-01

Infection is an important complication in patients with hematologic malignancies or solid tumors undergoing intensive cytotoxic chemotherapy. In only 20 to 30% of the febrile neutropenic episodes, an infectious agent is detected by conventional cultures. In this prospective study, the performance of broad-range PCR coupled with electrospray ionization time of flight mass spectrometry (PCR/ESI-MS) technology was compared to conventional blood cultures (BC) in a consecutive series of samples from high-risk hematology patients. In 74 patients, BC and a whole-blood sample for PCR/ESI-MS (Iridica BAC BSI; Abbott, Carlsbad, CA, USA) were collected at the start of each febrile neutropenic episode and, in case of persistent fever, also at day 5. During 100 different febrile episodes, 105 blood samples were collected and analyzed by PCR/ESI-MS. There was evidence of a bloodstream infection (BSI) in 36/105 cases (34%), based on 14 cases with both PCR/ESI-MS and BC positivity, 17 cases with BC positivity only, and 5 cases with PCR/ESI-MS positivity only. The sensitivity of PCR/ESI-MS was 45%, specificity was 93%, and the negative predictive value was 80% compared to blood culture. PCR/ESI-MS detected definite pathogens (Fusobacterium nucleatum and Streptococcus pneumoniae) missed by BC, whereas it missed both Gram-negative and Gram-positive organisms detected by BC. PCR/ESI-MS testing detected additional microorganisms but showed a low sensitivity (45%) compared to BC in neutropenic patients. Our results indicate a lower concordance between BC and PCR/ESI-MS in the neutropenic population than what has been previously reported in other patient groups with normal white blood cell distribution, and a lower sensitivity than other PCR-based methods. PMID:27440820

Ictal and interictal electric source imaging in presurgical evaluation: a prospective study.

PubMed

Sharma, Praveen; Scherg, Michael; Pinborg, Lars H; Fabricius, Martin; Rubboli, Guido; Pedersen, Birthe; Leffers, Anne-Mette; Uldall, Peter; Jespersen, Bo; Brennum, Jannick; Mølby Henriksen, Otto; Beniczky, Sándor

2018-05-11

Accurate localization of the epileptic focus is essential for surgical treatment of patients with drug- resistant epilepsy. EEG source imaging (ESI) is increasingly used in presurgical evaluation. However, most previous studies analysed interictal discharges. Prospective studies comparing feasibility and accuracy of interictal (II) and ictal (IC) ESI are lacking. We prospectively analysed long-term video EEG recordings (LTM) of patients admitted for presurgical evaluation. We performed ESI of II and IC signals, using two methods: equivalent current dipole (ECD) and distributed source model (DSM). LTM recordings employed the standard 25-electrode array (including inferior temporal electrodes). An age-matched template head-model was used for source analysis. Results were compared with intracranial recordings (ICR), conventional neuroimaging methods (MRI, PET, SPECT) and outcome one year after surgery. Eighty-seven consecutive patients were analysed. ECD gave a significantly higher proportion of patients with localised focal abnormalities (94%) compared to MRI (70%), PET (66%) and SPECT (64%). Agreement between the ESI methods and ICR was moderate to substantial (k=0.56-0.79). Fifty-four patients were operated (47 for more than one year ago) and 62% of them became seizure-free. Localization accuracy of II-ESI was 51% for DSM and 57% for ECD; for IC-ESI this was 51% (DSM) and 62% (ECD). The differences between the ESI methods were not significant. Differences in localization accuracy between ESI and MRI (55%), PET (33%) and SPECT (40%) were not significant. II and IC ESI of LTM-data have high feasibility and their localisation accuracy is similar to the conventional neuroimaging methods. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Dan Says - Continuum Magazine | NREL

Science.gov Websites

Dan Says Leading Energy Systems Integration A headshot of a man in a suit, smiling. Photo by Dennis U.S. dedicated to solving the complex problems associated with energy systems integration (ESI) on a national scale. Our 185,000-square-foot Energy Systems Integration Facility (ESIF) is designed to provide a

Predicting ESI/MS Signal Change for Anions in Different Solvents.

PubMed

Kruve, Anneli; Kaupmees, Karl

2017-05-02

LC/ESI/MS is a technique widely used for qualitative and quantitative analysis in various fields. However, quantification is currently possible only for compounds for which the standard substances are available, as the ionization efficiency of different compounds in ESI source differs by orders of magnitude. In this paper we present an approach for quantitative LC/ESI/MS analysis without standard substances. This approach relies on accurately predicting the ionization efficiencies in ESI source based on a model, which uses physicochemical parameters of analytes. Furthermore, the model has been made transferable between different mobile phases and instrument setups by using a suitable set of calibration compounds. This approach has been validated both in flow injection and chromatographic mode with gradient elution.

Detecting Protein-Glycolipid Interactions Using Glycomicelles and CaR-ESI-MS

NASA Astrophysics Data System (ADS)

Han, Ling; Kitova, Elena N.; Klassen, John S.

2016-11-01

This study reports on the use of the catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS) assay, combined with glycomicelles, as a method for detecting specific interactions between water-soluble proteins and glycolipids (GLs) in aqueous solution. The B subunit homopentamers of cholera toxin (CTB5) and Shiga toxin type 1 B (Stx1B5) and the gangliosides GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2 served as model systems for this study. The CTB5 exhibits broad specificity for gangliosides and binds to GM1, GM2, GM3, GD1a, GD1b, and GT1b; Stx1B5 does not recognize gangliosides. The CaR-ESI-MS assay was used to analyze solutions of CTB5 or Stx1B5 and individual gangliosides (GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2) or mixtures thereof. The high affinity interaction of CTB5 with GM1 was successfully detected. However, the apparent affinity, as determined from the mass spectra, is significantly lower than that of the corresponding pentasaccharide or when GM1 is presented in model membranes such as nanodiscs. Interactions between CTB5 and the low affinity gangliosides GD1a, GD1b, and GT1b, as well as GD2, which served as a negative control, were detected; no binding of CTB5 to GM2 or GM3 was observed. The CaR-ESI-MS results obtained for Stx1B5 reveal that nonspecific protein-ganglioside binding can occur during the ESI process, although the extent of binding varies between gangliosides. Consequently, interactions detected for CTB5 with GD1a, GD1b, and GT1b are likely nonspecific in origin. Taken together, these results reveal that the CaR-ESI-MS/glycomicelle approach for detecting protein-GL interactions is prone to false positives and false negatives and must be used with caution.

Detecting Protein-Glycolipid Interactions Using Glycomicelles and CaR-ESI-MS.

PubMed

Han, Ling; Kitova, Elena N; Klassen, John S

2016-11-01

This study reports on the use of the catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS) assay, combined with glycomicelles, as a method for detecting specific interactions between water-soluble proteins and glycolipids (GLs) in aqueous solution. The B subunit homopentamers of cholera toxin (CTB 5 ) and Shiga toxin type 1 B (Stx1B 5 ) and the gangliosides GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2 served as model systems for this study. The CTB 5 exhibits broad specificity for gangliosides and binds to GM1, GM2, GM3, GD1a, GD1b, and GT1b; Stx1B 5 does not recognize gangliosides. The CaR-ESI-MS assay was used to analyze solutions of CTB 5 or Stx1B 5 and individual gangliosides (GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2) or mixtures thereof. The high affinity interaction of CTB 5 with GM1 was successfully detected. However, the apparent affinity, as determined from the mass spectra, is significantly lower than that of the corresponding pentasaccharide or when GM1 is presented in model membranes such as nanodiscs. Interactions between CTB 5 and the low affinity gangliosides GD1a, GD1b, and GT1b, as well as GD2, which served as a negative control, were detected; no binding of CTB 5 to GM2 or GM3 was observed. The CaR-ESI-MS results obtained for Stx1B 5 reveal that nonspecific protein-ganglioside binding can occur during the ESI process, although the extent of binding varies between gangliosides. Consequently, interactions detected for CTB 5 with GD1a, GD1b, and GT1b are likely nonspecific in origin. Taken together, these results reveal that the CaR-ESI-MS/glycomicelle approach for detecting protein-GL interactions is prone to false positives and false negatives and must be used with caution. Graphical Abstract .

Production of highly charged ion beams Kr32+, Xe44+, Au54+ with Electron String Ion Source (ESIS) Krion-2 and corresponding basic and applied studies

NASA Astrophysics Data System (ADS)

Donets, D. E.; Donets, E. D.; Donets, E. E.; Salnikov, V. V.; Shutov, V. B.

2010-09-01

Electron String Ion Source (ESIS) Krion-2 (JINR, Dubna) was used for basic and applied research in various aspects of multiply charged heavy ions production. Energy recuperation mode in ESIS has been proofed first and used for production of highly charged ions 84Kr28+÷84Kr32+, 124Xe40÷124Xe44 and Au51+÷ Au54+. Krion-2 ESIS was mounted on high voltage (HV) platform of LU-20 Linac and used as an injector of highly charged ions during Nuclotron run N° 41. Krion-2 ESIS has produced 3.0.107 124Xe42+ ions per pulse of 7 μs duration. This ion beam was injected into LU-20 and Nuclotron, accelerated up to energy of 186 GeV and the extracted Xe beam was used for physics experiments. Electron String Ion Source Krion-2 demonstrated the high reliability and stability running during 30 days on HV platform. We believe that it is due to an extremely low electron beam power, provided by using the electron string mode of operation: 50 W pulse power and about 10 W average power. Other possible application of ESIS could be its use in injection complexes of synchrotrons and cyclotrons for cancer therapy. Slow and fast extraction of C4+ and C6+ beams from Krion-2 ESIS were preliminary studied towards ESIS optimization for medical accelerators requirements.

Versatile telluracycle synthesis via the sequential electrophilic telluration of C(sp2)–Zn and C(sp2)–H bonds† †Electronic supplementary information (ESI) available. CCDC 1523262–1523264. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01162h Click here for additional data file. Click here for additional data file.

PubMed Central

Wu, Bin; Melvina; Wu, Xiangyang; Lee Yeow, Edwin Kok

2017-01-01

We report herein a new approach for the synthesis of tellurium-bridged aromatic compounds based on the sequential electrophilic telluration of C(sp2)–Zn and C(sp2)–H bonds with tellurium(iv) chlorides. A combination of transition metal-catalyzed (migratory) arylmetalation of alkynes and sequential telluration allows for the expedient construction of a library of functionalized benzo[b]tellurophenes. Furthermore, a variety of heteroarene-fused benzotellurophenes and other novel tellurium-embedded polycyclic aromatics can be readily synthesized from the corresponding 2-iodoheterobiaryls. PMID:28970880

Application of the accurate mass and time tag approach in studies of the human blood lipidome

PubMed Central

Ding, Jie; Sorensen, Christina M.; Jaitly, Navdeep; Jiang, Hongliang; Orton, Daniel J.; Monroe, Matthew E.; Moore, Ronald J.; Smith, Richard D.; Metz, Thomas O.

2008-01-01

We report a preliminary demonstration of the accurate mass and time (AMT) tag approach for lipidomics. Initial data-dependent LC-MS/MS analyses of human plasma, erythrocyte, and lymphocyte lipids were performed in order to identify lipid molecular species in conjunction with complementary accurate mass and isotopic distribution information. Identified lipids were used to populate initial lipid AMT tag databases containing 250 and 45 entries for those species detected in positive and negative electrospray ionization (ESI) modes, respectively. The positive ESI database was then utilized to identify human plasma, erythrocyte, and lymphocyte lipids in high-throughput LC-MS analyses based on the AMT tag approach. We were able to define the lipid profiles of human plasma, erythrocytes, and lymphocytes based on qualitative and quantitative differences in lipid abundance. PMID:18502191

Access to benzo-fused nine-membered heterocyclic alkenes with a trifluoromethyl carbinol moiety via a double decarboxylative formal ring-expansion process under palladium catalysis† †Electronic supplementary information (ESI) available: CCDC 1575063, 1575065, 1575062, 1589030. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc05447e

PubMed Central

Das, Pulakesh; Gondo, Satoshi; Nagender, Punna; Uno, Hiroto; Tokunaga, Etsuko

2018-01-01

Direct access to pharmaceutically attractive benzo-fused nine-membered heterocyclic alkenes 3 with a trifluoromethyl carbinol moiety was achieved via a palladium-catalyzed double-decarboxylative formal ring-expansion process from six-membered trifluoromethyl benzo[d][1,3]oxazinones 1 to nine-membered trifluoromethyl benzo[c][1,5]oxazonines 3 in the presence of vinylethylene carbonates 2. Generation of a Pd-π-allyl zwitterionic intermediate was proposed in the catalytic cycle. The trifluoromethyl group in the benzoxazinanones 1 plays an important role throughout the transformation. Diastereoselective chemical transformations of products 3 were also demonstrated. PMID:29732106

Predictors of Extradyadic Sexual Involvement in Unmarried Opposite-Sex Relationships

PubMed Central

Maddox Shaw, Amanda M.; Rhoades, Galena K.; Allen, Elizabeth S.; Stanley, Scott M.; Markman, Howard J.

2012-01-01

Using a sample of unmarried individuals in opposite-sex romantic relationships that was representative of the United States (N = 933), the current study prospectively evaluated predictors of extradyadic sexual involvement (ESI) over 20-months. Data were collected with self-report questionnaires via U.S. mail. Participants were 18–35 years old and were 34.9% male. Variables tested as predictors included involved-partner factors such as demographic characteristics, sexual history, and mental health, as well as relationship-related factors including communication, sexual dynamics, and aspects of commitment. Future ESI was significantly predicted by lower baseline relationship satisfaction, negative communication, aggression, lower dedication, absence of plans to marry, suspicion of partner’s ESI, and partner’s ESI. It was not predicted by sexual frequency, sexual dissatisfaction, or cohabitation status. Although more problems with alcohol use, more previous sex partners, and having parents who never married one another predicted future ESI, there were many involved-partner demographic factors that did not predict later ESI (e.g., gender, age, education, religiosity, having divorced parents, and having children). None of the results were moderated by gender. These results suggest that compared to demographic characteristics, relationship dynamics and negative interactions are more strongly predictive of future ESI. Implications for future research are discussed. PMID:22524318

National and State-Specific Health Insurance Disparities for Adults in Same-Sex Relationships

PubMed Central

Blewett, Lynn A.

2014-01-01

Objectives. We examined national and state-specific disparities in health insurance coverage, specifically employer-sponsored insurance (ESI) coverage, for adults in same-sex relationships. Methods. We used data from the American Community Survey to identify adults (aged 25–64 years) in same-sex relationships (n = 31 947), married opposite-sex relationships (n = 3 060 711), and unmarried opposite-sex relationships (n = 259 147). We estimated multinomial logistic regression models and state-specific relative differences in ESI coverage with predictive margins. Results. Men and women in same-sex relationships were less likely to have ESI than were their married counterparts in opposite-sex relationships. We found ESI disparities among adults in same-sex relationships in every region, but we found the largest ESI gaps for men in the South and for women in the Midwest. ESI disparities were narrower in states that had extended legal same-sex marriage, civil unions, and broad domestic partnerships. Conclusions. Men and women in same-sex relationships experience disparities in health insurance coverage across the country, but residing in a state that recognizes legal same-sex marriage, civil unions, or broad domestic partnerships may improve access to ESI for same-sex spouses and domestic partners. PMID:24328616

Study of rat hypothalamic proteome by HPLC/ESI ion trap and HPLC/ESI-Q-TOF MS.

PubMed

Iqbal, Javed; Li, Wang; Ullah, Kaleem; Hasan, Murtaza; Linna, Guo; Awan, Umer; Zhang, Yongqian; Batool, Sajida; Qing, Hong; Deng, Yulin

2013-08-01

The proteomic profile of hypothalamus, a key organ of CNS, is explored here by employing two widely used MS techniques, i.e. HPLC/ESI-ion trap and HPLC/ESI-quadrupole-TOF MS. Strong cation exchange is used for the fractionation of peptides and protein search engine MASCOT is employed for data query. One hundred and thirty six proteins with 10 973 peptides were identified by HPLC/ESI-ion trap MS, while 140 proteins with 32 183 peptides were characterized by HPLC/ESI-quadrupole-TOF MS. Among the total 198 proteins identified in both experiments, 78 proteins were common in both sets of conditions. The rest of the 120 proteins were identified distinctly in both MS strategies, i.e. 58 unique proteins were found using the quadrupole-TOF while 62 were found with the HPLC/ESI-ion trap. Moreover, these proteins were classified into groups based on their functions performed in the body. Results presented here identified some important signal and cellular defense proteins inevitable for survival in stressed conditions. Additionally, it is also shown that any single MS strategy is not reliable for good results due to loss of data depending on sensitivity of the instrument used. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multicomponent Supramolecular Systems: Self-Organization in Coordination-Driven Self-Assembly

PubMed Central

Zheng, Yao-Rong; Yang, Hai-Bo; Ghosh, Koushik; Zhao, Liang; Stang, Peter J.

2009-01-01

The self-organization of multicomponent supramolecular systems involving a variety of two-dimensional (2-D) polygons and three-dimensional (3-D) cages is presented. Nine self-organizing systems, SS1–SS9, have been studied. Each involving the simultaneous mixing of organoplatinum acceptors and pyridyl donors of varying geometry and their selective self-assembly into three to four specific 2-D (rectangular, triangular, and rhomboid) and/or 3-D (triangular prism and distorted and nondistorted trigonal bipyramidal) supramolecules. The formation of these discrete structures is characterized using NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). In all cases, the self-organization process is directed by: (1) the geometric information encoded within the molecular subunits and (2) a thermodynamically driven dynamic self-correction process. The result is the selective self-assembly of multiple discrete products from a randomly formed complex. The influence of key experimental variables – temperature and solvent – on the self-correction process and the fidelity of the resulting self-organization systems is also described. PMID:19544512

Stability and oxidation products of hydrolysable tannins in basic conditions detected by HPLC/DAD-ESI/QTOF/MS.

PubMed

Tuominen, Anu; Sundman, Terhi

2013-01-01

Hydrolysable tannins occur in plants that are used for food or medicine by humans or herbivores. Basic conditions can alter the structures of tannins, that is, the oxidation of phenolic groups can lead to the formation of toxic quinones. Previously, these labile quinones and other oxidation products have been studied with colorimetric or electron paramagnetic resonance methods, which give limited information about products. To study the stability and oxidation products of hydrolysable tannins in basic conditions using HPLC with a diode-array detector (DAD) combined with electrospray ionisation (ESI) and quadrupole time-of-flight (QTOF) MS. Three galloyl glucoses, four galloyl derivatives with different polyols and three ellagitannins were purified from plants. The incubation reactions of tannins were monitored by HPLC/DAD at five pH values and in reduced oxygen conditions. Reaction products were identified based on UV spectra and mass spectral fragmentation obtained with the high-resolution HPLC/DAD-ESI/QTOF/MS. The use of a base-resistant HPLC column enabled injections without the sample pre-treatment and thus detection of short-lived products. Hydrolysable tannins were unstable in basic conditions and half-lives were mostly less than 10 min at pH 10. Degradation rates were faster at pH 11 but slower at milder pH. The HPLC analyses revealed that various products were formed and identified to be the result of hydrolysis, deprotonation and oxidation. Interestingly, the main hydrolysis product was ellagic acid; it was also formed from galloyl glucoses that do not contain oxidatively coupled galloyl groups in their initial structures. HPLD/DAD-ESI/QTOF/MS was an efficient method for the identification of polyphenol oxidation products and showed how different pH conditions determine the fate of hydrolysable tannins. Copyright © 2013 John Wiley & Sons, Ltd.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Positive and negative ion mode ESI-MS and MS/MS for studying drug-DNA complexes

NASA Astrophysics Data System (ADS)

Rosu, Frédéric; Pirotte, Sophie; Pauw, Edwin De; Gabelica, Valérie

2006-07-01

We report systematic investigation of duplex DNA complexes with minor groove binders (Hoechsts 33258 and 33342, netropsin and DAPI) and intercalators (daunomycin, doxorubicin, actinomycin D, ethidium, cryptolepine, neocryptolepine, m-Amsacrine, proflavine, ellipticine and mitoxantrone) by ESI-MS and ESI-MS/MS in the negative ion mode and in the positive ion mode. The apparent solution phase equilibrium binding constants can be determined by measuring relative intensities in the ESI-MS spectrum. While negative ion mode gives reliable results, positive ion mode gives a systematic underestimation of the binding constants and even a complete suppression of the complexes for intercalators lacking functional groups capable of interacting in the grooves. In the second part of the paper we systematically compare MS/MS fragmentation channels and breakdown curves in the positive and the negative modes, and discuss the possible uses and caveats of MS/MS in drug-DNA complexes. In the negative mode, the drugs can be separated in three groups: (1) those that leave the complex with no net charge; (2) those that leave the complex with a negative charge; and (3) those that remain attached on the strands upon dissociation of the duplex due to their positive charge. In the positive ion mode, all complexes fragment via the loss of protonated drug. Information on the stabilization of the complex by drug-DNA noncovalent interactions can be obtained straightforwardly only in the case of neutral drug loss. In all other cases, proton affinity (in the positive ion mode), gas-phase basicity (in the negative ion mode) and coulombic repulsion are the major factors influencing the fragmentation channel and the dissociation kinetics.

Revealing the glycation sites in synthetic neoglycoconjugates formed by conjugation of the antigenic monosaccharide hapten of Vibrio cholerae O1, serotype Ogawa with the BSA protein carrier using LC-ESI-QqTOF-MS/MS

PubMed Central

Jahouh, Farid; Saksena, Rina; Kováč, Pavol; Banoub, Joseph

2012-01-01

In this manuscript, we present the determination of glycation sites in synthetic neoglycoconjugates formed by conjugation of the antigenic monosaccharide hapten of Vibrio cholerae O1 serotype Ogawa to BSA using nano- liquid chromatography electrospray ionization quadrupole time-of-flight tandem mass spectroscopy (LC-ESI-QqTOF-MS/MS). The matrix-assisted laser desorption/ionization-TOF/TOF-MS/MS analyses of the tryptic digests of the glycoconjugates having a hapten:BSA ratio of 4.3:1, 6.6:1 and 13.2:1 revealed only three glycation sites, on the following lysine residues: Lys 235, Lys 437 and Lys 455. Digestion of the neoglycoconjugates with the proteases trypsin and GluC V8 gave complementary structural information and was shown to maximize the number of recognized glycation sites. Here, we report identification of 20, 27 and 33 glycation sites using LC-ESI-QqTOF-MS/MS analysis of a series of synthetic neoglycoconjugates with a hapten:BSA ratio of, respectively, 4.3:1, 6.6:1 and 13.2:1. We also tentatively propose that all the glycated lysine residues are located mainly near the outer surface of the protein. PMID:22791257

Research Staff | Energy Systems Integration Facility | NREL

Science.gov Websites

Research Staff Research Staff NREL's Energy Systems Integration directorate includes the Power investments in advanced energy research, and the security and resilience team under the DOE's multi-lab effort to modernize the nation's electrical grid. juan.torres@nrel.gov | 303-275-3094 ESI Research

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization.

PubMed

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed. Graphical Abstract ᅟ.

Measurement of total acid number (TAN) and TAN boiling point distribution in petroleum products by electrospray ionization mass spectrometry.

PubMed

Qian, Kuangnan; Edwards, Kathleen E; Dechert, Gary J; Jaffe, Stephen B; Green, Larry A; Olmstead, William N

2008-02-01

We report a new method for rapid measurement of total acid number (TAN) and TAN boiling point (BP) distribution for petroleum crude and products. The technology is based on negative ion electrospray ionization mass spectrometry (ESI-MS) for selective ionization of petroleum acid and quantification of acid structures and molecular weight distributions. A chip-based nanoelectrospray system enables microscale (<200 mg) and higher throughput (20 samples/h) measurement. Naphthenic acid structures were assigned based on nominal masses of a set of predefined acid structures. Stearic acid is used as an internal standard to calibrate ESI-MS response factors for quantification purposes. With the use of structure-property correlations, boiling point distributions of TAN values can be calculated from the composition. The rapid measurement of TAN BP distributions by ESI is demonstrated for a series of high-TAN crudes and distillation cuts. TAN values determined by the technique agree well with those by the titration method. The distributed properties compare favorably with those measured by distillation and measurement of TAN of corresponding cuts.

Monitoring protein glycation by electrospray ionization (ESI) quadrupole time-of-flight (Q-TOF) mass spectrometer.

PubMed

Akıllıoğlu, H Gül; Çelikbıçak, Ömür; Salih, Bekir; Gökmen, Vural

2017-02-15

In this study electrospray ionization quadrupole time-of-flight (ESI-Q-TOF) mass spectrometry was used to investigate protein glycation. The glycated species of cytochrome C, lysozyme, and β-casein formed during glycation with d-glucose were identified and monitored in binary systems heated at 70°C under dry and aqueous conditions. Cytochrome C had multiple charges in non-glycated state, primarily changing from +13 to +17 positive charges, whereas β-casein had charge states up to +30. Upon heating with glucose at 70°C in aqueous state, attachment of one glucose molecule onto proteins was observed in each charge state. However, heating in dry state caused much more glucose attachment, leading to the formation of multiple glycoforms of proteins. By using ESI-QTOF-MS technique, formation of glycated cytochrome C containing up to 12 glucose moieties were observed, while glycated species containing 6 and 8 glucose moieties were observed for lysozyme and β-casein, respectively in various heating conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

HPLC/ESI-quadrupole ion trap mass spectrometry for characterization and direct quantification of amphoteric and nonionic surfactants in aqueous samples

NASA Technical Reports Server (NTRS)

Levine, Lanfang H.; Garland, Jay L.; Johnson, Jodie V.

2002-01-01

An amphoteric (cocamidopropylbetaine, CAPB) and a nonionic (alcohol polyethoxylate, AE) surfactant were characterized by electrospray ionization quadrupole ion trap mass spectrometry (ESI-MS) as to their homologue distribution and ionization/fragmentation chemistry. Quantitative methods involving reversed-phase gradient HPLC and (+)ESI-MSn were developed to directly determine these surfactants in hydroponic plant growth medium that received simulated graywater. The predominant homologues, 12 C alkyl CAPB and 9 EO AE, were monitored to represent the total amount of the respective surfactants. The methods demonstrated dynamic linear ranges of 0.5-250 ng (r2 > 0.996) for CAPB and 8-560 ng (r2 > 0.998) for AE homologue mixture, corresponding to minimum quantification limits of 25 ppb CAPB and 0.4 ppm AE with 20-microL injections. This translated into an even lower limit for individual components due to the polydispersive nature of the surfactants. The procedure was successfully employed for the assessment of CAPB and AE biodegradation in a hydroponic plant growth system used as a graywater bioreactor.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization

NASA Astrophysics Data System (ADS)

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed.

A comparison of the y-Radiolysis of TODGA and T(EH)DGA using UHPLC-ESI-MS analysis

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

Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.

2015-04-27

Solutions of the diglycolamide extractants TODGA and T(EH)DGA in n-dodecane were subjected to γ- irradiation in the presence and absence of an acidic aqueous phase. These solutions were then analyzed using UHPLC-ESI-MS to determine the rates of radiolytic decay of the two extractants neat and in contact with respect to the acidity of the contacted aqueous phase, as well as to identify radiolysis products. The presence or absence of an acidic aqueous phase was shown to have no influence on the measured decay rates, nor did the side-chain have an influence. A number of radiolysis products were identified, consistent with thosemore » previously identified for these two compounds using GC-MS. The identity of these radiolysis products suggests that the bonds most vulnerable to radiolytic attack are those in the dyglycolamide center of these molecules, and not on the side-chains.  The agreement of these results with previous work using GC-MS indicates supports the further use of UHPLC-ESI-MS as a tool for studying diglycolamide extractant systems.« less

Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence† †Electronic supplementary information (ESI) available: General details, synthesis and spectroscopy data of new compounds. Experimental details on optical, chiroptical, electrochemical and on-surface measurements. Crystal data and structure refinement of compounds 1, and 6. Further details on theoretical calculations and Cartesian coordinates of computed structures. VT-H1NMR, 2D-NMR and HRMS spectra of 1. CCDC 1561552 and 1561553. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00427g

PubMed Central

Cruz, Carlos M.; Márquez, Irene R.; Mariz, Inês F. A.; Blanco, Victor; Sánchez-Sánchez, Carlos; Sobrado, Jesús M.; Martín-Gago, José A.; Cuerva, Juan M.

2018-01-01

Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects that promote the distortion of the otherwise planar lattice. The edge defects are an aromatic saddle-shaped ketone unit and a [5]carbohelicene moiety. This system is shown to combine two-photon absorption and circularly polarized luminescence and a remarkably long emission lifetime of 21.5 ns. The [5]helicene is responsible for the chiroptical activity while the push–pull geometry and the extended network of sp2 carbons are factors favoring the nonlinear absorption. Electronic structure theoretical calculations support the interpretation of the results. PMID:29780523

Extended School Year (ESY) Services: Iowa Standards for Students with Disabilities.

ERIC Educational Resources Information Center

Iowa State Dept. of Education, Des Moines. Bureau of Children, Family and Community Services.

This publication is intended to ensure that consideration for and provision of extended school year services (ESY services) for students with disabilities are consistent with the requirements of federal law, Iowa state rules, and Iowa's adopted educational standards. Part 1 of the document discusses the specific addition of ESY services to the…

Rapid detection of illegal colorants on traditional Chinese pastries through mass spectrometry with an interchangeable thermal desorption electrospray ionization source.

PubMed

Chao, Yu-Ying; Chen, Yen-Ling; Chen, Wei-Chu; Chen, Bai-Hsiun; Huang, Yeou-Lih

2018-06-30

Ambient mass spectrometry using an interchangeable thermal desorption/electrospray ionization source (TD-ESI) is a relatively new technique that has had only a limited number of applications to date. Nevertheless, this direct-analysis technique has potential for wider use in analytical chemistry (e.g., in the rapid direct detection of contaminants, residues, and adulterants on and in food) when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to a TD-ESI source from a conventional ESI source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants on traditional Chinese pastries (TCPs), as a proof-of-concept for the detection of illegal colorants. While TD-ESI can offer direct (i.e., without any sample preparation) qualitative screening analyses for TCPs with adequate sensitivity within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous matrices (e.g., tang yuan). Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical derivatization for enhancing sensitivity during LC/ESI-MS/MS quantification of steroids in biological samples: a review.

PubMed

Higashi, Tatsuya; Ogawa, Shoujiro

2016-09-01

Sensitive and specific methods for the detection, characterization and quantification of endogenous steroids in body fluids or tissues are necessary for the diagnosis, pathological analysis and treatment of many diseases. Recently, liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) has been widely used for these purposes due to its specificity and versatility. However, the ESI efficiency and fragmentation behavior of some steroids are poor, which lead to a low sensitivity. Chemical derivatization is one of the most effective methods to improve the detection characteristics of steroids in ESI-MS/MS. Based on this background, this article reviews the recent advances in chemical derivatization for the trace quantification of steroids in biological samples by LC/ESI-MS/MS. The derivatization in ESI-MS/MS is based on tagging a proton-affinitive or permanently charged moiety on the target steroid. Introduction/formation of a fragmentable moiety suitable for the selected reaction monitoring by the derivatization also enhances the sensitivity. The stable isotope-coded derivatization procedures for the steroid analysis are also described. Copyright © 2015 Elsevier Ltd. All rights reserved.

MicroSPE-nanoLC-ESI-MS/MS Using 10-μm-i.d. Silica-Based Monolithic Columns for Proteomics

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

Luo, Quanzhou; Page, Jason S.; Tang, Keqi

2007-01-01

Silica-based monolithic narrow bore capillary columns (25 cm x 10 µm i.d.) with an integrated nanoESI emitter has been developed to provide high quality and robust microSPE-nanoLC-ESI-MS analyses. The integrated nanoESI emitter adds no dead volume to the LC separation, allowing stable electrospray performance to be obtained at flow rates of ~10 nL/min. In an initial application we identified 5510 unique peptides covering 1443 distinct Shewanella oneidensis proteins from a 300 ng tryptic digest sample in a single 4-h LC-MS/MS analysis using a linear ion trap MS (LTQ). We found the use of an integrated monolithic ESI emitter provided enhancedmore » resistance to clogging and good run-to-run reproducibility.« less

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

PubMed

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

2018-02-01

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

NACE-ESI-TOF MS to reveal phenolic compounds from olive oil: introducing enriched olive oil directly inside capillary.

PubMed

Gómez-Caravaca, Ana María; Carrasco-Pancorbo, Alegría; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

2009-09-01

Most CE methods for the analysis of phenols from olive oil use an aqueous electrolyte separation medium, although the importance of NACE is obvious, as this kind of CE seems to be more compatible with the hydrophobic olive oil matrix and could facilitate its direct injection. In the current work we develop a method involving SPE and NACE coupled to ESI-TOF MS. All the CE and ESI-TOF MS parameters were optimized in order to maximize the number of phenolic compounds detected and the sensitivity in their determination. Electrophoretic separation was carried out using a CE buffer system consisting of 25 mM NH(4)OAc/AcH in methanol/ACN (1/1 v/v) at an apparent pH value of 5.0. We studied in depth the effect of the nature and concentration of different electrolytes dissolved in different organic solvents and other experimental and instrumental CE variables. The results were compared with those obtained by CZE (with aqueous buffers) coupled to ESI-TOF MS; both methods offered to the analyst the chance to study phenolic compounds of different families (such as phenolic alcohols, lignans, complex phenols, flavonoids, etc.) from virgin olive oil by injecting methanolic extracts with efficient and fast CE separations. In the case of NACE method, we also studied the direct injection of the investigated matrix introducing a plug of olive oil directly into the capillary.

Capillary electrophoresis-electrospray ionization-mass spectrometry method to determine the phenolic fraction of extra-virgin olive oil.

PubMed

Carrasco-Pancorbo, Alegría; Arráez-Román, David; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

2006-06-01

We describe the first analytical method involving SPE and CZE coupled to ESI-IT MS (CZE-ESI-MS) used to identify and characterize phenolic compounds in olive oil samples. The SPE, CZE and ESI-MS parameters were optimized in order to maximize the number of phenolic compounds detected and the sensitivity of their determination. To this end we have devised a detailed method to find the best conditions for CE separation and the detection by MS of the phenolic compounds present in olive oil using a methanol-water extract of Picual extra-virgin olive oil (VOO). Electrophoretic separation was carried out using an aqueous CE buffer system consisting of 60 mM NH(4)OAc at pH 9.5 with 5% of 2-propanol, a sheath liquid containing 2-propanol/water 60:40 v/v and 0.1% v/v triethylamine. This method offers to the analyst the chance to study important phenolic compounds such as phenolic alcohols (tyrosol (TY), hydroxytyrosol (HYTY) and 2-(4-hydroxyphenyl)ethyl acetate), lignans ((+)-pinoresinol and (+)-1-acetoxypinoresinol), complex phenols (ligstroside aglycon (Lig Agl), oleuropein aglycon, their respective decarboxylated derivatives and several isomeric forms of these (dialdehydic form of oleuropein aglycon, dialdehydic form of ligstroside aglycon, dialdehydic form of decarboxymethyl elenolic acid linked to HYTY, dialdehydic form of decarboxymethyl elenolic acid linked to TY) and 10-hydroxy-oleuropein aglycon) and one other phenolic compound (elenolic acid) in extra-VOO by using a simple SPE before CE-ESI-MS analysis.

Physicochemical Parameters Affecting the Electrospray Ionization Efficiency of Amino Acids after Acylation

PubMed Central

2017-01-01

Electrospray ionization (ESI) is widely used in liquid chromatography coupled to mass spectrometry (LC–MS) for the analysis of biomolecules. However, the ESI process is still not completely understood, and it is often a matter of trial and error to enhance ESI efficiency and, hence, the response of a given set of compounds. In this work we performed a systematic study of the ESI response of 14 amino acids that were acylated with organic acid anhydrides of increasing chain length and with poly(ethylene glycol) (PEG) changing certain physicochemical properties in a predictable manner. By comparing the ESI response of 70 derivatives, we found that there was a strong correlation between the calculated molecular volume and the ESI response, while correlation with hydrophobicity (log P values), pKa, and the inverse calculated surface tension was significantly lower although still present, especially for individual derivatized amino acids with increasing acyl chain lengths. Acylation with PEG containing five ethylene glycol units led to the largest gain in ESI response. This response was maximal independent of the calculated physicochemical properties or the type of amino acid. Since no actual physicochemical data is available for most derivatized compounds, the responses were also used as input for a quantitative structure–property relationship (QSPR) model to find the best physicochemical descriptors relating to the ESI response from molecular structures using the amino acids and their derivatives as a reference set. A topological descriptor related to molecular size (SPAN) was isolated next to a descriptor related to the atomic composition and structural groups (BIC0). The validity of the model was checked with a test set of 43 additional compounds that were unrelated to amino acids. While prediction was generally good (R2 > 0.9), compounds containing halogen atoms or nitro groups gave a lower predicted ESI response. PMID:28737384

Broad-Range PCR Coupled with Electrospray Ionization Time of Flight Mass Spectrometry for Detection of Bacteremia and Fungemia in Patients with Neutropenic Fever.

PubMed

Desmet, S; Maertens, J; Bueselinck, K; Lagrou, K

2016-10-01

Infection is an important complication in patients with hematologic malignancies or solid tumors undergoing intensive cytotoxic chemotherapy. In only 20 to 30% of the febrile neutropenic episodes, an infectious agent is detected by conventional cultures. In this prospective study, the performance of broad-range PCR coupled with electrospray ionization time of flight mass spectrometry (PCR/ESI-MS) technology was compared to conventional blood cultures (BC) in a consecutive series of samples from high-risk hematology patients. In 74 patients, BC and a whole-blood sample for PCR/ESI-MS (Iridica BAC BSI; Abbott, Carlsbad, CA, USA) were collected at the start of each febrile neutropenic episode and, in case of persistent fever, also at day 5. During 100 different febrile episodes, 105 blood samples were collected and analyzed by PCR/ESI-MS. There was evidence of a bloodstream infection (BSI) in 36/105 cases (34%), based on 14 cases with both PCR/ESI-MS and BC positivity, 17 cases with BC positivity only, and 5 cases with PCR/ESI-MS positivity only. The sensitivity of PCR/ESI-MS was 45%, specificity was 93%, and the negative predictive value was 80% compared to blood culture. PCR/ESI-MS detected definite pathogens (Fusobacterium nucleatum and Streptococcus pneumoniae) missed by BC, whereas it missed both Gram-negative and Gram-positive organisms detected by BC. PCR/ESI-MS testing detected additional microorganisms but showed a low sensitivity (45%) compared to BC in neutropenic patients. Our results indicate a lower concordance between BC and PCR/ESI-MS in the neutropenic population than what has been previously reported in other patient groups with normal white blood cell distribution, and a lower sensitivity than other PCR-based methods. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

48 CFR 2452.204-70 - Preservation of, and access to, contract records (tangible and electronically stored information...

Code of Federal Regulations, 2013 CFR

2013-10-01

... or data storage). ESI devices and media include, but are not be limited to: (1) Computers (mainframe...) Personal data assistants (PDAs); (5) External data storage devices including portable devices (e.g., flash drive); and (6) Data storage media (magnetic, e.g., tape; optical, e.g., compact disc, microfilm, etc...

48 CFR 2452.204-70 - Preservation of, and access to, contract records (tangible and electronically stored information...

Code of Federal Regulations, 2014 CFR

2014-10-01

... or data storage). ESI devices and media include, but are not be limited to: (1) Computers (mainframe...) Personal data assistants (PDAs); (5) External data storage devices including portable devices (e.g., flash drive); and (6) Data storage media (magnetic, e.g., tape; optical, e.g., compact disc, microfilm, etc...

Composite nanoplatelets combining soft-magnetic iron oxide with hard-magnetic barium hexaferrite

NASA Astrophysics Data System (ADS)

Primc, D.; Makovec, D.

2015-01-01

By coupling two different magnetic materials inside a single composite nanoparticle, the shape of the magnetic hysteresis can be engineered to meet the requirements of specific applications. Sandwich-like composite nanoparticles composed of a hard-magnetic Ba-hexaferrite (BaFe12O19) platelet core in between two soft-magnetic spinel iron oxide maghemite (γ-Fe2O3) layers were synthesized using a new, simple and inexpensive method based on the co-precipitation of Fe3+/Fe2+ ions in an aqueous suspension of hexaferrite core nanoparticles. The required close control of the supersaturation of the precipitating species was enabled by the controlled release of the Fe3+ ions from the nitrate complex with urea ([Fe((H2N)2C&z.dbd;O)6](NO3)3) and by using Mg(OH)2 as a solid precipitating agent. The platelet Ba-hexaferrite nanoparticles of different sizes were used as the cores. The controlled coating resulted in an exclusively heterogeneous nucleation and the topotactic growth of the spinel layers on both basal surfaces of the larger hexaferrite nanoplatelets. The direct magnetic coupling between the core and the shell resulted in a strong increase of the energy product |BH|max. Ultrafine core nanoparticles reacted with the precipitating species and homogeneous product nanoparticles were formed, which differ in terms of the structure and composition compared to any other compound in the BaO-Fe2O3 system.By coupling two different magnetic materials inside a single composite nanoparticle, the shape of the magnetic hysteresis can be engineered to meet the requirements of specific applications. Sandwich-like composite nanoparticles composed of a hard-magnetic Ba-hexaferrite (BaFe12O19) platelet core in between two soft-magnetic spinel iron oxide maghemite (γ-Fe2O3) layers were synthesized using a new, simple and inexpensive method based on the co-precipitation of Fe3+/Fe2+ ions in an aqueous suspension of hexaferrite core nanoparticles. The required close control of the supersaturation of the precipitating species was enabled by the controlled release of the Fe3+ ions from the nitrate complex with urea ([Fe((H2N)2C&z.dbd;O)6](NO3)3) and by using Mg(OH)2 as a solid precipitating agent. The platelet Ba-hexaferrite nanoparticles of different sizes were used as the cores. The controlled coating resulted in an exclusively heterogeneous nucleation and the topotactic growth of the spinel layers on both basal surfaces of the larger hexaferrite nanoplatelets. The direct magnetic coupling between the core and the shell resulted in a strong increase of the energy product |BH|max. Ultrafine core nanoparticles reacted with the precipitating species and homogeneous product nanoparticles were formed, which differ in terms of the structure and composition compared to any other compound in the BaO-Fe2O3 system. Electronic supplementary information (ESI) available: Synthesis (ESI #1) and properties (ESI #2) of the barium hexaferrite core nanoparticles, TEM of the nanoparticles synthesized under an excessive supersaturation (ESI #3), and magnetic properties of physical mixtures of the hard-magnetic hexaferrite and the soft-magnetic spinel ferrite (ESI #4). See DOI: 10.1039/c4nr05854b

Employer-sponsored health insurance coverage limitations: results from the Childhood Cancer Survivor Study.

PubMed

Kirchhoff, Anne C; Kuhlthau, Karen; Pajolek, Hannah; Leisenring, Wendy; Armstrong, Greg T; Robison, Leslie L; Park, Elyse R

2013-02-01

The Affordable Care Act (ACA) will expand health insurance options for cancer survivors in the USA. It is unclear how this legislation will affect their access to employer-sponsored health insurance (ESI). We describe the health insurance experiences for survivors of childhood cancer with and without ESI. We conducted a series of qualitative interviews with 32 adult survivors from the Childhood Cancer Survivor Study to assess their employment-related concerns and decisions regarding health insurance coverage. Interviews were performed from August to December 2009 and were recorded, transcribed, and content analyzed using NVivo 8. Uninsured survivors described ongoing employment limitations, such as being employed at part-time capacity, which affected their access to ESI coverage. These survivors acknowledged they could not afford insurance without employer support. Survivors on ESI had previously been denied health insurance due to their preexisting health conditions until they obtained coverage through an employer. Survivors feared losing their ESI coverage, which created a disincentive to making career transitions. Others reported worries about insurance rescission if their cancer history was discovered. Survivors on ESI reported financial barriers in their ability to pay for health care. Childhood cancer survivors face barriers to obtaining ESI. While ACA provisions may mitigate insurance barriers for cancer survivors, many will still face cost barriers to affording health care without employer support.

Metabolite profiling and fingerprinting of Suillus species (Basidiomycetes) by electrospray mass spectrometry.

PubMed

Heinke, Ramona; Schöne, Pia; Arnold, Norbert; Wessjohann, Ludger; Schmidt, Jürgen; Schmidt, Jürgen

2014-01-01

The genus Suillus is known for the occurrence of a series of prenylated phenols and boviquinones. The extracts of four different Suillus species [S. bovinus, S. granulatus, S. tridentinus and S.variegatus) were investigated by using rapid ultra-performance Liquid chromatography/electrospray ionization mass spectrometry (UPLC/ESI-MS) and direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). While direct infusion ESI-FT-ICR mass spectra give a fast overview concerning the elemental compositions of the compounds and, therefore, hints to the main metabolites, UPLC/ESI-tandem mass spectrometry is shown to be a useful tool for their identification. A principal component analysis (PCA) and hierarchical cluster analysis (HCA) based on the UPLC/ESI-MS clearly showed that the metabolite profiles can be used not only for the identification and classification of such fungi but also as a sophisticated and powerful tool for the chemotaxonomy of fungi. Furthermore, a clear discrimination of various types of biological samples (fruiting bodies versus mycelial cultures) is also possible. The orthogonal partial least squares (OPLS) two-class models of both UPLC/ESI-MS and ESI-FT-ICR-MS possess a clear differentiation of two compared Suillus species representing the between class variation and the within class variation. Based on generated S-plots and Loading plots, statistically significant metabolites could be identified as potential biomarker for one species.

Bimetallic nanosized solids with acid and redox properties for catalytic activation of C–C and C–H bonds† †Electronic supplementary information (ESI) available: General procedures, additional figures and tables, compound characterization and NMR copies. See DOI: 10.1039/c6sc03335k Click here for additional data file.

PubMed Central

Cabrero-Antonino, Jose R.; Tejeda-Serrano, María; Quesada, Manuel; Vidal-Moya, Jose A.

2017-01-01

A new approach is presented to form self-supported bimetallic nanosized solids with acid and redox catalytic properties. They are water-, air- and H2-stable, and are able to activate demanding C–C and C–H reactions. A detailed mechanistic study on the formation of the Ag–Fe bimetallic system shows that a rapid redox-coupled sequence between Ag+, O2 (air) and Fe2+ occurs, giving monodisperse Ag nanoparticles supported by O-bridged diatomic Fe3+ triflimides. The system can be expanded to Ag nanoparticles embedded within a matrix of Cu2+, Bi3+ and Yb3+ triflimide. PMID:28451218

Vibrational spectroscopy and imaging for concurrent cellular trafficking of co-localized doxorubicin and deuterated phospholipid vesicles

NASA Astrophysics Data System (ADS)

Misra, S. K.; Mukherjee, P.; Ohoka, A.; Schwartz-Duval, A. S.; Tiwari, S.; Bhargava, R.; Pan, D.

2016-01-01

Simultaneous tracking of nanoparticles and encapsulated payload is of great importance and visualizing their activity is arduous. Here we use vibrational spectroscopy to study the in vitro tracking of co-localized lipid nanoparticles and encapsulated drug employing a model system derived from doxorubicin-encapsulated deuterated phospholipid (dodecyl phosphocholine-d38) single tailed phospholipid vesicles.Simultaneous tracking of nanoparticles and encapsulated payload is of great importance and visualizing their activity is arduous. Here we use vibrational spectroscopy to study the in vitro tracking of co-localized lipid nanoparticles and encapsulated drug employing a model system derived from doxorubicin-encapsulated deuterated phospholipid (dodecyl phosphocholine-d38) single tailed phospholipid vesicles. Electronic supplementary information (ESI) available: Raman and confocal images of the Deuto-DOX-NPs in cells, materials and details of methods. See DOI: 10.1039/c5nr07975f

Fortified interpenetrating polymers – bacteria resistant coatings for medical devices† †Electronic supplementary information (ESI) available: Supporting figures and tables, and additional experimental procedures. See DOI: 10.1039/c6tb01110a Click here for additional data file.

PubMed Central

Venkateswaran, Seshasailam; Henrique Dos Santos, Orlando David; Scholefield, Emma; Lilienkampf, Annamaria; Gwynne, Peter J.; Swann, David G.; Dhaliwal, Kevin

2016-01-01

Infections arising from contaminated medical devices are a serious global issue, contributing to antibiotic resistance and imposing significant strain on healthcare systems. Since the majority of medical device-associated infections are biofilm related, efforts are being made to generate either bacteria-repellent or antibacterial coatings aimed at preventing bacterial colonisation. Here, we utilise a nanocapsule mediated slow release of a natural antimicrobial to improve the performance of a bacteria repellent polymer coating. Poly(lauryl acrylate) nanocapsules containing eugenol (4-allyl-2-methoxyphenol) were prepared and entrapped within a interpenetrating network designed to repel bacteria. When coated on a catheter and an endotracheal tube, this hemocompatible system allowed slow-release of eugenol, resulting in notable reduction in surface-bound Klebsiella pneumoniae and methicillin resistant Staphylococcus aureus. PMID:27746915

Electrospray ion source with reduced analyte electrochemistry

DOEpatents

Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

2011-08-23

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

Electrospray ion source with reduced analyte electrochemistry

DOEpatents

Kertesz, Vilmos; Van Berkel, Gary J

2013-07-30

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution† †Electronic supplementary information (ESI) available: Tables containing crystallographic data and structure refinements for Na[V(L)2]·2H2O(cr) (CCDC 1413557) (Table S1) and Na[VO2(HL)](cr) (CCDC 1418830) (Table S2), concentrations of the solution samples for NMR (Table S3), 13C NMR spectra of V(v)/glutaroimide-dioxime complexes in H2 17O (Fig. S1), ESI-MS spectra of V(v)/glutaroimide-dioxime complexes in 17O-enriched H2O diluted and sprayed in methanol (Fig. S2), and EPR spectra of Na[V(L)2]·2H2O(s) at 4 K and 300 K (Fig. S3). CCDC 1413557–1418830. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03958d Click here for additional data file. Click here for additional data file.

PubMed Central

Leggett, C. J.; Parker, B. F.; Zhang, Z.; Dau, P. D.; Lukens, W. W.; Peterson, S. M.; Cardenas, A. J. P.; Warner, M. G.; Gibson, J. K.; Arnold, J.

2016-01-01

A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3–) coordinating to V5+, each in a tridentate mode via the imide N (R V–N = 1.96 Å) and oxime O atoms (R V–O = 1.87–1.90 Å). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bonds by glutaroimide-dioxime and verified the existence of the “bare” V5+/glutaroimide-dioxime complex, [V(L)2]–, in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]–, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido VO bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications. PMID:28660055

Drug-loaded nanoparticles induce gene expression in human pluripotent stem cell derivatives

NASA Astrophysics Data System (ADS)

Gajbhiye, Virendra; Escalante, Leah; Chen, Guojun; Laperle, Alex; Zheng, Qifeng; Steyer, Benjamin; Gong, Shaoqin; Saha, Krishanu

2013-12-01

Tissue engineering and advanced manufacturing of human stem cells requires a suite of tools to control gene expression spatiotemporally in culture. Inducible gene expression systems offer cell-extrinsic control, typically through addition of small molecules, but small molecule inducers typically contain few functional groups for further chemical modification. Doxycycline (DXC), a potent small molecule inducer of tetracycline (Tet) transgene systems, was conjugated to a hyperbranched dendritic polymer (Boltorn H40) and subsequently reacted with polyethylene glycol (PEG). The resulting PEG-H40-DXC nanoparticle exhibited pH-sensitive drug release behavior and successfully controlled gene expression in stem-cell-derived fibroblasts with a Tet-On system. While free DXC inhibited fibroblast proliferation and matrix metalloproteinase (MMP) activity, PEG-H40-DXC nanoparticles maintained higher fibroblast proliferation levels and MMP activity. The results demonstrate that the PEG-H40-DXC nanoparticle system provides an effective tool to controlling gene expression in human stem cell derivatives.Tissue engineering and advanced manufacturing of human stem cells requires a suite of tools to control gene expression spatiotemporally in culture. Inducible gene expression systems offer cell-extrinsic control, typically through addition of small molecules, but small molecule inducers typically contain few functional groups for further chemical modification. Doxycycline (DXC), a potent small molecule inducer of tetracycline (Tet) transgene systems, was conjugated to a hyperbranched dendritic polymer (Boltorn H40) and subsequently reacted with polyethylene glycol (PEG). The resulting PEG-H40-DXC nanoparticle exhibited pH-sensitive drug release behavior and successfully controlled gene expression in stem-cell-derived fibroblasts with a Tet-On system. While free DXC inhibited fibroblast proliferation and matrix metalloproteinase (MMP) activity, PEG-H40-DXC nanoparticles maintained higher fibroblast proliferation levels and MMP activity. The results demonstrate that the PEG-H40-DXC nanoparticle system provides an effective tool to controlling gene expression in human stem cell derivatives. Electronic supplementary information (ESI) available: ESI containing 1H NMR spectra and additional fibroblast characterization data. See DOI: 10.1039/c3nr04794f

Michigan Extended School Year Programs 1992-1995. An Evaluation of a State Grant Initiative.

ERIC Educational Resources Information Center

Axelrad-Lentz, Susan F.

Michigan lawmakers funded a competitive grant program for school districts to plan and implement extended school year (ESY) programs of 200 days. The primary purpose was to raise academic achievement. In the spring of 1992, 16 diverse school districts were awarded ESY planning grants. Continuation grants funded 2 ESY implementation years, for…

Remote sensing techniques for monitoring drought hazards: an intercomparison (Invited)

NASA Astrophysics Data System (ADS)

Brown, J. F.; Anderson, M. C.; Wardlow, B. D.; Svoboda, M. D.

2009-12-01

Drought events are frequently described using many different terms; for example, recurring climate phenomena, creeping natural hazards, agricultural disasters, and moisture deficiencies. In addition, droughts operate at many different spatial and temporal scales and affect different societal sectors, making them quite challenging to monitor, map, and assess impacts. Because of these factors, determining drought severity often requires using a convergence of evidence assisted by an analysis of multiple drought indicators. Frequent optical and thermal observations collected by daily polar-orbiting and geostationary satellites allow for regular monitoring of the land surface. In recent decades, with the launching of more advanced sensors and the maturation of remote sensing techniques, a variety of tools have been designed for improved understanding and tracking of drought events as they are occurring. These applications are intended to provide key decision makers with timely geospatial drought information to support various drought planning and mitigation activities. Two such tools highlighted in this study, are the Vegetation Drought Response Index (VegDRI) and the Evaporative Stress Index (ESI). While both indices incorporate satellite-based inputs, they are involved in different modeling approaches and observations from different parts of the electromagnetic spectrum. The VegDRI is a hybrid remote sensing and climate based indicator of drought-induced vegetation stress that combines satellite-based vegetation index observations from Moderate Resolution Imaging Spectroradiometer (MODIS) and Advanced Very High Resolution Radiometer (AVHRR) sensors with climate-based drought index data and other biophysical parameters (such as land use/land cover type and soil characteristics). VegDRI provides near real-time vegetation drought severity information at relatively higher spatial resolution (1-km2) than traditional climatic drought indices such as the Standardized Precipitation Index (SPI) or the U.S. Drought Monitor (USDM), which tend to depicted broad-scale spatial drought patterns. . The ESI is an indicator of anomalous land-surface evaporation and soil moisture deficiency. The ESI is related to the ratio of actual-to-potential evapotranspiration (ET), where actual ET is estimated with a thermal-infrared (TIR) based surface energy balance algorithm. The ESI product is generated in near-real time at 10-km2 resolution over the continental U.S. using TIR imagery from the Geostationary Operational Environmental Satellites (GOES). Because it does not use precipitation data as an input, it is a valuable complement to existing precipitation-based indices and is readily portable to data-poor regions with sparse ground-based rainfall monitoring networks. In this study, we present an intercomparison of the VegDRI and the ESI for the 2009 growing season, highlighting weekly, monthly, and seasonal patterns of moisture flux from soils and vegetation.

Comparison of HPLC/ESI-FTICR MS Versus MALDI-TOF/TOF MS for Glycopeptide Analysis of a Highly Glycosylated HIV Envelope Glycoprotein

PubMed Central

Irungu, Janet; Go, Eden P.; Zhang, Ying; Dalpathado, Dilusha S.; Liao, Hua-Xin; Haynes, Barton F.; Desaire, Heather

2013-01-01

Defining the structures and locations of the glycans attached on secreted proteins and virus envelope proteins is important in understanding how glycosylation affects their biological properties. Glycopeptide mass spectrometry (MS)-based analysis is a very powerful, emerging approach to characterize glycoproteins, in which glycosylation sites and the corresponding glycan structures are elucidated in a single MS experiment. However, to date there is not a consensus regarding which mass spectrometric platform provides the best glycosylation coverage information. Herein, we employ two of the most widely used MS approaches, online high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC/ESI-MS) and offline HPLC followed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), to determine which of the two approaches provides the best glycosylation coverage information of a complex glycoprotein, the group M consensus HIV-1 envelope, CON-S gp140ΔCFI, which has 31 potential glycosylation sites. Our results highlight differences in the informational content obtained between the two methods such as the overall number of glycosylation sites detected, the numbers of N-linked glycans present at each site, and the type of confirmatory information obtained about the glycopeptide using MS/MS experiments. The two approaches are quite complementary, both in their coverage of glycopeptides and in the information they provide in MS/MS experiments. The information in this study contributes to the field of mass spectrometry by demonstrating the strengths and limitations of two widely used MS platforms in glycoprotein analysis. PMID:18565761

On-Chip Spyhole Nanoelectrospray Ionization Mass Spectrometry for Sensitive Biomarker Detection in Small Volumes

NASA Astrophysics Data System (ADS)

Zhong, Xiaoqin; Qiao, Liang; Stauffer, Géraldine; Liu, Baohong; Girault, Hubert H.

2018-03-01

A polyimide microfluidic chip with a microhole emitter (Ø 10-12 μm) created on top of a microchannel by scanning laser ablation has been designed for nanoelectrospray ionization (spyhole-nanoESI) to couple microfluidics with mass spectrometry. The spyhole-nanoESI showed higher sensitivity compared to standard ESI and microESI from the end of the microchannel. The limits of detection (LOD) for peptide with the spyhole-nanoESI MS reached 50 pM, which was 600 times lower than that with standard ESI. The present microchip emitter allows the analysis of small volumes of samples. As an example, a small cell lung cancer biomarker, neuron-specific enolase (NSE), was detected by monitoring the transition of its unique peptide with the spyhole-nanoESI MS/MS. NSE at 0.2 nM could be well identified with a signal to noise ratio (S/N) of 50, and thereby its LOD was estimated to be 12 pM. The potential application of the spyhole-nanoESI MS/MS in cancer diagnosis was further demonstrated with the successful detection of 2 nM NSE from 1 μL of human serum. Before the detection, the serum sample spiked with NSE was first depleted with immune spin column, then desalted by centrifugal filter device, and finally digested by trypsin, without any other complicated preparation steps. The concentration matched the real condition of clinical samples. In addition, the microchips can be disposable to avoid any cross contamination. The present technique provides a highly efficient way to couple microfluidics with MS, which brings additional values to various microfluidics and MS-based analysis.

Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool.

PubMed

Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

2018-03-01

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H] - . Nevertheless, NH 3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous C x H y O z bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. Graphical Abstract ᅟ.

Continuous EEG source imaging enhances analysis of EEG-fMRI in focal epilepsy.

PubMed

Vulliemoz, S; Rodionov, R; Carmichael, D W; Thornton, R; Guye, M; Lhatoo, S D; Michel, C M; Duncan, J S; Lemieux, L

2010-02-15

EEG-correlated fMRI (EEG-fMRI) studies can reveal haemodynamic changes associated with Interictal Epileptic Discharges (IED). Methodological improvements are needed to increase sensitivity and specificity for localising the epileptogenic zone. We investigated whether the estimated EEG source activity improved models of the BOLD changes in EEG-fMRI data, compared to conventional < event-related > designs based solely on the visual identification of IED. Ten patients with pharmaco-resistant focal epilepsy underwent EEG-fMRI. EEG Source Imaging (ESI) was performed on intra-fMRI averaged IED to identify the irritative zone. The continuous activity of this estimated IED source (cESI) over the entire recording was used for fMRI analysis (cESI model). The maps of BOLD signal changes explained by cESI were compared to results of the conventional IED-related model. ESI was concordant with non-invasive data in 13/15 different types of IED. The cESI model explained significant additional BOLD variance in regions concordant with video-EEG, structural MRI or, when available, intracranial EEG in 10/15 IED. The cESI model allowed better detection of the BOLD cluster, concordant with intracranial EEG in 4/7 IED, compared to the IED model. In 4 IED types, cESI-related BOLD signal changes were diffuse with a pattern suggestive of contamination of the source signal by artefacts, notably incompletely corrected motion and pulse artefact. In one IED type, there was no significant BOLD change with either model. Continuous EEG source imaging can improve the modelling of BOLD changes related to interictal epileptic activity and this may enhance the localisation of the irritative zone. Copyright 2009 Elsevier Inc. All rights reserved.

Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool

NASA Astrophysics Data System (ADS)

Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

2018-03-01

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H]-. Nevertheless, NH3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous CxHyOz bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. [Figure not available: see fulltext.

Ethnic Disparities in Emergency Severity Index Scores among U.S. Veteran’s Affairs Emergency Department Patients

PubMed Central

Vigil, Jacob M.; Alcock, Joe; Coulombe, Patrick; McPherson, Laurie; Parshall, Mark; Murata, Allison; Brislen, Heather

2015-01-01

Background The goal of these analyses was to determine whether there were systematic differences in Emergency Severity Index (ESI) scores, which are intended to determine priority of treatment and anticipate resource needs, across categories of race and ethnicity, after accounting for patient-presenting vital signs and examiner characteristics, and whether these differences varied among male and female Veterans Affairs (VA) ED patients. Methods and Findings We used a large national database of electronic medical records of ED patients from twenty-two U.S. Department of Veterans Affairs ED stations to determine whether ESI assignments differ systematically by race or ethnicity. Multi-level, random effects linear modeling was used to control for demographic characteristics and patient’s vital signs (heart rate, respiratory rate, and pain level), as well as age, gender, and experience of triage nurses. The dataset included 129,991 VA patients presenting for emergency care between 2008 and 2012 (91% males; 61% non-Hispanic White, 28% Black, 7% Hispanic, 2% Asian, <1% American Indian/Alaska Native, 1% mixed ethnicity) and 774 nurses for a total of 359,642 patient/examiner encounters. Approximately 13% of the variance in ESI scores was due to patient characteristics and 21% was due to the nurse characteristics. After controlling for characteristics of nurses and patients, Black patients were assigned less urgent ESI scores than White patients, and this effect was more prominent for Black males compared with Black females. A similar interaction was found for Hispanic males. It remains unclear how these results may generalize to EDs and patient populations outside of the U.S. VA Health Care system. Conclusions The findings suggest the possibility that subgroups of VA patients receive different ESI ratings in triage, which may have cascading, downstream consequences for patient treatment quality, satisfaction with care, and trust in the health equity of emergency care. PMID:26024515

Comparison of hydrodynamically closed isotachophoresis-capillary zone electrophoresis with hydrodynamically open capillary zone electrophoresis hyphenated with tandem mass spectrometry in drug analysis: pheniramine, its metabolite and phenylephrine in human urine.

PubMed

Piešťanský, Juraj; Maráková, Katarína; Kovaľ, Marián; Mikuš, Peter

2014-09-05

The advanced two dimensional isotachophoresis (ITP)-capillary zone electrophoresis (CZE) hyphenated with tandem mass spectrometry (MS/MS, here triple quadrupole, QqQ) was developed in this work to demonstrate analytical potentialities of this approach in the analysis of drugs in multicomponent ionic matrices. Pheniramine (PHM), phenylephrine (PHE), paracetamol (PCM) and their potential metabolic products were taken for the analysis by the ITP-CZE-ESI-QqQ technique working in hydrodynamically closed CE separation system and then a comparison with the conventional (hydrodynamically open) CZE-ESI-QqQ technique was made. The ITP-CZE-ESI-QqQ method was favorable in terms of obtainable selectivity (due to highly effective heart-cut analysis), concentration limits of detection (LOD at pgmL(-1) levels due to enhanced sample load capacity and ITP preconcentration), sample handling (on-line sample pretreatment, i.e. clean-up, preconcentration, preseparation), and, by that, possibilities for future automation and miniaturization. On the other hand, this experimental arrangement, in contrast to the CZE-ESI-QqQ arrangement supported by an electroosmotic flow, is principally limited to the analysis of uniformly (i.e. positively or negatively) charged analytes in one run without any possibilities to analyze neutral compounds (here, PCM and neutral or acidic metabolites of the drugs had to be excluded from the analysis). Hence, these general characteristics should be considered when choosing a proper analytical CE-MS approach for a given biomedical application. Here, the analytical potential of the ITP-CZE-ESI-QqQ method was demonstrated showing the real time profiles of excreted targeted drugs and metabolite (PHM, PHE, M-PHM) in human urine after the administration of one dose of Theraflu(®) to the volunteers. Copyright © 2014 Elsevier B.V. All rights reserved.

Evaluation of analytical performance and reliability of direct nanoLC-nanoESI-high resolution mass spectrometry for profiling the (xeno)metabolome.

PubMed

Chetwynd, Andrew J; David, Arthur; Hill, Elizabeth M; Abdul-Sada, Alaa

2014-10-01

Mass spectrometry (MS) profiling techniques are used for analysing metabolites and xenobiotics in biofluids; however, detection of low abundance compounds using conventional MS techniques is poor. To counter this, nanoflow ultra-high-pressure liquid chromatography-nanoelectrospray ionization-time-of-flight MS (nUHPLC-nESI-TOFMS), which has been used primarily for proteomics, offers an innovative prospect for profiling small molecules. Compared to conventional UHPLC-ESI-TOFMS, nUHPLC-nESI-TOFMS enhanced detection limits of a variety of (xeno)metabolites by between 2 and 2000-fold. In addition, this study demonstrates for the first time excellent repeatability and reproducibility for analysis of urine and plasma samples using nUHPLC-nESI-TOFMS, supporting implementation of this platform as a novel approach for high-throughput (xeno)metabolomics. Copyright © 2014 John Wiley & Sons, Ltd.

Energy Systems Integration News | Energy Systems Integration Facility |

Science.gov Websites

NREL six people standing at a table with various containers of pet food. NREL's ESI program included with this release. Register for the webinar. Presentations Available from Last Month's High withstand the crucial first minute after severe grid disturbances with high penetrations of wind and solar

A sulphonated carbon dot-chitosan hybrid hydrogel nanocomposite as an efficient ion-exchange film for Ca2+ and Mg2+ removal

NASA Astrophysics Data System (ADS)

Baruah, Upama; Konwar, Achyut; Chowdhury, Devasish

2016-04-01

We have developed a hybrid hydrogel nanocomposite film via conjugation of oxidised carbon dots synthesized from 11-mercaptoundecanoic acid with chitosan. The potential applicability of the film was then successfully tested for the removal of Ca2+ and Mg2+ ions from solution.We have developed a hybrid hydrogel nanocomposite film via conjugation of oxidised carbon dots synthesized from 11-mercaptoundecanoic acid with chitosan. The potential applicability of the film was then successfully tested for the removal of Ca2+ and Mg2+ ions from solution. Electronic supplementary information (ESI) available: The ESI includes the detailed synthesis and characterization of carbon dots both before and after oxidation and of the carbon dot-chitosan nanocomposite films viz. DLS, SEM, UV-visible, FTIR, PL spectroscopy and TGA. See DOI: 10.1039/c6nr01129b

A thermochromic silver nanocluster exhibiting dual emission character

NASA Astrophysics Data System (ADS)

Xu, Qing-Qing; Dong, Xi-Yan; Huang, Ren-Wu; Li, Bo; Zang, Shuang-Quan; Mak, Thomas C. W.

2015-01-01

A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow.A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow. Electronic supplementary information (ESI) available: Experimental section and supporting Fig. S1-S6. CCDC 1004246. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr05122j

An ambient stable core-substituted perylene bisimide dianion: isolation and single crystal structure analysis† †Electronic supplementary information (ESI) available: Synthesis, spectroelectrochemistry, UV-vis, electrochemistry, X-ray diffraction, NMR and mass spectra. CCDC 1032959. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03671a Click here for additional data file. Click here for additional data file.

PubMed Central

Seifert, Sabine; Schmidt, David

2015-01-01

Here we report the first example of an isolable, ambient stable perylene bisimide (PBI) dianion which was synthesized by catalytic reduction of a highly electron deficient PBI derivative. The remarkable stability of this unprecedented dianion in air for months facilitated its complete characterization by different methods, including single crystal X-ray analysis. Furthermore, solvent dependent cyclic and square wave voltammetry studies revealed that the formation of PBI dianions is preferred in more polar solvents, whereas the generation of PBI radical anions should be favoured in less polar solvents. PMID:28717450

Cobalt catalyzed carbonylation of unactivated C(sp3)–H bonds† †Electronic supplementary information (ESI) available. CCDC 1507203 (2t) & 1507204 (2a). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05026c Click here for additional data file. Click here for additional data file.

PubMed Central

Barsu, Nagaraju; Bolli, Shyam Kumar

2017-01-01

A general efficient regioselective cobalt catalyzed carbonylation of unactivated C(sp3)–H bonds of aliphatic amides was demonstrated using atmospheric (1–2 atm) carbon monoxide as a C1 source. This straightforward approach provides access to α-spiral succinimide regioselectively in a good yield. Cobalt catalyzed sp3 C–H bond carbonylation is reported for the first time including the functionalization of (β)-C–H bonds of α-1°, 2°, 3° carbons and even internal (β)-C–H bonds. Our initial mechanistic investigation reveals that the C–H activation step is irreversible and will possibly be the rate determining step. PMID:28451350

Direct chemical profiling of olive (Olea europaea) fruit epicuticular waxes by direct electrospray-ultrahigh resolution mass spectrometry.

PubMed

Vichi, Stefania; Cortés-Francisco, Nuria; Romero, Agustí; Caixach, Josep

2015-03-01

In the present paper, an electrospray ionization (ESI)-Orbitrap method is proposed for the direct chemical profiling of epicuticular wax (EW) from Olea europaea fruit. It constitutes a rapid and efficient tool suitable for a wide-ranging screening of a large number of samples. In a few minutes, the method provides a comprehensive characterization of total EW extracts, based on the molecular formula of their components. Accurate mass measurements are obtained by ultrahigh resolution mass spectrometry, and compositional restrictions are set on the basis of the information available from previous studies of olive EW. By alternating positive and negative ESI modes within the same analysis, complementary results are obtained and a wide range of chemical species is covered. This provides a detailed compositional overview that otherwise would only be available by applying multiple analytical techniques. Copyright © 2015 John Wiley & Sons, Ltd.

A molecular-sized tunnel-porous crystal with a ratchet gear structure and its one-way guest-molecule transportation property

NASA Astrophysics Data System (ADS)

Kataoka, Keisuke; Yasumoto, Tetsuaki; Manabe, Yousuke; Sato, Hiroyasu; Yamano, Akihito; Katagiri, Toshimasa

2013-01-01

An anisotropic tunnel microporous crystal was prepared. Active transportation of anthracene as a guest molecule in the anisotropic tunnels was observed. The direction of anthracene movement implies that the anisotropic tunnel did not work as a flap-check valve. The direction of the movement was consistent with that caused by a Brownian ratchet.An anisotropic tunnel microporous crystal was prepared. Active transportation of anthracene as a guest molecule in the anisotropic tunnels was observed. The direction of anthracene movement implies that the anisotropic tunnel did not work as a flap-check valve. The direction of the movement was consistent with that caused by a Brownian ratchet. Electronic supplementary information (ESI) available. CCDC reference numbers 837539 and 837540. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30880k

Flexibility transition and guest-driven reconstruction in a ferroelastic metal-organic framework†Electronic supplementary information (ESI) available: Atomic coordinates and lattice parameter data. CCDC 1016797. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4ce01572jClick here for additional data file.

PubMed

Hunt, Sarah J; Cliffe, Matthew J; Hill, Joshua A; Cairns, Andrew B; Funnell, Nicholas P; Goodwin, Andrew L

2015-01-14

The metal-organic framework copper(i) tricyanomethanide, Cu(tcm), undergoes a ferroelastic transition on cooling below T f = 240 K. Thermal expansion measurements reveal an order-of-magnitude variation in framework flexibility across T f . The low-temperature phase α-Cu(tcm) exhibits colossal positive and negative thermal expansion that is the strongest ever reported for a framework material. On exposure to acetonitrile, Cu(tcm) undergoes a reconstructive solid-phase transition to acetonitrilocopper(i) tricyanomethanide. This transition can be reversed by heating under vacuum. Infrared spectroscopy measurements are sensitive to the phase change, suggesting that Cu(tcm) may find application in solid-phase acetonitrile sensing.

Collaboration and Compromise: The Big Picture of Energy Systems Integration

Science.gov Websites

research direction at NREL. Photo by Dennis Schroeder Portrait of ESI researcher Mark O'Malley Mark by Dennis Schroeder Mark O'Malley is a research fellow at the National Renewable Energy Laboratory

75 FR 54914 - Notice Pursuant to the National Cooperative Research and Production Act of 1993-Robotics...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-09

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Nine Tips for Creating an Effective Extended School Year Program for Students with Disabilities

ERIC Educational Resources Information Center

Sobeck, Emily Eyrolles

2017-01-01

Extended school year (ESY) is a summer program available for students with disabilities who meet specific qualifying criteria. Teachers are often hesitant to accept the position of the ESY teacher due to the ambiguities and demands of the position. The purpose of this article is to briefly share the impetus and focus of ESY and give special…

Two competing ionization processes in electrospray mass spectrometry of indolyl benzo[b]carbazoles: formation of M⁺• versus [M + H]⁺.

PubMed

Zhang, Xiaoping; Jiang, Kezhi; Zou, Jingfeng; Li, Zuguang

2015-02-15

Ionization in electrospray ionization mass spectrometry (ESI-MS) mainly occurs as a result of acid-base reactions or coordination with metal cations. Formation of the radical cation M(+•) in the ESI process has attracted our interest to perform further investigation. A series of indolyl benzo[b]carbazoles were investigated using a quadrupole ion trap mass spectrometer equipped with an ESI source or an atmospheric pressure chemical ionization (APCI) source in the positive-ion mode. Theoretical calculations were performed using the density functional theory (DFT) method at the B3LYP/6-31G(d) level. Both the radical ion M(+•) and the protonated molecule [M + H](+) were obtained by ESI-MS analysis of indolyl benzo[b]carbazoles, while only [M + H](+) was observed in the APCI-MS analysis. The relative intensities of M(+•) and [M + H](+) were significantly affected by several ESI operating parameters and the nature of the substituents. Formation of M(+•) and [M + H](+) was rationalized as two competing ionization processes in the ESI-MS analysis of indolyl benzo[b]carbazoles. Copyright © 2014 John Wiley & Sons, Ltd.

PCR Followed by Electrospray Ionization Mass Spectrometry for Broad-Range Identification of Fungal Pathogens

PubMed Central

Massire, Christian; Buelow, Daelynn R.; Zhang, Sean X.; Lovari, Robert; Matthews, Heather E.; Toleno, Donna M.; Ranken, Raymond R.; Hall, Thomas A.; Metzgar, David; Sampath, Rangarajan; Blyn, Lawrence B.; Ecker, David J.; Gu, Zhengming; Walsh, Thomas J.

2013-01-01

Invasive fungal infections are a significant cause of morbidity and mortality among immunocompromised patients. Early and accurate identification of these pathogens is central to direct therapy and to improve overall outcome. PCR coupled with electrospray ionization mass spectrometry (PCR/ESI-MS) was evaluated as a novel means for identification of fungal pathogens. Using a database grounded by 60 ATCC reference strains, a total of 394 clinical fungal isolates (264 molds and 130 yeasts) were analyzed by PCR/ESI-MS; results were compared to phenotypic identification, and discrepant results were sequence confirmed. PCR/ESI-MS identified 81.4% of molds to either the genus or species level, with concordance rates of 89.7% and 87.4%, respectively, to phenotypic identification. Likewise, PCR/ESI-MS was able to identify 98.4% of yeasts to either the genus or species level, agreeing with 100% of phenotypic results at both the genus and species level. PCR/ESI-MS performed best with Aspergillus and Candida isolates, generating species-level identification in 94.4% and 99.2% of isolates, respectively. PCR/ESI-MS is a promising new technology for broad-range detection and identification of medically important fungal pathogens that cause invasive mycoses. PMID:23303501

A self optimizing synthetic organic reactor system using real-time in-line NMR spectroscopy† †Electronic supplementary information (ESI) available: Details about the methodology, LabView scripts, experimental set-ups, additional spectra and self-optimization can be found in the SI. See DOI: 10.1039/c4sc03075c Click here for additional data file.

PubMed Central

Sans, Victor; Porwol, Luzian; Dragone, Vincenza

2015-01-01

A configurable platform for synthetic chemistry incorporating an in-line benchtop NMR that is capable of monitoring and controlling organic reactions in real-time is presented. The platform is controlled via a modular LabView software control system for the hardware, NMR, data analysis and feedback optimization. Using this platform we report the real-time advanced structural characterization of reaction mixtures, including 19F, 13C, DEPT, 2D NMR spectroscopy (COSY, HSQC and 19F-COSY) for the first time. Finally, the potential of this technique is demonstrated through the optimization of a catalytic organic reaction in real-time, showing its applicability to self-optimizing systems using criteria such as stereoselectivity, multi-nuclear measurements or 2D correlations. PMID:29560211

Methodology of analysis of very weak acids by isotachophoresis with electrospray-ionization mass-spectrometric detection: Anionic electrolyte systems for the medium-alkaline pH range.

PubMed

Malá, Zdena; Gebauer, Petr

2018-01-15

This work describes for the first time a functional electrolyte system setup for anionic isotachophoresis (ITP) with electrospray-ionization mass-spectrometric (ESI-MS) detection in the neutral to medium-alkaline pH range. So far no application was published on the analysis of very weak acids by anionic ITP-MS although there is a broad spectrum of potential analytes with pK a values in the range 5-10, where application of this technique promises interesting gains in both sensitivity and specificity. The problem so far was the lack of anionic ESI-compatible ITP systems in the mentioned pH range as all typical volatile anionic system components are fully ionized at neutral and alkaline pH and thus too fast to suit as terminators. We propose an original solution of the problem based on the combination of two ITP methods: (i) use of the hydroxyl ion as a natural and ESI-compatible terminator, and (ii) use of configurations based on moving-boundary ITP. The former method ensures effective stacking of analytes by an alkaline terminator of sufficiently low mobility and the latter offers increased flexibility for tuning of the separation window and selectivity according to actual needs. A theoretical description of the proposed model is presented and applied to the design of very simple functional electrolyte configurations. The properties of example systems are demonstrated by both computer simulation and experiments with a group of model analytes. Potential effects of carbon dioxide present in the solutions are demonstrated for particular systems. Experimental results confirm that the proposed methodology is well capable of performing sensitive and selective ITP-MS analyses of very weak acidic analytes (e.g. sulfonamides or chlorophenols). Copyright © 2017 Elsevier B.V. All rights reserved.

Target-guided separation of Bougainvillea glabra betacyanins by direct coupling of preparative ion-pair high-speed countercurrent chromatography and electrospray ionization mass-spectrometry.

PubMed

Jerz, Gerold; Wybraniec, Sławomir; Gebers, Nadine; Winterhalter, Peter

2010-07-02

In this study, preparative ion-pair high-speed countercurrent chromatography was directly coupled to an electrospray ionization mass-spectrometry device (IP-HSCCC/ESI-MS-MS) for target-guided fractionation of high molecular weight acyl-oligosaccharide linked betacyanins from purple bracts of Bougainvillea glabra (Nyctaginaceae). The direct identification of six principal acyl-oligosaccharide linked betacyanins in the mass range between m/z 859 and m/z 1359 was achieved by positive ESI-MS ionization and gave access to the genuine pigment profile already during the proceeding of the preparative separation. Inclusively, all MS/MS-fragmentation data were provided during the chromatographic run for a complete analysis of substitution pattern. On-line purity evaluation of the recovered fractions is of high value in target-guided screening procedures and for immediate decisions about suitable fractions used for further structural analysis. The applied preparative hyphenation was shown to be a versatile screening method for on-line monitoring of countercurrent chromatographic separations of polar crude pigment extracts and also traced some minor concentrated compounds. For the separation of 760mg crude pigment extract the biphasic solvent system tert.-butylmethylether/n-butanol/acetonitrile/water 2:2:1:5 (v/v/v/v) was used with addition of ion-pair forming reagent trifluoroacetic acid. The preparative HSCCC-eluate had to be modified by post-column addition of a make-up solvent stream containing formic acid to reduce ion-suppression caused by trifluoroacetic acid and later significantly maximized response of ESI-MS/MS detection of target substances. A variable low-pressure split-unit guided a micro-eluate to the ESI-MS-interface for sensitive and direct on-line detection, and the major volume of the effluent stream was directed to the fraction collector for preparative sample recovery. The applied make-up solvent mixture significantly improved smoothness of the continuously measured IP-HSCCC-ESI-MS base peak ion trace in the experimental range of m/z 50-2200 by masking stationary phase bleeding and generating a stable single solvent phase for ESI-MS/MS detection. Immediate structural data were retrieved throughout the countercurrent chromatography run containing complete MS/MS-fragmentation pattern of the separated acyl-substituted betanidin oligoglycosides. Single ion monitoring indicated clearly the base-line separation of higher concentrated acylated betacyanin components. Copyright 2010 Elsevier B.V. All rights reserved.

Broad-Range Detection of Microorganisms Directly from Bronchoalveolar Lavage Specimens by PCR/Electrospray Ionization-Mass Spectrometry

PubMed Central

Ullberg, Måns; Lüthje, Petra; Mölling, Paula; Strålin, Kristoffer

2017-01-01

The clinical demand on rapid microbiological diagnostic is constantly increasing. PCR coupled to electrospray ionization-mass spectrometry, PCR/ESI-MS, offers detection and identification of over 750 bacteria and Candida species directly from clinical specimens within 6 hours. In this study, we investigated the clinical performance of the IRIDICA BAC LRT Assay for detection of bacterial pathogens in 121 bronchoalveolar lavage (BAL) samples that were received consecutively at our bacterial laboratory for BAL culture. Commensal or pathogenic microorganisms were detected in 118/121 (98%) BAL samples by PCR/ESI-MS, while in 104/121 (86%) samples by routine culture (P<0.01). Detection of potentially pathogenic microorganisms by PCR/ESI-MS was evaluated in comparison with conventional culture-based or molecular methods. The agreement between positive findings was overall good. Most Staphylococcus aureus-positive PCR/ESI-MS results were confirmed by culture or species-specific PCR (27/33, 82%). The identity of Streptococcus pneumoniae could however be confirmed for only 6/17 (35%) PCR/ESI-MS-positive samples. Non-cultivable and fastidious pathogens, which were not covered by standard culture procedures were readily detected by PCR/ESI-MS, including Legionella pneumophila, Bordetella pertussis, Norcadia species and Mycoplasma pneumoniae. In conclusion, PCR/ESI-MS detected a broad range of potential pathogens with equal or superior sensitivity compared to conventional methods within few hours directly from BAL samples. This novel method might thus provide a relevant tool for diagnostics in critically ill patients. PMID:28085931

High-performance liquid chromatography-mass spectrometry for mapping and sequencing glycosaminoglycan-derived oligosaccharides

PubMed Central

Volpi, Nicola; Linhardt, Robert J

2012-01-01

Glycosaminoglycans (GAGs) have proven to be very difficult to analyze and characterize because of their high negative charge density, polydispersity and sequence heterogeneity. As the specificity of the interactions between GAGs and proteins results from the structure of these polysaccharides, an understanding of GAG structure is essential for developing a structure–activity relationship. Electrospray ionization (ESI) mass spectrometry (MS) is particularly promising for the analysis of oligosaccharides chemically or enzymatically generated by GAGs because of its relatively soft ionization capacity. Furthermore, on-line high-performance liquid chromatography (HPLC)-MS greatly enhances the characterization of complex mixtures of GAG-derived oligosaccharides, providing important structural information and affording their disaccharide composition. A detailed protocol for producing oligosaccharides from various GAGs, using controlled, specific enzymatic or chemical depolymerization, is presented, together with their HPLC separation, using volatile reversed-phase ion-pairing reagents and on-line ESI-MS structural identification. This analysis provides an oligosaccharide map together with sequence information from a reading frame beginning at the nonreducing end of the GAG chains. The preparation of oligosaccharides can be carried out in 10 h, with subsequent HPLC analysis in 1–2 h and HPLC-MS analysis taking another 2 h. PMID:20448545

Electrospray Ionization Mass Spectrometry

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

Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

2014-06-13

Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

Separation and characterisation of five polar herbicides using countercurrent chromatography with detection by negative ion electrospray ionisation mass spectrometry.

PubMed

Kidwell, H; Jones, J J; Games, D E

2001-01-01

Five polar herbicides were separated and characterised using high-speed analytical countercurrent chromatography (HSACCC) in conjunction with online electrospray mass spectrometry (ESI-MS). The countercurrent chromatography used a standard isocratic biphasic solvent system of hexane/ethyl acetate/methanol/water in reverse phase to effect the separation of these five environmentally important compounds. The chromatograph was coupled to a triple quadrupole mass spectrometer via a standard electrospray liquid chromatography interface that was able to give mass spectra in negative ion mode of each compound. Limits of detection are reported for this series of compounds along with representative negative ion ESI-MS data and calibrations for the separation. Copyright 2001 John Wiley & Sons, Ltd.

Assessing Jasminum grandiflorum L. authenticity by HPLC-DAD-ESI/MS(n) and effects on physiological enzymes and oxidative species.

PubMed

Ferreres, Federico; Grosso, Clara; Gil-Izquierdo, Angel; Valentão, Patrícia; Andrade, Paula B

2014-01-01

The dried flower buds of Jasminum grandiflorum L. are widely consumed as infusion and used in traditional medicine for psychiatric disorders. It is important to have a well-established method for the chemical characterization of J. grandiflorum since there are resemblances with a toxic species, Gelsemium sempervirens (L.) Jaume Saint-Hilaire. HPLC-DAD-ESI/MS(n) analysis allowed identifying six phenolic compounds for the first time. Moreover, the evaluation of in vitro activity against central nervous system (CNS) related enzymes was undertaken for the first time, as well as against reactive species in order to support the efficacy towards CNS disorders. Copyright © 2013 Elsevier B.V. All rights reserved.

Antimicrobial residues in animal waste and water resources proximal to large-scale swine and poultry feeding operations

USGS Publications Warehouse

Campagnolo, E.R.; Johnson, K.R.; Karpati, A.; Rubin, C.S.; Kolpin, D.W.; Meyer, M.T.; Esteban, J. Emilio; Currier, R.W.; Smith, K.; Thu, K.M.; McGeehin, M.

2002-01-01

Expansion and intensification of large-scale animal feeding operations (AFOs) in the United States has resulted in concern about environmental contamination and its potential public health impacts. The objective of this investigation was to obtain background data on a broad profile of antimicrobial residues in animal wastes and surface water and groundwater proximal to large-scale swine and poultry operations. The samples were measured for antimicrobial compounds using both radioimmunoassay and liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) techniques. Multiple classes of antimicrobial compounds (commonly at concentrations of >100 μg/l) were detected in swine waste storage lagoons. In addition, multiple classes of antimicrobial compounds were detected in surface and groundwater samples collected proximal to the swine and poultry farms. This information indicates that animal waste used as fertilizer for crops may serve as a source of antimicrobial residues for the environment. Further research is required to determine if the levels of antimicrobials detected in this study are of consequence to human and/or environmental ecosystems. A comparison of the radioimmunoassay and LC/ESI-MS analytical methods documented that radioimmunoassay techniques were only appropriate for measuring residues in animal waste samples likely to contain high levels of antimicrobials. More sensitive LC/ESI-MS techniques are required in environmental samples, where low levels of antimicrobial residues are more likely.

Identification of number and type of cations in water-soluble Cs+ and Na+ calix[4]arene-bis-crown-6 complexes by using ESI-TOF-MS.

PubMed

Kumagai, Shogo; Hayashi, Kotaro; Kameda, Tomohito; Morohashi, Naoya; Hattori, Tetsutaro; Yoshioka, Toshiaki

2018-04-01

The treatment of cesium-contaminated wastewater has become one of the biggest issues. The selective Cs + removal from wastewater containing competitive alkali metal ions such as Na + is desired to reduce the volume of sludge. Therefore, the present work focused on water-soluble calix[4]arene-bis-crown-6 (W-BisC6) to selectively capture Cs + . For characterization of the complex, UV-vis spectroscopy is commonly used, however, due to the limited availability of information it can be hard to quickly identify the specific structures of some complexes. In this work, the electrospray ionization time of flight spectrometry (ESI-TOF-MS) is successfully utilized to identify the number and type of cations in W-BisC6-cation complexes. ESI-TOF-MS accurately recognized 4 types of complex (W-BisC6-Na + , W-BisC6-Cs + , W-BisC6-2Na + , W-BisC6-Na + -Cs + ), and the experimental and simulated results were almost perfectly matched. It also revealed the difficulty of W-BisC6-2Cs + complex formation under the present conditions. Thus, this technique is significantly helpful for rapid identification of the specific structures of complexes during Cs + -contaminated wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand† †Electronic supplementary information (ESI) available: Complete experimental procedures and magnetic measurements and models. CCDC 1417565–1417567. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03006d Click here for additional data file. Click here for additional data file.

PubMed Central

Wong, Janice L.; Higgins, Robert F.; Bhowmick, Indrani; Cao, David Xi; Szigethy, Géza; Ziller, Joseph W.

2016-01-01

A new bimetallic platform comprising a six-coordinate Fe(ONO)2 unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONOcat)H3 = bis(3,5-di-tert-butyl-2-phenol)amine). Reaction of Fe(ONO)2 with either (ONOcat)Fe(py)3 or with (ONOq)FeCl2 under reducing conditions led to the formation of the bimetallic complex Fe2(ONO)3, which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO)2 with the new synthon (ONOsq˙)Zn(py)2 led to the formation of the heterobimetallic complex FeZn(ONO)3, with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO)3 are consistent with a ground state S = 3/2 spin system, generated from a high-spin iron(ii) center that is antiferromagnetically coupled to a single (ONOsq˙)2– radical ligand. In the case of Fe2(ONO)3, the magnetic data revealed a ground state S = 7/2 spin system arising from the interactions of one high-spin iron(ii) center, one high-spin iron(iii) center, and two (ONOsq˙)2– radical ligands. PMID:28808535

Quasar 2175 Å dust absorbers - I. Metallicity, depletion pattern and kinematics

NASA Astrophysics Data System (ADS)

Ma, Jingzhe; Ge, Jian; Zhao, Yinan; Prochaska, J. Xavier; Zhang, Shaohua; Ji, Tuo; Schneider, Donald P.

2017-12-01

We present 13 new 2175 Å dust absorbers at zabs = 1.0-2.2 towards background quasars from the Sloan Digital Sky Survey. These absorbers are examined in detail using data from the Echelle Spectrograph and Imager (ESI) on the Keck II telescope. Many low-ionization lines including Fe II, Zn II, Mg II, Si II, Al II, Ni II, Mn II, Cr II, Ti II and Ca II are present in the same absorber that gives rise to the 2175 Å bump. The relative metal abundances (with respect to Zn) demonstrate that the depletion patterns of our 2175 Å dust absorbers resemble that of the Milky Way clouds although some are disc-like and some are halo-like. The 2175 Å dust absorbers have significantly higher depletion levels compared to literature damped Lyman α absorbers (DLAs) and sub-DLAs. The dust depletion level indicator [Fe/Zn] tends to anticorrelate with bump strengths. The velocity profiles from the Keck/ESI spectra also provide kinematical information on the dust absorbers. The dust absorbers are found to have multiple velocity components with velocity widths extending from ∼100 to ∼600 km s-1, which are larger than those of most DLAs and sub-DLAs. Assuming the velocity width is a reliable tracer of stellar mass, the host galaxies of 2175 Å dust absorbers are expected to be more massive than DLA/sub-DLA hosts. Not all of the 2175 Å dust absorbers are intervening systems towards background quasars. The absorbers towards quasars J1006+1538 and J1047+3423 are proximate systems that could be associated with the quasar itself or the host galaxy.

Use of an ion mobility spectrometer for detecting uranium compounds

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

McLain, Derek R.; Steeb, Jennifer L.; Smith, Nicholas A.

The safeguards community currently lacks a method to rapidly determine the chemical form of radioactive and non-radioactive compounds in real time during inspection activities. Chemical speciation identification can provide important information on both the types of materials that are collected during environmental sampling and can inform inspectors as to where to focus efforts during inspections or complementary access visits. Ion Mobility Spectrometry (IMS) is an established field technique for the detection of explosives, narcotics, and other organic compounds. More recently, electrospray ionization (ESI) has been used to introduce inorganic compounds to IMS instruments for analysis. These techniques have shown themore » ability to supply chemical information about the compounds being analyzed. Although these laboratory based instruments use a liquid-based injection system, there is evidence in the literature of unaltered and intact pharmaceutical tablets being volatilized and ionized in open atmosphere using heat and a Ni-63 source. Lastly, this work determined that a commercial-off-the-shelf (COTS) IMS could be used for the identification of solid uranium compounds directly after sampling using a COTS sample swipe.« less

Use of an ion mobility spectrometer for detecting uranium compounds

DOE PAGES

McLain, Derek R.; Steeb, Jennifer L.; Smith, Nicholas A.

2018-03-09

The safeguards community currently lacks a method to rapidly determine the chemical form of radioactive and non-radioactive compounds in real time during inspection activities. Chemical speciation identification can provide important information on both the types of materials that are collected during environmental sampling and can inform inspectors as to where to focus efforts during inspections or complementary access visits. Ion Mobility Spectrometry (IMS) is an established field technique for the detection of explosives, narcotics, and other organic compounds. More recently, electrospray ionization (ESI) has been used to introduce inorganic compounds to IMS instruments for analysis. These techniques have shown themore » ability to supply chemical information about the compounds being analyzed. Although these laboratory based instruments use a liquid-based injection system, there is evidence in the literature of unaltered and intact pharmaceutical tablets being volatilized and ionized in open atmosphere using heat and a Ni-63 source. Lastly, this work determined that a commercial-off-the-shelf (COTS) IMS could be used for the identification of solid uranium compounds directly after sampling using a COTS sample swipe.« less

HPLC-ESI-QTOF-MS as a powerful analytical tool for characterising phenolic compounds in olive-leaf extracts.

PubMed

Quirantes-Piné, Rosa; Lozano-Sánchez, Jesús; Herrero, Miguel; Ibáñez, Elena; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

2013-01-01

Olea europaea L. leaves may be considered a cheap, easily available natural source of phenolic compounds. In a previous study we evaluated the possibility of obtaining bioactive phenolic compounds from olive leaves by pressurised liquid extraction (PLE) for their use as natural anti-oxidants. The alimentary use of these kinds of extract makes comprehensive knowledge of their composition essential. To undertake a comprehensive characterisation of two olive-leaf extracts obtained by PLE using high-performance liquid chromatography coupled to electrospray ionisation and quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS). Olive leaves were extracted by PLE using ethanol and water as extraction solvents at 150°C and 200°C respectively. Separation was carried out in a HPLC system equipped with a C₁₈-column working in a gradient elution programme coupled to ESI-QTOF-MS operating in negative ion mode. This analytical platform was able to detect 48 compounds and tentatively identify 31 different phenolic compounds in these extracts, including secoiridoids, simple phenols, flavonoids, cinnamic-acid derivatives and benzoic acids. Lucidumoside C was also identified for the first time in olive leaves. The coupling of HPLC-ESI-QTOF-MS led to the in-depth characterisation of the olive-leaf extracts on the basis of mass accuracy, true isotopic pattern and tandem mass spectrometry (MS/MS) spectra. We may conclude therefore that this analytical tool is very valuable in the study of phenolic compounds in plant matrices. Copyright © 2012 John Wiley & Sons, Ltd.

Electrosurgical injuries during robot assisted surgery: insights from the FDA MAUDE database

NASA Astrophysics Data System (ADS)

Fuller, Andrew; Vilos, George A.; Pautler, Stephen E.

2012-02-01

Introduction: The da Vinci surgical system requires the use of electrosurgical instruments. The re-use of such instruments creates the potential for stray electrical currents from capacitive coupling and/or insulation failure with subsequent injury. The morbidity of such injuries may negate many of the benefits of minimally invasive surgery. We sought to evaluate the rate and nature of electrosurgical injury (ESI) associated with this device. Methods: The Manufacturer and User Facility Device Experience (MAUDE) database is administered by the US Food and Drug Administration (FDA) and reports adverse events related to medical devices in the United States. We analyzed all incidents in the context of robotic surgery between January 2001 and June 2011 to identify those related to the use of electrosurgery. Results: In the past decade, a total of 605 reports have been submitted to the FDA with regard to adverse events related to the da Vinci robotic surgical platform. Of these, 24 (3.9%) were related to potential or actual ESI. Nine out of the 24 cases (37.5%) resulted in additional surgical intervention for repair. There were 6 bowel injuries of which only one was recognized and managed intra-operatively. The remainder required laparotomy between 5 and 8 days after the initial robotic procedure. Additionally, there were 3 skin burns. The remaining cases required conservative management or resulted in no harm. Conclusion: ESI in the context of robotic surgery is uncommon but remains under-recognized and under-reported. Surgeons performing robot assisted surgery should be aware that ESI can occur with robotic instruments and vigilance for intra- and post-operative complications is paramount.

Simultaneous separation and determination of 15 organic UV filters in sunscreen cosmetics by HPLC-ESI-MS/MS.

PubMed

Meng, X; Ma, Q; Bai, H; Wang, Z; Han, C; Wang, C

2017-08-01

A comprehensive methodology for the simultaneous determination of 15 multiclass organic UV filters in sunscreen cosmetics was developed using high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Sunscreen cosmetics of various matrices, such as toning lotion, emulsion, cream and lipstick, were analysed. Ultrasound-assisted extraction (UAE) was utilized as the extraction technique for sample preparation. The 15 UV filters were chromatographically separated by two groups of mobile phase system on an XBridge C 18 analytical column (150 × 2.1 mm I.D., 3.5 μm particle size) and quantified using HPLC-ESI-MS/MS. The quantitation was performed using the external calibration method. The established method was validated in terms of linearity, sensitivity, specificity, accuracy, stability, intraday and interday precisions, recovery and matrix effect. The method was also applied for the determination of UV filters in commercial sunscreen cosmetics. The experimental results demonstrated that the developed method was accurate, rapid and sensitive and can be used for the analytical control of sunscreen cosmetics. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Multiple neutral alkali halide attachments onto oligosaccharides in electrospray ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Striegel, André M.; Timpa, Judy D.; Piotrowiak, Piotr; Cole, Richard B.

1997-03-01

Oligosaccharides perform essential functions in a variety of biological and agricultural processes. Recent approaches to characterization of these molecules by mass spectrometry have utilized mainly soft-ionization methods such as electrospray ionization (ESI) and thermospray (TS), as well as fast atom bombardment (FAB). The behavior of a series of maltooligosaccharides with [alpha]-(1 --> 4) linkages, maltose (G2) through maltoheptaose (G7), under ESI conditions, has been investigated here. The oligosaccharides were dissolved in N,N-dimethylacetamide containing lithium chloride (DMAc/LiCl) prior to analysis by ESI-MS. A highly unusual feature, evident in all mass spectra obtained using this solvent system, was the presence of multiple [`]neutral' salt attachments onto lithium adducts of the sugars. Resultant ions took the form of [Gx + Li + nLiCl+, where n may reach a value as high as eight. Compared to LiCl, the propensity for alkali halide attachment using other alkali chlorides or lithium halides was greatly reduced. An investigation of this phenomenon is presented in which the organic and inorganic portions of the employed solvent were systematically varied, and semi-empirical computer modeling was performed to better understand lithium coordination by the sugars.

Ionization techniques in capillary electrophoresis-mass spectrometry: principles, design, and application.

PubMed

Hommerson, Paul; Khan, Amjad M; de Jong, Gerhardus J; Somsen, Govert W

2011-01-01

A major step forward in the development and application of capillary electrophoresis (CE) was its coupling to ESI-MS, first reported in 1987. More than two decades later, ESI has remained the principal ionization technique in CE-MS, but a number of other ionization techniques have also been implemented. In this review the state-of-the-art in the employment of soft ionization techniques for CE-MS is presented. First the fundamentals and general challenges of hyphenating conventional CE and microchip electrophoresis with MS are outlined. After elaborating on the characteristics and role of ESI, emphasis is put on alternative ionization techniques including sonic spray ionization (SSI), thermospray ionization (TSI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), matrix-assisted laser desorption ionization (MALDI) and continuous-flow fast atom bombardment (CF-FAB). The principle of each ionization technique is outlined and the experimental set-ups of the CE-MS couplings are described. The strengths and limitations of each ionization technique with respect to CE-MS are discussed and the applicability of the various systems is illustrated by a number of typical examples. Copyright © 2011 Wiley Periodicals, Inc.

Low Cost Entry, Descent, and Landing (EDL) Instrumentation for Planetary Missions

NASA Technical Reports Server (NTRS)

Hwang, H. H.; Munk, M. M.; Dillman, R. A.; Mahzari, M.; Swanson, G. T.; White, T. R.

2016-01-01

Missions that involve traversing through a planetary atmosphere are unique opportunities that require elements of entry, descent, and landing (EDL). Many aspects of the EDL sequence are qualified using analysis and simulation due to the inability to conduct appropriate ground tests, however validating flight data are often lacking, especially for missions not involving Earth re-entry. NASA has made strategic decisions to collect EDL flight data in order to improve future mission designs. For example, MEDLI1 and EFT-1 gathered hypersonic pressure and in-depth temperature data in the thermal protection system (TPS). However, the ability to collect EDL flight data from the smaller competed missions, such as Discovery and New Frontiers, has been limited in part due to the Principal Investigator-managed cost-caps (PIMCC). The recent NASA decision to consider EDL instrumentation earlier in the mission design cycle led to the inclusion of a requirement in the Discovery 2014 Announcement of Opportunity which requires all missions that involve EDL to include an Engineering Science Investigation (ESI).2 The ESI would involve sensors for aerothermal environment and TPS; atmosphere, aerodynamics, and flight dynamics; atmospheric decelerator; and/or vehicle structure.3 The ESI activity would be funded outside of the PIMCC.

A new approach to study cadmium complexes with oxalic acid in soil solution.

PubMed

Dytrtová, Jana Jaklová; Jakl, Michal; Sestáková, Ivana; Zins, Emilie-Laure; Schröder, Detlef; Navrátil, Tomáš

2011-05-05

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH(2)) were observed. In order to verify the possible formation of complexes with OAH(2), aqueous solutions of OAH(2) with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd(n)(X,Y)((2n+1))](-), where n is the number of cadmium atoms, X=Cl(-), and Y=OAH(-). Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of hydrostatic CCC-TLC-HPLC-ESI-TOF-MS for the bioguided fractionation of anticholinesterase alkaloids from Argemone mexicana L. roots.

PubMed

Kukula-Koch, Wirginia; Mroczek, Tomasz

2015-03-01

A rapid hydrostatic counter-current chromatography-thin-layer chromatography-electrospray-ionization time-of-flight mass spectrometry (CCC-TLC-ESI-TOF-MS) technique was established for use in seeking potent anti-Alzheimer's drugs among the acethylcholinesterase inhibitors in Argemone mexicana L. underground parts, with no need to isolate components in pure form. The dichloromethane extract from the roots of Mexican prickly poppy that was most rich in secondary metabolites was subjected to hydrostatic-CCC-based fractionation in descending mode, using a biphasic system composed of petroleum ether-ethyl acetate-methanol-water at the ratio of 1.5:3:2.1:2 (v/v). The obtained fractions were analyzed in a TLC-based AChE-inhibition "Fast Blue B" test. All active components in the fractions, including berberine, protopine, chelerithrine, sanguinarine, coptisine, palmatine, magnoflorine, and galanthamine, were identified in a direct TLC-HPLC-ESI-TOF-MS assay with high accuracy. This is the first time galanthamine has been reported in the extract of Mexican prickly poppy and the first time it has been identified in any member of the Papaveraceae family, in the significant quantity of 0.77%.

The Computerized Educational Guidance System. EDGUYD Manual.

ERIC Educational Resources Information Center

Cassel, Russell N.

The Computerized Educational Guidance System (EDGUYD) permits one to narrow post high school educational planning where consideration is given to all 1,448 4-year colleges and universities in the United States. This, to be sure, is a feat no human counselor is capable of without a computer. The Educational Success Index (ESI) is the means used by…

Nanospray mass spectrometry with indirect conductive graphite coating.

PubMed

Viberg, Peter; Nilsson, Staffan; Skog, Kerstin

2004-07-15

An easy and cost-effective method to manufacture a robust conductive graphite coating for nanospray mass spectrometry (nESI-MS) and capillary electrophoresis (CE)-nESI-MS is described. The method involves graphite coating of a tube sleeve, into which the nESI emitter is inserted and connected to a transfer capillary, instead of coating the actual emitter. The coating, made of graphite from a pencil and epoxy glue, was stable over long periods of use (>80 h) and showed excellent resistance toward various solvents. Stable electrospray was achieved in the investigated flow range (150-900 nL x min(-)(1)), and salbutamol, diphenhydramine, and nortriptyline (M(w): 239-263 g x mol(-)(1)) were detected in the nanomole per liter range during continuous pumping. CE-nESI-MS analysis gave excellent signal-to-noise ratios for 100-fmol injections. The technique allows simple exchange of the nESI emitter to suit a specific flow rate, and it minimizes risk of corona discharge.

Electrospray Modifications for Advancing Mass Spectrometric Analysis

PubMed Central

Meher, Anil Kumar; Chen, Yu-Chie

2017-01-01

Generation of analyte ions in gas phase is a primary requirement for mass spectrometric analysis. One of the ionization techniques that can be used to generate gas phase ions is electrospray ionization (ESI). ESI is a soft ionization method that can be used to analyze analytes ranging from small organics to large biomolecules. Numerous ionization techniques derived from ESI have been reported in the past two decades. These ion sources are aimed to achieve simplicity and ease of operation. Many of these ionization methods allow the flexibility for elimination or minimization of sample preparation steps prior to mass spectrometric analysis. Such ion sources have opened up new possibilities for taking scientific challenges, which might be limited by the conventional ESI technique. Thus, the number of ESI variants continues to increase. This review provides an overview of ionization techniques based on the use of electrospray reported in recent years. Also, a brief discussion on the instrumentation, underlying processes, and selected applications is also presented. PMID:28573082

Simultaneous ESI-APCI+ ionization and fragmentation pathways for nine benzodiazepines and zolpidem using single quadrupole LC-MS.

PubMed

Galaon, Toma; Vacaresteanu, Catalina; Anghel, Dan-Florin; David, Victor

2014-05-01

Nine important 1,4-benzodiazepines and zolpidem were characterized by liquid chromatography-mass spectrometry using a multimode ionization source able to generate ions using both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), and a single quadrupole mass analyzer. An optimum chromatographic separation was applied for all target compounds in less than 8 minutes using a Zorbax Eclipse Plus column (100 × 4.6 mm, 3.5 µm) kept at 35°C and a 0.3% HCOOH/ACN/IPA (61:34:5) mobile phase pumped at 1 ml/min. Optimization of LC-MS method generated low limit of quantitation (LOQ) values situated in the range 0.3-20.5 ng/ml. Comparison between differences in method sensitivity, under specified chromatographic conditions, when using ESI-only, APCI-only, and simultaneous ESI-APCI ionization with such a multimode source was discussed. Mixed ESI-APCI(+) mode proved to be the most sensitive ionization generating an average 35% detector response increase compared to ESI-only ionization and 350% detector response increase with respect to APCI-only ionization. Characterization of the nine benzodiazepines and zolpidem concerning their MS fragmentation pathway following 'in-source' collision-induced dissociation is discussed in detail and some general trends regarding these fragmentations are set. Copyright © 2013 John Wiley & Sons, Ltd.

Comparison of ESI- and APCI-LC-MS/MS methods: A case study of levonorgestrel in human plasma.

PubMed

Wang, Rulin; Zhang, Lin; Zhang, Zunjian; Tian, Yuan

2016-12-01

Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) techniques for liquid chromatography-tandem mass spectrometry (LC-MS/MS) determination of levonorgestrel were evaluated. In consideration of difference in ionization mechanism, the two ionization sources were compared in terms of LC conditions, MS parameters and performance of method. The sensitivity for detection of levonorgestrel with ESI was 0.25 ng/mL which was lower than 1 ng/mL with APCI. Matrix effects were evaluated for levonorgestrel and canrenone (internal standard, IS) in human plasma, and the results showed that APCI source appeared to be slightly less liable to matrix effect than ESI source. With an overall consideration, ESI was chosen as a better ionization technique for rapid and sensitive quantification of levonorgestrel. The optimized LC-ESI-MS/MS method was validated for a linear range of 0.25-50 ng/mL with a correlation coefficient ≥0.99. The intra- and inter-batch precision and accuracy were within 11.72% and 6.58%, respectively. The application of this method was demonstrated by a bioequivalence study following a single oral administration of 1.5 mg levonorgestrel tablets in 21 Chinese healthy female volunteers.

Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

USGS Publications Warehouse

Thurman, E.M.; Ferrer, I.; Barcelo, D.

2001-01-01

An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

Characterization, stoichiometry, and stability of salivary protein-tannin complexes by ESI-MS and ESI-MS/MS.

PubMed

Canon, Francis; Paté, Franck; Meudec, Emmanuelle; Marlin, Thérèse; Cheynier, Véronique; Giuliani, Alexandre; Sarni-Manchado, Pascale

2009-12-01

Numerous protein-polyphenol interactions occur in biological and food domains particularly involving proline-rich proteins, which are representative of the intrinsically unstructured protein group (IUP). Noncovalent protein-ligand complexes are readily detected by electrospray ionization mass spectrometry (ESI-MS), which also gives access to ligand binding stoichiometry. Surprisingly, the study of interactions between polyphenolic molecules and proteins is still an area where ESI-MS has poorly benefited, whereas it has been extensively applied to the detection of noncovalent complexes. Electrospray ionization mass spectrometry has been applied to the detection and the characterization of the complexes formed between tannins and a human salivary proline-rich protein (PRP), namely IB5. The study of the complex stability was achieved by low-energy collision-induced dissociation (CID) measurements, which are commonly implemented using triple quadrupole, hybrid quadrupole time-of-flight, or ion trap instruments. Complexes composed of IB5 bound to a model polyphenol EgCG have been detected by ESI-MS and further analyzed by MS/MS. Mild ESI interface conditions allowed us to observe intact noncovalent PRP-tannin complexes with stoichiometries ranging from 1:1 to 1:5. Thus, ESI-MS shows its efficiency for (1) the study of PRP-tannin interactions, (2) the determination of stoichiometry, and (3) the study of complex stability. We were able to establish unambiguously both their stoichiometries and their overall subunit architecture via tandem mass spectrometry and solution disruption experiments. Our results prove that IB5.EgCG complexes are maintained intact in the gas phase.

Lithium and an EPAC-specific inhibitor ESI-09 synergistically suppress pancreatic cancer cell proliferation and survival.

PubMed

Wang, Xinshuo; Luo, Cheng; Cheng, Xiaodong; Lu, Meiling

2017-07-01

Our previous studies showed that while lithium suppresses proliferation and induces apoptosis in pancreatic cancer cells, the inhibition of exchange proteins directly activated by cyclic adenosine monophosphate (cAMP) (EPAC)1 blocks pancreatic cancer cell migration and invasion. In this study, we further investigated the combinatory effects of lithium and EPAC-specific inhibitor (ESI)-09, an EPAC-specific inhibitor, on pancreatic cancer cell proliferation and viability, and explored whether lithium synergistically cooperates with EPAC inhibition in suppressing pancreatic cancer cell tumorigenicity. The cell viability of pancreatic cancer cell lines PANC-1 and MiaPaCa-2 was measured after 48 h of incubation with different dose combination of lithium and ESI-09. Flow cytometric analysis was carried out to further verify the impact of lithium and ESI-09 upon PANC-1 cell proliferation and apoptosis. To investigate the mechanism that the effects generated by lithium and ESI-09 on PANC-1 cells, the intracellular cAMP level was measured by an ELISA-based cAMP immunoassay. Our data showed that lithium and ESI-09 synergistically inhibit pancreatic cancer cell growth and survival. Furthermore, our results revealed a novel mechanism in which the synergism between lithium and ESI-09 is not mediated by the inhibitory effect of lithium toward GSK3β, but by lithium's ability to suppress cAMP/protein kinase A signaling. © The Author 2017. Published by Oxford University Press on behalf of the Institute of Biochemistry and Cell Biology, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Probing Protein Structure by Amino Acid-Specific Covalent Labeling and Mass Spectrometry

PubMed Central

Mendoza, Vanessa Leah; Vachet, Richard W.

2009-01-01

For many years, amino acid-specific covalent labeling has been a valuable tool to study protein structure and protein interactions, especially for systems that are difficult to study by other means. These covalent labeling methods typically map protein structure and interactions by measuring the differential reactivity of amino acid side chains. The reactivity of amino acids in proteins generally depends on the accessibility of the side chain to the reagent, the inherent reactivity of the label and the reactivity of the amino acid side chain. Peptide mass mapping with ESI- or MALDI-MS and peptide sequencing with tandem MS are typically employed to identify modification sites to provide site-specific structural information. In this review, we describe the reagents that are most commonly used in these residue-specific modification reactions, details about the proper use of these covalent labeling reagents, and information about the specific biochemical problems that have been addressed with covalent labeling strategies. PMID:19016300

Competition-Level Differences on the Lower Quarter Y-Balance Test in Baseball Players.

PubMed

Butler, Robert J; Bullock, Garrett; Arnold, Todd; Plisky, Phillip; Queen, Robin

2016-12-01

Decreased performance in dynamic balance has previously been associated with a history of ulnar collateral ligament injury in baseball players. Previous research on dynamic balance in soccer players has shown that test performance depends on competition level. However, dynamic balance has yet to be examined in baseball players. To understand normative values and determine differences in dynamic balance, as measured by the Lower Quarter Y-Balance Test, across competition levels in baseball players. Cross-sectional study. Preseason physical examinations. Dynamic balance was measured in 88 high school (HS), 78 collegiate (COL), and 90 professional (PRO) baseball players. All participants completed the Lower Quarter Y-Balance Test using the standard protocol. In unilateral stance, they reached with 1 foot in the anterior, posteromedial, and posterolateral directions. We calculated 1-way analyses of variance to compare performance, composite score, and reach asymmetry for each direction as well as the sum of the asymmetry values (P < .05). Composite score was calculated by averaging the maximum normalized reach scores. Reach asymmetry was determined by calculating bilateral differences in reach ability. In comparison with the HS and COL groups, the PRO players exhibited greater posteromedial (P < .01; effect size index [ESI] HS = 1.06, ESI COL = 0.95) and posterolateral reach (P < .01; ESI HS = 0.82, ESI COL = 0.84) as well as a greater composite score (P < .01; ESI HS = 0.60, ESI COL = 0.87). In contrast, HS baseball players exhibited increased anterior reach (P < .01; ESI COL = 0.60, ESI PRO = 0.39) compared with the COL and PRO cohorts. No significant differences in reach asymmetry were observed among groups. Lower extremity dynamic balance performance differed based on the baseball players' competition level. These baseline data may be helpful in identifying low-performing athletes who might benefit from neuromuscular interventions.

Comparison of PCR/electron spray ionization-time-of-flight-mass spectrometry versus traditional clinical microbiology for active surveillance of organisms contaminating high-use surfaces in a burn intensive care unit, an orthopedic ward and healthcare workers.

PubMed

Yun, Heather C; Kreft, Rachael E; Castillo, Mayra A; Ehrlich, Garth D; Guymon, Charles H; Crouch, Helen K; Chung, Kevin K; Wenke, Joseph C; Hsu, Joseph R; Spirk, Tracy L; Costerton, J William; Mende, Katrin; Murray, Clinton K

2012-10-10

Understanding nosocomial pathogen transmission is restricted by culture limitations. Novel platforms, such as PCR-based electron spray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS), may be useful as investigational tools. Traditional clinical microbiology (TCM) and PCR/ESI-TOF-MS were used to recover and detect microorganisms from the hands and personal protective equipment of 10 burn intensive care unit (ICU) healthcare workers providing clinical care at a tertiary care military referral hospital. High-use environmental surfaces were assessed in 9 burn ICU and 10 orthopedic patient rooms. Clinical cultures during the study period were reviewed for pathogen comparison with investigational molecular diagnostic methods. From 158 samples, 142 organisms were identified by TCM and 718 by PCR/ESI-TOF-MS. The molecular diagnostic method detected more organisms (4.5 ± 2.1 vs. 0.9 ± 0.8, p < 0.01) from 99% vs. 67% of samples (p < 0.01). TCM detected S. aureus in 13 samples vs. 21 by PCR/ESI-TOF-MS. Gram-negative organisms were less commonly identified than gram-positive by both methods; especially by TCM. Among all detected bacterial species, similar percentages were typical nosocomial pathogens (18-19%) for TCM vs. PCR/ESI-TOF-MS. PCR/ESI-TOF-MS also detected mecA in 112 samples, vanA in 13, and KPC-3 in 2. MecA was associated (p < 0.01) with codetection of coagulase negative staphylococci but not S. aureus. No vanA was codetected with enterococci; one KPC-3 was detected without Klebsiella spp. In this pilot study, PCR/ESI-TOF-MS detected more organisms, especially gram-negatives, compared to TCM, but the current assay format is limited by the number of antibiotic resistance determinants it covers. Further large-scale assessments of PCR/ESI-TOF-MS for hospital surveillance are warranted.

The potential of organic (electrospray- and atmospheric pressure chemical ionisation) mass spectrometric techniques coupled to liquid-phase separation for speciation analysis.

PubMed

Rosenberg, Erwin

2003-06-06

The use of mass spectrometry based on atmospheric pressure ionisation techniques (atmospheric pressure chemical ionisation, APCI, and electrospray ionisation, ESI) for speciation analysis is reviewed with emphasis on the literature published in and after 1999. This report accounts for the increasing interest that atmospheric pressure ionisation techniques, and in particular ESI, have found in the past years for qualitative and quantitative speciation analysis. In contrast to element-selective detectors, organic mass spectrometric techniques provide information on the intact metal species which can be used for the identification of unknown species (particularly with MS-MS detection) or the confirmation of the actual presence of species in a given sample. Due to the complexity of real samples, it is inevitable in all but the simplest cases to couple atmospheric pressure MS detection to a separation technique. Separation in the liquid phase (capillary electrophoresis or liquid chromatography in reversed phase, ion chromatographic or size-exclusion mode) is particularly suitable since the available techniques cover a very wide range of analyte polarities and molecular mass. Moreover, derivatisation can normally be avoided in liquid-phase separation. Particularly in complex environmental or biological samples, separation in one dimension is not sufficient for obtaining adequate resolution for all relevant species. In this case, multi-dimensional separation, based on orthogonal separation techniques, has proven successful. ESI-MS is also often used in parallel with inductively coupled plasma MS detection. This review is structured in two parts. In the first, the fundamentals of atmospheric pressure ionisation techniques are briefly reviewed. The second part of the review discusses recent applications including redox species, use of ESI-MS for structural elucidation of metal complexes, characterisation and quantification of small organometallic species with relevance to environment, health and food. Particular attention is given to the characterisation of biomolecules and metalloproteins (metallothioneins and phytochelatins) and to the investigation of the interaction of metals and biomolecules. Particularly in the latter field, ESI-MS is the ideal technique due to the softness of the ionisation process which allows to assume that the detected gas-phase ions are a true representation of the ions or ion-biomolecule complexes prevalent in solution. It is particularly this field, important to biochemistry, physiology and medical chemistry, where we can expect significant developments also in the future.

Analysis of Compounds Dissolved in Nonpolar Solvents by Electrospray Ionization on Conductive Nanomaterials

NASA Astrophysics Data System (ADS)

Xia, Bing; Gao, Yuanji; Ji, Baocheng; Ma, Fengwei; Ding, Lisheng; Zhou, Yan

2018-03-01

Electrospray ionization mass spectrometry (ESI-MS) technique has limitations in analysis of compounds that are dissolved in nonpolar solvents. In this study, ambient ionization of compounds in solvents that are not "friendly" to electrospray ionization, such as n-hexane, is achieved by conductive nanomaterials spray ionization (CNMSI) on nanomaterial emitters, including carbon nanotubes paper and mesodendritic silver covered metal, which applies high voltages to emitters made of these materials without the assistance of polar solvents. Although the time intensity curves (TIC) commonly vary from 4.5% to 23.7% over analyses, protonated molecular ions were found to be the most abundant species, demonstrating good reproducibility of the technique in terms of ionized species. Higher mass spectrometric responses are observed in analyzing nonpolar systems than polar systems. 2-Methoxyacetophenone, 4-methylacetophenone, benzothiazole, quinolone, and cycloheptanone as low as 2 pg in n-hexane can be directly detected using the developed method. The developed technique expands the analysis capability of ESI-MS for direct, online analysis of nonpolar systems, such as low polarity extracts, normal phase liquid chromatography eluates, and synthetic mixtures. [Figure not available: see fulltext.

Contested Domains of Science and Science Learning in Contemporary Native American Communities: Three Case Studies from a National Science Foundation Grant Titled, "Archaeology Pathways for Native Learners"

ERIC Educational Resources Information Center

Parent, Nancy Brossard

2012-01-01

This dissertation provides a critical analysis of three informal science education partnerships that resulted from a 2003-2006 National Science Foundation grant titled, "Archaeology Pathways for Native Learners" (ESI-0307858), hosted by the Mashantucket Pequot Museum and Research Center. This dissertation is designed to contribute to…

Large-scale fabrication of single crystalline tin nanowire arrays

NASA Astrophysics Data System (ADS)

Luo, Bin; Yang, Dachi; Liang, Minghui; Zhi, Linjie

2010-09-01

Large-scale single crystalline tin nanowire arrays with preferred lattice orientation along the [100] direction were fabricated in porous anodic aluminium oxide (AAO) membranes by the electrodeposition method using copper nanorod as a second electrode.Large-scale single crystalline tin nanowire arrays with preferred lattice orientation along the [100] direction were fabricated in porous anodic aluminium oxide (AAO) membranes by the electrodeposition method using copper nanorod as a second electrode. Electronic supplementary information (ESI) available: Experimental details and the information for single crystalline copper nanorods. See DOI: 10.1039/c0nr00206b

Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

PubMed

Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

2012-03-01

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

ALLocator: an interactive web platform for the analysis of metabolomic LC-ESI-MS datasets, enabling semi-automated, user-revised compound annotation and mass isotopomer ratio analysis.

PubMed

Kessler, Nikolas; Walter, Frederik; Persicke, Marcus; Albaum, Stefan P; Kalinowski, Jörn; Goesmann, Alexander; Niehaus, Karsten; Nattkemper, Tim W

2014-01-01

Adduct formation, fragmentation events and matrix effects impose special challenges to the identification and quantitation of metabolites in LC-ESI-MS datasets. An important step in compound identification is the deconvolution of mass signals. During this processing step, peaks representing adducts, fragments, and isotopologues of the same analyte are allocated to a distinct group, in order to separate peaks from coeluting compounds. From these peak groups, neutral masses and pseudo spectra are derived and used for metabolite identification via mass decomposition and database matching. Quantitation of metabolites is hampered by matrix effects and nonlinear responses in LC-ESI-MS measurements. A common approach to correct for these effects is the addition of a U-13C-labeled internal standard and the calculation of mass isotopomer ratios for each metabolite. Here we present a new web-platform for the analysis of LC-ESI-MS experiments. ALLocator covers the workflow from raw data processing to metabolite identification and mass isotopomer ratio analysis. The integrated processing pipeline for spectra deconvolution "ALLocatorSD" generates pseudo spectra and automatically identifies peaks emerging from the U-13C-labeled internal standard. Information from the latter improves mass decomposition and annotation of neutral losses. ALLocator provides an interactive and dynamic interface to explore and enhance the results in depth. Pseudo spectra of identified metabolites can be stored in user- and method-specific reference lists that can be applied on succeeding datasets. The potential of the software is exemplified in an experiment, in which abundance fold-changes of metabolites of the l-arginine biosynthesis in C. glutamicum type strain ATCC 13032 and l-arginine producing strain ATCC 21831 are compared. Furthermore, the capability for detection and annotation of uncommon large neutral losses is shown by the identification of (γ-)glutamyl dipeptides in the same strains. ALLocator is available online at: https://allocator.cebitec.uni-bielefeld.de. A login is required, but freely available.

Liquid chromatography-mass spectrometry (LC-MS): a powerful combination for selenium speciation in garlic (Allium sativum).

PubMed

Dumont, Emmie; Ogra, Yasumitsu; Vanhaecke, Frank; Suzuki, Kazuo T; Cornelis, Rita

2006-03-01

Liquid chromatography (LC) hyphenated with both elemental and molecular mass spectrometry has been used for Se speciation in Se-enriched garlic. Different species were separated by ion-pair liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) after hot-water extraction. They were identified by on-line reversed-phase liquid chromatography-electrospray ionization tandem mass spectrometry (RPLC-ESI-MS-MS). Se-methionine and Se-methylselenocysteine were determined by monitoring their product ions. Another compound, gamma-glutamyl-Se-methylselenocysteine, shown to be the most abundant form of Se in the garlic, was determined without any additional sample pre-treatment after extraction and without the need for a synthesized standard. Product ions for this dipeptide were detected by LC-ESI-MS-MS for three isotopes of Se-78 Se, 80Se: and 82Se. The method was extended to the species extracted during in-vitro gastrointestinal digestion. Because both Se-methylselenocysteine and gamma-glutamyl-Se-methylselenocysteine have anticarcinogenic properties, their extractability and stability during human digestion are very important. Garlic was also treated with saliva, to enable detection and analysis of species extracted during mastication. Detailed information on the extractability of selenium species by both simulated gastric and intestinal fluid are given, and variation of the distribution of Se among the different species with time is discussed. Although the main species in garlic is the dipeptide gamma-glutamyl-Se-methylselenocysteine, Se-methylselenocysteine is the main compound present in the extracts after treatment with gastrointestinal fluids. Two more, so far unknown compounds were observed in the chromatogram. The extracted species and their transformations were analysed by combining LC-ICP-MS and LC-ESI-MS-MS. In both the simulated gastric and intestinal digests, Se-methionine, Se-methylselenocysteine, and gamma-glutamyl-Se-methylselenocysteine could be determined by LC-ESI-MS-MS by measuring their typical product ions.

A multifunctional metal-organic framework based tumor targeting drug delivery system for cancer therapy

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Dong, Zhi-Yue; Cheng, Hong; Wan, Shuang-Shuang; Chen, Wei-Hai; Zou, Mei-Zhen; Huo, Jia-Wei; Deng, He-Xiang; Zhang, Xian-Zheng

2015-09-01

Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects.Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects. Electronic supplementary information (ESI) available: Synthesis procedure, 1HNMR, ESI-MS and additional data. See DOI: 10.1039/c5nr04045k

Induced in-source fragmentation pattern of certain novel (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides by electrospray mass spectrometry (ESI-MS/MS)

PubMed Central

2013-01-01

Background Collision induced dissociation (CID) in the triple quadrupole mass spectrometer system (QQQ) typically yields more abundant fragment ions than those produced with resonance excitation in the presence of helium gas in the ion trap mass spectrometer system (IT). Detailed product ion spectra can be obtained from one stage MS2 scan using the QQQ. In contrast, generating the same number of fragment ions in the ion trap requires multiple stages of fragmentation (MSn) using CID via in-trap resonance excitation with the associated time penalties and drop in sensitivity. Results The use of in-source fragmentation with electrospray ionization (ESI) followed by product ion scan (MS2) in a triple quadrupole mass spectrometer system, was demonstrated. This process enhances the qualitative power of tandem mass spectrometry to simulate the MS3 of ion trap for a comprehensive study of fragmentation mechanisms. A five pharmacologically significant (1Z, 2E)-N-arylpropanehydrazonoyl chlorides (3a-e) were chosen as model compounds for this study. In this work, detailed fragmentation pathways were elucidated by further dissociation of each fragment ion in the ion spectrum, essentially, by incorporating fragmentor voltage induced dissociation (in-source fragmentation) and isolation of fragments in a quadrupole cell Q1. Subsequently, CID occurs in cell, Q2, and fragment ions are analyzed in Q3 operated in product ion mode this process can be referred to as pseudo-MS3 scan mode. Conclusions This approach allowed unambiguous assignment of all fragment ions using tandem mass spectrometer and provided adequate sensitivity and selectivity. It is beneficial for structure determination of unknown trace components. The data presented in this paper provide useful information on the effect of different substituents on the ionization/fragmentation processes and can be used in the characterization of this important class of compounds. PMID:23351484

New techniques on oil spill modelling applied in the Eastern Mediterranean sea

NASA Astrophysics Data System (ADS)

Zodiatis, George; Kokinou, Eleni; Alves, Tiago; Lardner, Robin

2016-04-01

Small or large oil spills resulting from accidents on oil and gas platforms or due to the maritime traffic comprise a major environmental threat for all marine and coastal systems, and they are responsible for huge economic losses concerning the human infrastructures and the tourism. This work aims at presenting the integration of oil-spill model, bathymetric, meteorological, oceanographic, geomorphological and geological data to assess the impact of oil spills in maritime regions such as bays, as well as in the open sea, carried out in the Eastern Mediterranean Sea within the frame of NEREIDs, MEDESS-4MS and RAOP-Med EU projects. The MEDSLIK oil spill predictions are successfully combined with bathymetric analyses, the shoreline susceptibility and hazard mapping to predict the oil slick trajectories and the extend of the coastal areas affected. Based on MEDSLIK results, oil spill spreading and dispersion scenarios are produced both for non-mitigated and mitigated oil spills. MEDSLIK model considers three response combating methods of floating oil spills: a) mechanical recovery using skimmers or similar mechanisms; b) destruction by fire, c) use of dispersants or other bio-chemical means and deployment of booms. Shoreline susceptibility map can be compiled for the study areas based on the Environmental Susceptibility Index. The ESI classification considers a range of values between 1 and 9, with level 1 (ESI 1) representing areas of low susceptibility, impermeable to oil spilt during accidents, such as linear shorelines with rocky cliffs. In contrast, ESI 9 shores are highly vulnerable, and often coincide with natural reserves and special protected areas. Additionally, hazard maps of the maritime and coastal areas, possibly exposed to the danger on an oil spill, evaluate and categorize the hazard in levels from low to very high. This is important because a) Prior to an oil spill accident, hazard and shoreline susceptibility maps are made available to design preparedness and prevention plans in an effective way, b) After an oil spill accident, oil spill predictions can be combined with hazard maps to provide information on the oil spill dispersion and their impacts. This way, prevention plans can be directly modified at any time after the accident.

Sheathless interface to match flow rate of capillary electrophoresis with electrospray mass spectrometry using regular-sized capillary.

PubMed

Yin, Yue; Li, Gongyu; Guan, Yafeng; Huang, Guangming

2016-08-01

The flow rate match has been a great challenge when coupling capillary electrophoresis (CE) with electrospray ionization mass spectrometry (ESI-MS). Conventional CE-ESI-MS interfaces used liquid sheath flow, narrowed capillary or additional pressure to meet this requirement; sacrifice of either capillary inner diameter (i.d.) or separation efficiency is often inevitable. Thus, a regular-sized capillary-based sheathless interface would be attractive for flow rate match in CE-MS. The regular-sized capillary-based CE-MS interface was achieved by coupling CE with induced electrospray ionization (iESI) which was stimulated by the fact that the iESI could both achieve flow rate down to 0.2 μL/min and retain ionization efficiency. The CE-iESI-MS interface was completed with an intact separation capillary, outside the outlet end of which a metal electrode was attached for the application of alternating current (ac) high voltage (HV). The feasibility of this CE-iESI-MS interface was demonstrated through the stable total ion chromatograms obtained by continuous CE infusion of tripropylamine with regular-sized capillaries. Tripropylamine and atenolol were separated and detected successfully in phosphate buffer solution (PBS) by CE-iESI-MS using a 50 or 75 μm i.d. capillary. Furthermore, this new interface showed a better signal-to-noise (S/N) of 3 to 7 times enhancement compared with another sheathless CE-ESI-MS interface that using one high voltage for both separation and electrospray when analyzing the mixture of tripropylamine and proline in NH4 OAc buffer. In addition, the reproducibility of this interface gave satisfactory results with relative standard deviation (RSD) in retention time in the range between 1% and 3%. The novel sheathless CE-MS interface introduced here could match conventional electroosmotic flow (EOF) with electrospray which could also preserve the separation efficiency and sensitivity of CE-MS. This newly developed CE-iESI-MS interface was also demonstrated to be effective for different buffers, PBS and NH4 OAc, without any additives such as methanol and acetic acid. Hence, we believe that this sheathless CE-MS interface could be operated with other nonvolatile and volatile buffers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Immediate drop on demand technology (I-DOT) coupled with mass spectrometry via an open port sampling interface.

PubMed

Van Berkel, Gary J; Kertesz, Vilmos; Boeltz, Harry

2017-11-01

The aim of this work was to demonstrate and evaluate the analytical performance of coupling the immediate drop on demand technology to a mass spectrometer via the recently introduced open port sampling interface and ESI. Methodology & results: A maximum sample analysis throughput of 5 s per sample was demonstrated. Signal reproducibility was 10% or better as demonstrated by the quantitative analysis of propranolol and its stable isotope-labeled internal standard propranolol-d7. The ability of the system to multiply charge and analyze macromolecules was demonstrated using the protein cytochrome c. This immediate drop on demand technology/open port sampling interface/ESI-MS combination allowed for the quantitative analysis of relatively small mass analytes and was used for the identification of macromolecules like proteins.

Localizing value of electrical source imaging: Frontal lobe, malformations of cortical development and negative MRI related epilepsies are the best candidates.

PubMed

Abdallah, Chifaou; Maillard, Louis G; Rikir, Estelle; Jonas, Jacques; Thiriaux, Anne; Gavaret, Martine; Bartolomei, Fabrice; Colnat-Coulbois, Sophie; Vignal, Jean-Pierre; Koessler, Laurent

2017-01-01

We aimed to prospectively assess the anatomical concordance of electric source localizations of interictal discharges with the epileptogenic zone (EZ) estimated by stereo-electroencephalography (SEEG) according to different subgroups: the type of epilepsy, the presence of a structural MRI lesion, the aetiology and the depth of the EZ. In a prospective multicentric observational study, we enrolled 85 consecutive patients undergoing pre-surgical SEEG investigation for focal drug-resistant epilepsy. Electric source imaging (ESI) was performed before SEEG. Source localizations were obtained from dipolar and distributed source methods. Anatomical concordance between ESI and EZ was defined according to 36 predefined sublobar regions. ESI was interpreted blinded to- and subsequently compared with SEEG estimated EZ. 74 patients were finally analyzed. 38 patients had temporal and 36 extra-temporal lobe epilepsy. MRI was positive in 52. 41 patients had malformation of cortical development (MCD), 33 had another or an unknown aetiology. EZ was medial in 27, lateral in 13, and medio-lateral in 34. In the overall cohort, ESI completely or partly localized the EZ in 85%: full concordance in 13 cases and partial concordance in 50 cases. The rate of ESI full concordance with EZ was significantly higher in (i) frontal lobe epilepsy (46%; p  = 0.05), (ii) cases of negative MRI (36%; p  = 0.01) and (iii) MCD (27%; p  = 0.03). The rate of ESI full concordance with EZ was not statistically different according to the depth of the EZ. We prospectively demonstrated that ESI more accurately estimated the EZ in subgroups of patients who are often the most difficult cases in epilepsy surgery: frontal lobe epilepsy, negative MRI and the presence of MCD.

Rapid detection and ruling out of neonatal sepsis by PCR coupled with Electrospray Ionization Mass Spectrometry (PCR/ESI-MS).

PubMed

Delcò, Cristina; Karam, Oliver; Pfister, Riccardo; Gervaix, Alain; Renzi, Gesuele; Emonet, Stéphane; Schrenzel, Jacques; Posfay-Barbe, Klara M

2017-05-01

Sepsis is an important cause of morbidity and mortality in neonates and clinicians are typically required to administer empiric antibiotics while waiting for blood culture results. However, prolonged and inappropriate use of antibiotics is associated with various complications and adverse events. Better tools to rapidly rule out bacterial infections are therefore needed. We aimed to assess the negative predictive value of PCR coupled with Electrospray Ionization Mass Spectrometry (PCR/ESI-MS) compared to conventional blood cultures in neonatal sepsis. Prospective observational study. All consecutive neonates (<28days old) with clinical suspicion of sepsis. Samples for PCR/ESI-MS analysis were collected at the same time as samples for the blood culture, before the initiation of antibiotics. Our primary objective was to evaluate the negative predictive value of PCR/ESI-MS for the detection of bacteria in the bloodstream of newborns with suspected sepsis. Our secondary objective was the evaluation of the sensitivity, specificity and positive predictive value of the PCR/ESI-MS in such a neonatal population. We analysed 114 samples over 14months. The median age and weight were 32weeks+3days and 1840g, respectively. Two patients had negative PCR/ESI-MS results, but positive blood cultures. Overall, the negative predictive value was 98% (95%CI: 92% to 100%). Based on these results, PCR/ESI-MS analysis of blood samples of neonates with suspected sepsis appears to have a very good negative predictive value when compared to blood cultures as gold standard. This novel test might allow for early reassessment of the need for antibiotics. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrospray Ionization-Induced Protein Unfolding

NASA Astrophysics Data System (ADS)

Lin, Hong; Kitova, Elena N.; Johnson, Margaret A.; Eugenio, Luiz; Ng, Kenneth K. S.; Klassen, John S.

2012-12-01

Electrospray ionization mass spectrometry (ESI-MS) measurements were performed under a variety of solution conditions on a highly acidic sub-fragment (B3C) of the C-terminal carbohydrate-binding repeat region of Clostridium difficile toxin B, and two mutants (B4A and B4B) containing fewer acidic residues. ESI-MS measurements performed in negative ion mode on aqueous ammonium acetate solutions of B3C at low ionic strength ( I < 80 mM) revealed evidence, based on the measured charge state distribution, of protein unfolding. In contrast, no evidence of unfolding was detected from ESI-MS measurements made in positive ion mode at low I or in either mode at higher I. The results of proton nuclear magnetic resonance and circular dichroism spectroscopy measurements and gel filtration chromatography performed on solutions of B3C under low and high I conditions suggest that the protein exists predominantly in a folded state in neutral aqueous solutions with I > 10 mM. The results of ESI-MS measurements performed on B3C in a series of solutions with high I at pH 5 to 9 rule out the possibility that the structural changes are related to ESI-induced changes in pH. It is proposed that unfolding of B3C, observed in negative mode for solutions with low I, occurs during the ESI process and arises due to Coulombic repulsion between the negatively charged residues and liquid/droplet surface charge. ESI-MS measurements performed in negative ion mode on B4A and B4B also reveal a shift to higher charge states at low I but the magnitude of the changes are smaller than observed for B3C.

The spatio-temporal mapping of epileptic networks: Combination of EEG–fMRI and EEG source imaging

PubMed Central

Vulliemoz, S.; Thornton, R.; Rodionov, R.; Carmichael, D.W.; Guye, M.; Lhatoo, S.; McEvoy, A.W.; Spinelli, L.; Michel, C.M.; Duncan, J.S.; Lemieux, L.

2009-01-01

Simultaneous EEG–fMRI acquisitions in patients with epilepsy often reveal distributed patterns of Blood Oxygen Level Dependant (BOLD) change correlated with epileptiform discharges. We investigated if electrical source imaging (ESI) performed on the interictal epileptiform discharges (IED) acquired during fMRI acquisition could be used to study the dynamics of the networks identified by the BOLD effect, thereby avoiding the limitations of combining results from separate recordings. Nine selected patients (13 IED types identified) with focal epilepsy underwent EEG–fMRI. Statistical analysis was performed using SPM5 to create BOLD maps. ESI was performed on the IED recorded during fMRI acquisition using a realistic head model (SMAC) and a distributed linear inverse solution (LAURA). ESI could not be performed in one case. In 10/12 remaining studies, ESI at IED onset (ESIo) was anatomically close to one BOLD cluster. Interestingly, ESIo was closest to the positive BOLD cluster with maximal statistical significance in only 4/12 cases and closest to negative BOLD responses in 4/12 cases. Very small BOLD clusters could also have clinical relevance in some cases. ESI at later time frame (ESIp) showed propagation to remote sources co-localised with other BOLD clusters in half of cases. In concordant cases, the distance between maxima of ESI and the closest EEG–fMRI cluster was less than 33 mm, in agreement with previous studies. We conclude that simultaneous ESI and EEG–fMRI analysis may be able to distinguish areas of BOLD response related to initiation of IED from propagation areas. This combination provides new opportunities for investigating epileptic networks. PMID:19408351

Simultaneous determination of five coumarins in Angelicae dahuricae Radix by HPLC/UV and LC-ESI-MS/MS.

PubMed

Park, Ah Yeon; Park, So-Young; Lee, Jaehyun; Jung, Mihye; Kim, Jinwoong; Kang, Sam Sik; Youm, Jeong-Rok; Han, Sang Beom

2009-10-01

Rapid, simple and reliable HPLC/UV and LC-ESI-MS/MS methods for the simultaneous determination of five active coumarins of Angelicae dahuricae Radix, byakangelicol (1), oxypeucedanin (2), imperatorin (3), phellopterin (4) and isoimperatorin (5) were developed and validated. The separation condition for HPLC/UV was optimized using a Develosil RPAQUEOUS C(30) column using 70% acetonitrile in water as the mobile phase. This HPLC/UV method was successful for providing the baseline separation of the five coumarins with no interfering peaks detected in the 70% ethanol extract of Angelicae dahuricae Radix. The specific determination of the five coumarins was also accomplished by a triple quadrupole tandem mass spectrometer equipped with an electrospray ionization source (LC-ESI-MS/MS). Multiple reaction monitoring (MRM) in the positive mode was used to enhance the selectivity of detection. The LC-ESI-MS/MS methods were successfully applied for the determination of the five major coumarins in Angelicae dahuricae Radix. These HPLC/UV and LC-ESI-MS/MS methods were validated in terms of recovery, linearity, accuracy and precision (intra- and inter-day validation). Taken together, the shorter analysis time involved makes these HPLC/UV and LC-ESI-MS/MS methods valuable for the commercial quality control of Angelicae dahuricae Radix extracts and its pharmaceutical preparations. Copyright (c) 2009 John Wiley & Sons, Ltd.

Prospective comparison of RT-PCR/ESI-MS to Prodesse ProFlu Plus and Cepheid GenXpert for the detection of Influenza A and B viruses.

PubMed

Hardick, Justin; Dugas, Andrea; Goheen, Joshua; Rothman, Richard; Gaydos, Charlotte

2015-03-01

RT-PCR/ESI-MS has previously demonstrated the capability to detect and identify respiratory viral pathogens in nasopharyngeal swabs. This study expands on previous research by performing a prospective evaluation of RT-PCR/ESI-MS to detect and identify Influenza A and B viruses compared to Prodesse ProFlu Plus and combined ProFlu Plus and Cepheid Xpert Flu. ProFlu Plus was also used as a gold standard for comparison for respiratory syncytial virus detection. Using ProFlu Plus as a gold standard, RT-PCR/ESI-MS had sensitivity and specificity of 82.1% (23/28) and 100% (258/258), respectively, for Influenza A, 100% (16/16) and 99.6% (269/270), respectively for Influenza B, and 88.6% (39/44) and 99.6% (241/242) for any Influenza virus. Using matching results from ProFlu Plus and Xpert Flu as a gold standard, RT-PCR/ESI-MS had 85.2% (23/27) and 100% (259/259) sensitivity and specificity respectively for Influenza A, 100% (14/14) and 99.6% (270/272), respectively for Influenza B virus. Overall, RT-PCR/ESI-MS was not as sensitive as the combined gold standard of ProFlu Plus and Xpert Flu, although it has the capability of detecting other respiratory viruses. Copyright © 2015 Elsevier B.V. All rights reserved.

Employer-Sponsored Health Insurance Coverage Limitations: Results from the Childhood Cancer Survivor Study

PubMed Central

Kirchhoff, Anne C.; Kuhlthau, Karen; Pajolek, Hannah; Leisenring, Wendy; Armstrong, Greg T.; Robison, Leslie L.; Park, Elyse R.

2013-01-01

Purpose The Affordable Care Act (ACA) will expand health insurance options for cancer survivors in the United States. It is unclear how this legislation will affect their access to employer-sponsored health insurance (ESI). We describe the health insurance experiences for survivors of childhood cancer with and without ESI. Methods We conducted a series of qualitative interviews with 32 adult survivors from the Childhood Cancer Survivor Study to assess their employment-related concerns and decisions regarding health insurance coverage. Interviews were performed from August to December 2009 and were recorded, transcribed, and content analyzed using NVivo 8. Results Uninsured survivors described ongoing employment limitations, such as being employed at part-time capacity, which affected their access to ESI coverage. These survivors acknowledged they could not afford insurance without employer support. Survivors on ESI had previously been denied health insurance due to their pre-existing health conditions until they obtained coverage through an employer. Survivors feared losing their ESI coverage, which created a disincentive to making career transitions. Others reported worries about insurance rescission if their cancer history was discovered. Survivors on ESI reported financial barriers in their ability to pay for health care. Conclusions Childhood cancer survivors face barriers to obtaining employer-sponsored health insurance. While Affordable Care Act provisions may mitigate insurance barriers for cancer survivors, many will still face cost barriers to affording health care without employer support. PMID:22717916

The Effect of Salts on Electrospray Ionization of Amino Acids in the Negative Mode

NASA Technical Reports Server (NTRS)

Kim, H. I.; Johnson, P. V.; Beegle, L. W.; Kanik, I.

2004-01-01

The continued search for organics on Mars will require the development of simplified procedures for handling and processing of soil or rock core samples prior to analysis by onboard instrumentation. Extraction of certain organic molecules such as amino acids from rock and soil samples using a liquid solvent (H2O) has been shown to be more efficient (by approximately an order of magnitude) than heat extraction methods. As such, liquid extraction (using H2O) of amino acid molecules from rock cores or regolith material is a prime candidate for the required processing. In this scenario, electrospray ionization (ESI) of the liquid extract would be a natural choice for ionization of the analyte prior to interrogation by one of a variety of potential analytical separation techniques (mass spectroscopy, ion mobility spectroscopy, etc.). Aside from the obvious compatibility of ESI and liquid samples, ESI offers simplicity and a soft ionization capability. In order to demonstrate that liquid extraction and ESI can work as part of an in situ instrument on Mars, we must better understand and quantify the effect salts have on the ESI process. In the current work, we have endeavored to investigate the feasibility and limitations of negative mode ESI of Martian surface samples in the context of sample salt content using ion mobility spectroscopy (IMS).

Theoretical investigation of low detection sensitivity for underivatized carbohydrates in ESI and MALDI.

PubMed

Chen, Jien-Lian; Lee, Chuping; Lu, I-Chung; Chien, Chia-Lung; Lee, Yuan-Tseh; Hu, Wei-Ping; Ni, Chi-Kung

2016-12-01

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mainly generate protonated ions from peptides and proteins but sodiated (or potassiated) ions from carbohydrates. The ion intensities of sodiated (or potassiated) carbohydrates generated by ESI and MALDI are generally lower than those of protonated peptides and proteins. Ab initio calculations and transition state theory were used to investigate the reasons for the low detection sensitivity for underivatized carbohydrates. We used glucose and cellobiose as examples and showed that the low detection sensitivity is partly attributable to the following factors. First, glucose exhibits a low proton affinity. Most protons generated by ESI or MALDI attach to water clusters and matrix molecules. Second, protonated glucose and cellobiose can easily undergo dehydration reactions. Third, the sodiation affinities of glucose and cellobiose are small. Some sodiated glucose and cellobiose dissociate into the sodium cations and neutral carbohydrates during ESI or MALDI process. The increase of detection sensitivity of carbohydrates in mass spectrometry by various methods can be rationalized according to these factors. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Comparative evaluation of three different ELISA assays and HPLC-ESI-ITMS/MS for the analysis of Nε-carboxymethyl lysine in food samples.

PubMed

Gómez-Ojeda, Armando; Jaramillo-Ortíz, Sarahi; Wrobel, Katarzyna; Wrobel, Kazimierz; Barbosa-Sabanero, Gloria; Luevano-Contreras, Claudia; de la Maza, Maria Pia; Uribarri, Jaime; Del Castillo, Ma Dolores; Garay-Sevilla, Ma Eugenia

2018-03-15

N ε -carboxymethyl-lysine (CML) is measured in food, but there is a controversy concerning the most convenient yet reliable method(s) for this task. This work compares three different ELISA assays and HPLC-ESI-ITMS/MS for the analysis of CML in several food items. The four methods showed the same decreasing order of CML concentration: beef, bacon>chicken > fish>dairy products>grain products>fruits/vegetables. HPLC-ESI-ITMS/MS results highly correlated with those obtained by ELISA performed with monoclonal CML-antibody (β=0.98, p<0.0001) whereas My Bio Source® kit results were not correlated with those provided by Lamider®. Small differences of CML concentrations in food items prepared by different culinary treatment were clearly distinguished by HPLC-ESI-ITMS/MS, but could not always be detected by ELISA. This work demonstrates a reasonable relationship between CM determined by ELISA and HPLC-ESI-ITMS/MS and therefore supports the implementation of ELISA in food CML/AGEs screening. Copyright © 2017. Published by Elsevier Ltd.

Optimizing Efficiency of Psychopathology Assessment through Quantitative Modeling: Development of a Brief Form of the Externalizing Spectrum Inventory

PubMed Central

Patrick, Christopher J.; Kramer, Mark D.; Krueger, Robert F.; Markon, Kristian E.

2014-01-01

The Externalizing Spectrum Inventory (ESI; Krueger, Markon, Patrick, Benning, & Kramer, 2007) provides for integrated, hierarchical assessment of a broad range of problem behaviors and traits in the domain of deficient impulse control. The ESI assesses traits and problems in this domain through 23 lower-order facet scales organized around three higher-order dimensions, reflecting general disinhibition, callous-aggression, and substance abuse. The full-form ESI contains 415 items, and a shorter form would be useful for questionnaire screening studies or multi-domain research protocols. The current work employed item response theory and structural modeling methods to create a 160-item brief form (ESI-bf) that provides for efficient measurement of the ESI’s lower-order facets and quantification of its higher-order dimensions either as scale-based factors or as item-based composites. The ESI-bf is recommended for use in research on psychological or neurobiological correlates of problems such as risk-taking, delinquency, aggression, and substance abuse, and studies of general and specific mechanisms that give rise to problems of these kinds. PMID:24320765

A novel isoflavone profiling method based on UPLC-PDA-ESI-MS.

PubMed

Zhang, Shuang; Zheng, Zong-Ping; Zeng, Mao-Mao; He, Zhi-Yong; Tao, Guan-Jun; Qin, Fang; Chen, Jie

2017-03-15

A novel non-targeted isoflavone profiling method was developed using the diagnostic fragment-ion-based extension strategy, based on ultra-high performance liquid chromatography coupled with photo-diode array detector and electrospray ionization-mass spectrometry (UPLC-PDA-ESI-MS). 16 types of isoflavones were obtained in positive mode, but only 12 were obtained in negative mode due to the absence of precursor ions. Malonyldaidzin and malonylgenistin glycosylated at the 4'-O position or malonylated at the 4″-O position of glucose were indicated by their retention behavior and fragmentation pattern. Three possible quantification methods in one run based on UPLC-PDA and UPLC-ESI-MS were validated and compared, suggesting that methods based on UPLC-ESI-MS possess remarkable selectivity and sensitivity. Impermissible quantitative deviations induced by the linearity calibration with 400-fold dynamic range was observed for the first time and was recalibrated with a 20-fold dynamic range. These results suggest that isoflavones and their stereoisomers can be simultaneously determined by positive-ion UPLC-ESI-MS in soymilk. Copyright © 2016. Published by Elsevier Ltd.

A new method for differentiating adducts of common drinking water DBPs from higher molecular weight DBPs in electrospray ionization-mass spectrometry analysis.

PubMed

Zhai, Hongyan; Zhang, Xiangru

2009-05-01

With the presence of bromide in source waters, numerous brominated disinfection byproducts (DBPs) are formed during chlorination. Many of them are polar/highly polar DBPs and thus hard to be detected by gas chromatography mass spectrometry. Electrospray ionization triple quadrupole mass spectrometry (ESI-MS/MS) is reported to be an effective method in finding polar brominated DBPs by setting precursor ion scans of m/z 79 and 81. But as a soft ionization technique, ESI could form adducts of common DBPs, which may complicate ESI-MS/MS spectra and hinder the efforts in finding new brominated DBPs. In this paper, a new method was developed for differentiating adducts of common DBPs from higher molecular weight DBPs. This method was based on the ESI-MS/MS precursor ion scans of the fragments that correspond to the molecular ions of common DBPs. Adducts of common DBPs were selectively detected in the ESI-MS/MS spectra of a simulated drinking water sample. Moreover, the structures of several new brominated DBPs in the sample were tentatively proposed.

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.

Ultra-performance liquid chromatography/tandem mass spectrometric quantification of structurally diverse drug mixtures using an ESI-APCI multimode ionization source.

PubMed

Yu, Kate; Di, Li; Kerns, Edward; Li, Susan Q; Alden, Peter; Plumb, Robert S

2007-01-01

We report in this paper an ultra-performance liquid chromatography/tandem mass spectrometric (UPLC(R)/MS/MS) method utilizing an ESI-APCI multimode ionization source to quantify structurally diverse analytes. Eight commercial drugs were used as test compounds. Each LC injection was completed in 1 min using a UPLC system coupled with MS/MS multiple reaction monitoring (MRM) detection. Results from three separate sets of experiments are reported. In the first set of experiments, the eight test compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes (ESI+, ESI-, APCI-, and APCI+) during an LC run. Approximately 8-10 data points were collected across each LC peak. This was insufficient for a quantitative analysis. In the second set of experiments, four compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes during an LC run. Approximately 15 data points were obtained for each LC peak. Quantification results were obtained with a limit of detection (LOD) as low as 0.01 ng/mL. For the third set of experiments, the eight test compounds were analyzed as a batch. During each LC injection, a single compound was analyzed. The mass spectrometer was detecting at a particular ionization mode during each LC injection. More than 20 data points were obtained for each LC peak. Quantification results were also obtained. This single-compound analytical method was applied to a microsomal stability test. Compared with a typical HPLC method currently used for the microsomal stability test, the injection-to-injection cycle time was reduced to 1.5 min (UPLC method) from 3.5 min (HPLC method). The microsome stability results were comparable with those obtained by traditional HPLC/MS/MS.

Combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for qualitative analysis of drugs.

PubMed

Pavlic, Marion; Libiseller, Kathrin; Oberacher, Herbert

2006-09-01

The potential of the combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for the identification of therapeutic and illicit drugs has been evaluated. Reserpine was used for standardizing experimental conditions and for characterization of the performance of the applied mass spectrometric system. Experiments revealed that because of the mass accuracy, the stability of calibration, and the reproducibility of fragmentation, the QqTOF mass spectrometer is an appropriate platform for establishment of a tandem-mass-spectral library. Three-hundred and nineteen substances were used as reference samples to build the spectral library. For each reference compound, product-ion spectra were acquired at ten different collision-energy values between 5 eV and 50 eV. For identification of unknown compounds, a library search algorithm was developed. The closeness of matching between a measured product-ion spectrum and a spectrum stored in the library was characterized by a value called "match probability", which took into account the number of matched fragment ions, the number of fragment ions observed in the two spectra, and the sum of the intensity differences calculated for matching fragments. A large value for the match probability indicated a close match between the measured and the reference spectrum. A unique feature of the library search algorithm-an implemented spectral purification option-enables characterization of multi-contributor fragment-ion spectra. With the aid of this software feature, substances comprising only 1.0% of the total amount of binary mixtures were unequivocally assigned, in addition to the isobaric main contributors. The spectral library was successfully applied to the characterization of 39 forensic casework samples.

ESiWACE: A Center of Excellence for HPC applications to support cloud resolving earth system modelling

NASA Astrophysics Data System (ADS)

Biercamp, Joachim; Adamidis, Panagiotis; Neumann, Philipp

2017-04-01

With the exa-scale era approaching, length and time scales used for climate research on one hand and numerical weather prediction on the other hand blend into each other. The Centre of Excellence in Simulation of Weather and Climate in Europe (ESiWACE) represents a European consortium comprising partners from climate, weather and HPC in their effort to address key scientific challenges that both communities have in common. A particular challenge is to reach global models with spatial resolutions that allow simulating convective clouds and small-scale ocean eddies. These simulations would produce better predictions of trends and provide much more fidelity in the representation of high-impact regional events. However, running such models in operational mode, i.e with sufficient throughput in ensemble mode clearly will require exa-scale computing and data handling capability. We will discuss the ESiWACE initiative and relate it to work-in-progress on high-resolution simulations in Europe. We present recent strong scalability measurements from ESiWACE to demonstrate current computability in weather and climate simulation. A special focus in this particular talk is on the Icosahedal Nonhydrostatic (ICON) model used for a comparison of high resolution regional and global simulations with high quality observation data. We demonstrate that close-to-optimal parallel efficiency can be achieved in strong scaling global resolution experiments on Mistral/DKRZ, e.g. 94% for 5km resolution simulations using 36k cores on Mistral/DKRZ. Based on our scalability and high-resolution experiments, we deduce and extrapolate future capabilities for ICON that are expected for weather and climate research at exascale.

Nanoelectrospray ion generation for high-throughput mass spectrometry using a micromachined ultrasonic ejector array

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

Aderogba, S.; Meacham, J.M.; Degertekin, F.L.

2005-05-16

Ultrasonic electrospray ionization (ESI) for high-throughput mass spectrometry is demonstrated using a silicon micromachined microarray. The device uses a micromachined ultrasonic atomizer operating in the 900 kHz-2.5 MHz range for droplet generation and a metal electrode in the fluid cavity for ionization. Since the atomization and ionization processes are separated, the ultrasonic ESI source shows the potential for operation at low voltages with a wide range of solvents in contrast with conventional capillary ESI technology. This is demonstrated using the ultrasonic ESI microarray to obtain the mass spectrum of a 10 {mu}M reserpine sample on a time of flight massmore » spectrometer with 197:1 signal-to-noise ratio at an ionization potential of 200 V.« less

Analysis of Arsenicals and their Sulfur Analogs Using HPLC with Collision Cell ICP-MS and ESI-MS

EPA Science Inventory

Recent metabolic and exposure assessment studies have found sulfur analogs (thioarsenicals) of common oxoarsenicals in environmental and biological systems. The occurrence of thioarsenicals raises questions regarding their origin and transport, and their roles in metabolism of a...

Non-covalent S···O interactions control conformation in a scaffold that disrupts islet amyloid polypeptide fibrillation† †Electronic supplementary information (ESI) available: Experimental procedures; 1H, 13C and NOESY spectra; HRMS, and IR values. CCDC 1453550 (24), ThT assay data, computation, electron microscopy. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc00756b Click here for additional data file.

PubMed Central

Peacock, Hayden; Luo, Jinghui; Yamashita, Tohru; Luccarelli, James

2016-01-01

Conformationally-constrained molecules that selectively recognise the surfaces of proteins have the potential to direct the path of protein folding. Such molecules are of therapeutic interest because the misfolding of proteins, especially that which results in fibrillation and aggregation, is strongly correlated with numerous diseases. Here we report the novel use of S···O interactions as a conformational control element in a new class of non-peptidic scaffold that mimics key elements of protein surfaces. These molecules disrupt the fibrillation of islet amyloid polypeptide (IAPP), a process that is implicated in the pathology of type II diabetes. PMID:28451100

Multi-functional bis(alkynyl)gold(iii) N⁁C complexes with distinct mechanochromic luminescence and electroluminescence properties† †Electronic supplementary information (ESI) available: CCDC 1552808. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02410j

PubMed Central

Wong, Ben Yiu-Wing; Wong, Hok-Lai; Wong, Yi-Chun; Au, Vonika Ka-Man

2017-01-01

A new class of donor–acceptor type luminescent bis(alkynyl)gold(iii) N⁁C complexes has been synthesized and characterized. These gold(iii) complexes not only exhibit high photoluminescence quantum yields of up to 0.81, but also interesting mechanochromic luminescence behaviors that are reversible. Upon grinding, a dramatic luminescence color change from green to red can be observed in solid samples of the gold(iii) complexes, and the mechanochromic luminescence can be readily tuned via a judicious selection of substituents on the pyridine ring. In addition, solution-processable OLEDs based on this class of complexes with EQE values of up to 4.0% have been realized, representing the first demonstration of bis(alkynyl)gold(iii) N⁁C complexes as emissive materials in solution-processable OLEDs. PMID:29147519

Glycan profiling of monoclonal antibodies using zwitterionic-type hydrophilic interaction chromatography coupled with electrospray ionization mass spectrometry detection.

PubMed

Mauko, Lea; Nordborg, Anna; Hutchinson, Joseph P; Lacher, Nathan A; Hilder, Emily F; Haddad, Paul R

2011-01-15

We present a new method for the analysis of glycans enzymatically released from monoclonal antibodies (MAbs) employing a zwitterionic-type hydrophilic interaction chromatography (ZIC-HILIC) column coupled with electrospray ionization mass spectrometry (ESI-MS). Both native and reduced glycans were analyzed, and the developed procedure was compared with a standard HILIC procedure used in the pharmaceutical industry whereby fluorescent-labeled glycans are analyzed using a TSK Amide-80 column coupled with fluorescence detection. The separation of isobaric alditol oligosaccharides present in monoclonal antibodies and ribonuclease B is demonstrated, and ZIC-HILIC is shown to have good capability for structural recognition. Glycan profiles obtained with the ZIC-HILIC column and ESI-MS provided detailed information on MAb glycosylation, including identification of some less abundant glycan species, and are consistent with the profiles generated with the standard procedure. This new ZIC-HILIC method offers a simpler and faster approach for glycosylation analysis of therapeutic antibodies. Copyright © 2010 Elsevier Inc. All rights reserved.

Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C60† †Electronic supplementary information (ESI) available. CCDC 1579079 and 1579080. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04453d

PubMed Central

Yokoi, Hiroki; Sakamaki, Daisuke; Seki, Shu

2017-01-01

A directly connected azabuckybowl dimer was synthesized via a palladium-catalysed C–H/C–Br coupling. The electron-donating nature of the pyrrolic nitrogen atoms of the azabuckybowl enabled a strong complexation with pristine C60. In the presence of two equivalents of C60, the azabuckybowl dimer formed crystals with a 1 : 2 stoichiometry. Conversely, in diluted solution, complexes with a 1 : 1 stoichiometry of the dimer and C60 were detected predominantly, and these precipitated upon increasing the concentration of C60. Scanning electron microscopy images of the precipitate showed fibre-like aggregates, indicating the formation of supramolecular assemblies with 1D chain structures. A variable-temperature 1H NMR analysis revealed that the precipitate consists of the dimer and C60 in a 1 : 1 ratio. PMID:29629149

Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia† †Electronic supplementary information (ESI) available. CCDC 1001632–1001634. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt02537k Click here for additional data file. Click here for additional data file.

PubMed Central

Alam, Israt S.; Arrowsmith, Rory L.; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W.; Dilworth, Jonathan R.

2016-01-01

We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under ‘cold’ and ‘hot’ biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. 68Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration. PMID:26583314

Anti-cooperative ligand binding and dimerisation in the glycopeptide antibiotic dalbavancin† †Electronic supplementary information (ESI) available. See DOI: 10.1039/C3OB42428F Click here for additional data file.

PubMed Central

Cheng, Mu; Ziora, Zyta M.; Hansford, Karl A.; Blaskovich, Mark A.; Butler, Mark S.

2014-01-01

Dalbavancin, a semi-synthetic glycopeptide with enhanced antibiotic activity compared to vancomycin and teicoplanin, binds to the C-terminal lysyl-d-alanyl-d-alanine subunit of Lipid II, inhibiting peptidoglycan biosynthesis. In this study, micro-calorimetry and electrospray ionization (ESI)-MS have been used to investigate the relationship between oligomerisation of dalbavancin and binding of a Lipid II peptide mimic, diacetyl-Lys-d-Ala-d-Ala (Ac2-Kaa). Dalbavancin dimerised strongly in an anti-cooperative manner with ligand-binding, as was the case for ristocetin A, but not for vancomycin and teicoplanin. Dalbavancin and ristocetin A both adopt an ‘closed’ conformation upon ligand binding, suggesting anti-cooperative dimerisation with ligand-binding may be a general feature of dalbavancin/ristocetin A-like glycopeptides. Understanding these effects may provide insight into design of novel dalbavancin derivatives with cooperative ligand-binding and dimerisation characteristics that could enhance antibiotic activity. PMID:24608916

A metabolomics-based approach identifies changes in the small molecular weight compound composition of the peanut as a result of dry-roasting.

PubMed

Klevorn, Claire M; Dean, Lisa L

2018-02-01

Raw peanuts in the USA are subjected to thermal processing, such as dry-roasting, prior to consumption. A multi-instrument metabolomics-based platform along with targeted analyses was used to determine changes in the low-molecular-weight compound composition of peanuts due to dry-roasting. Runner and virginia-type peanut seeds were characterized using several analytical platforms including (RP)/UPLC-MS/MS (positive and negative ion mode ESI) and HILIC/UPLC-MS/MS with negative ion mode ESI. Of the 383 compounds identified, 16 compounds were unique to the roasted peanuts. Using pathway analysis, compounds associated with arginine and proline metabolism were found to be the most changed. Products of chemical degradation and compounds contained within the vesicular bodies of the peanut increased after roasting. Dry-roasting had a significant impact on the levels and types of low-molecular-weight compounds present. These findings provide useful information about composition changes due to roasting. Published by Elsevier Ltd.

The electronic structure of Au25 clusters: between discrete and continuous

NASA Astrophysics Data System (ADS)

Katsiev, Khabiboulakh; Lozova, Nataliya; Wang, Lu; Sai Krishna, Katla; Li, Ruipeng; Mei, Wai-Ning; Skrabalak, Sara E.; Kumar, Challa S. S. R.; Losovyj, Yaroslav

2016-08-01

Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies.Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies. Electronic supplementary information (ESI) available: Experimental details including chemicals, sample preparation, and characterization methods. Computation techniques, SV-AUC, GIWAXS, XPS, UPS, MALDI-TOF, ESI data of Au25 clusters. See DOI: 10.1039/c6nr02374f

Reversible mechanical protection: building a 3D “suit” around a T-shaped benzimidazole axle† †Electronic supplementary information (ESI) available: Synthetic details and full characterisation of all new compounds. CCDC 1533271 and 1533272. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00790f Click here for additional data file. Click here for additional data file.

PubMed Central

Baggi, Giorgio; Vukotic, V. Nicholas

2017-01-01

The T-shaped benzimidazolium/crown ether recognition motif was used to prepare suit[1]anes. These novel mechanically interlocked molecules (MIMs) were fully characterized by 1H and 13C NMR spectroscopy, single-crystal X-ray diffraction, UV-vis absorption and fluorescence spectroscopy. By conversion to a suit[1]ane, a simple benzimidazole was shown to be protected from deprotonation by strong base. Moreover, it was demonstrated that this unique three-dimensional encapsulation can be made reversible, thus introducing the concept of “reversible mechanical protection”; a protecting methodology that may have potential applications in synthetic organic chemistry and the design of molecular machinery. PMID:28626559

Alternating Mupirocin/Gentamicin is Associated with Increased Risk of Fungal Peritonitis as Compared with Gentamicin Alone - Results of a Randomized Open-Label Controlled Trial.

PubMed

Wong, Ping-Nam; Tong, Gensy M W; Wong, Yuk-Yi; Lo, Kin-Yee; Chan, Shuk-Fan; Lo, Man-Wai; Lo, Kwok-Chi; Ho, Lo-Yi; Tse, Cindy W S; Mak, Siu-Ka; Wong, Andrew K M

2016-01-01

♦ Catheter-related infection, namely exit-site infection (ESI) and peritonitis, is a major infectious complication and remains a main cause of technique failure for patients receiving peritoneal dialysis (PD). Topical application of antibiotic cream might reduce catheter-related infection but emergence of resistant or opportunistic organisms could be a concern. Optimal topical agents and regimens remain to be determined. We did a study to examine the effect of an alternating topical antibiotic regimen in preventing catheter-related infection. ♦ We performed a single-center, randomized, open-label study to compare daily topical application of gentamicin cream with a gentamicin/mupirocin alternate regimen to the exit site. Patients randomized to alternating regimen were asked to have daily application of gentamicin cream in odd months and mupirocin cream in even months. Primary outcomes were ESI and peritonitis. Secondary outcomes were catheter removal or death caused by catheter-related infection. A total of 146 patients (71, gentamicin group; 75, alternating regimen group) were enrolled with a total follow-up duration of 174 and 181 patient-years for gentamicin and alternating groups, respectively. All patients were followed up until catheter removal, death, transfer to another unit, transplantation or the end of the study on March 31, 2014. There were no significant differences in the age, sex, dialysis vintage, and rate of diabetes, helper-assisted dialysis and methicillin-resistant Staphylococcus aureus (MRSA) carriage state. ♦ No difference was seen in the time to first ESI or peritonitis. However, the time to first gram-negative peritonitis seemed longer for the gentamicin group (p = 0.055). The 2 groups showed a similar rate of ESI (0.17/yr vs 0.19/yr, p = 0.93) but P. aeruginosa ESI was less common in the gentamicin group (0.06/yr vs 0.11/yr, p < 0.001). There was no difference in the incidence of ESI due to non-tuberculous mycobacteria. Peritonitis rate was significantly lower in the gentamicin group (0.22/yr vs 0.32/yr, p < 0.001), with a striking decrease in gram-negative peritonitis (0.08/yr vs 0.14/yr, p < 0.001), and fungal peritonitis (0.006/yr vs 0.03/yr, p < 0.001), which was all antibiotics-related episodes with antecedent use of systemic antibiotics for the treatment of catheter-related infections. There was no significant difference in the catheter loss or death related to catheter-related infection. ♦ Alternating gentamicin/mupirocin cream application appeared as effective as gentamicin alone in preventing ESI except for P. aeruginosa. However, it was inferior to gentamicin in the prevention of peritonitis episodes, especially for those caused by gram-negative organisms. It was also not useful in reducing catheter-related infection due to opportunistic organisms but instead associated with a higher incidence of antibiotic-related fungal peritonitis. Copyright © 2016 International Society for Peritoneal Dialysis.

Speciation and identification of tellurium-containing metabolites in garlic, Allium sativum.

PubMed

Anan, Yasumi; Yoshida, Miyuki; Hasegawa, Saki; Katai, Ryota; Tokumoto, Maki; Ouerdane, Laurent; Łobiński, Ryszard; Ogra, Yasumitsu

2013-09-01

Tellurium (Te) is a widely used metalloid in industry because of its unique chemical and physical properties. However, information about the biological and toxicological activities of Te in plants and animals is limited. Although Te is expected to be metabolized in organisms via the same pathway as sulfur and selenium (Se), no precise metabolic pathways are known in organisms, particularly in plants. To reveal the metabolic pathway of Te in plants, garlic, a well-known Se accumulator, was chosen as the model plant. Garlic was hydroponically cultivated and exposed to sodium tellurate, and Te-containing metabolites in the water extract of garlic leaves were identified using HPLC coupled with inductively coupled plasma mass spectrometry (ICP-MS) or electrospray tandem mass spectrometry (ESI-MS-MS). At least three Te-containing metabolites were detected using HPLC-ICP-MS, and two of them were subjected to HPLC-ESI-MS-MS for identification. The MS spectra obtained by ESI-MS-MS indicated that the metabolite was Te-methyltellurocysteine oxide (MeTeCysO). Then, MeTeCysO was chemically synthesized and its chromatographic behavior matched with that of the Te-containing metabolite in garlic. The other was assigned as cysteine S-methyltellurosulfide. These results suggest that garlic can assimilate tellurate, an inorganic Te compound, and tellurate is transformed into a Te-containing amino acid, the so-called telluroamino acid. This is the first report addressing that telluroamino acid is de novo synthesized in a higher plant.

The syntheses, characterization and in vitro metabolism of nitracaine, methoxypiperamide and mephtetramine.

PubMed

Power, John D; Scott, Kenneth R; Gardner, Elizabeth A; Curran McAteer, Bronagh M; O'Brien, John E; Brehon, Margaret; Talbot, Brian; Kavanagh, Pierce V

2014-01-01

Three legal highs; nitracaine (3-(diethylamino)-2,2-dimethylpropyl 4-nitrobenzoate), methoxypiperamide (MEOP, (4-methoxyphenyl)(4-methylpiperazin-1-yl)methanone) and mephtetramine (MTTA, 2-((methylamino)methyl)-3,4-dihydronaphthalen-1(2H)-one) appeared in 2013 as new psychoactive substances (NPS) on Internet websites selling 'research chemicals'. These compounds were synthesized and analyzed via our synthesize, analyze, and metabolize (SAM) protocol. Nitracaine was synthesized by the transesterification of methyl 4-nitrobenzoate with 3-(diethylamino)-2,2-dimethylpropan-1-ol. Methoxypiperamide was synthesized by the reaction of 4-methoxybenzoyl chloride with 1-methylpiperazine, and mephtetramine through the Mannich reaction of 1-tetralone with paraformaldehyde and methylamine hydrochloride. Each compound was characterized by nuclear magnetic resonance (NMR), gas chromatography with electron impact mass spectrometry (GC-EIMS), liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and high resolution electrospray ionization mass spectrometry (HR-ESI-MS). A sample of nitracaine was also test-purchased from an Internet vendor and its structure confirmed by GC-EIMS and LC-ESI-MS. Finally, the in vitro metabolism of the nitracaine, mephtetramine, and methoxypiperamide was investigated, using a human microsomal liver extract, in order to tentatively identify potential metabolites that may be encountered in the analysis of biological samples in clinical or toxicology labs. The use of our SAM protocol highlights the ability of academic research labs to quickly respond to and disseminate information about emerging NPS. Copyright © 2014 John Wiley & Sons, Ltd.

The Portuguese version of the Epilepsy Surgery Inventory (ESI-55): cross-cultural adaptation and evaluation of psychometric properties.

PubMed

Alonso, Neide Barreira; Ciconelli, Rozana Mesquita; da Silva, Tatiana Indelicato; Westphal-Guitti, Ana Carolina; Azevedo, Auro Mauro; da Silva Noffs, Maria Helena; Caboclo, Luís Otávio Sales Ferreira; Sakamoto, Américo Ceiki; Targas Yacubian, Elza Márcia

2006-08-01

The purpose of this study was to develop a Portuguese version of the Epilepsy Surgery Inventory (ESI-55) and to assess its psychometric properties. Sixty patients with temporal lobe epilepsy related to unilateral mesial temporal sclerosis who underwent presurgical evaluation at the Universidade Federal de São Paulo (UNIFESP) formed the sample for this study. The psychometric properties of the ESI-55 included: reliability, validity, and responsiveness. Internal consistency was high in all domains (Cronbach's alpha ranging from 0.76 for Social Function to 0.88 for Physical Function) except Overall Quality of Life (alpha=0.45). Test-retest reliability after 1 week was good, with the intraclass correlation coefficient ranging from 0.79 (Energy/Fatigue) to 0.92 (Role Limitations due to Emotional Problems). Interrater reliability ranged from 0.84 (Cognitive Function) to 0.94 (Role Limitations due to Physical Problems). For construct validity, we verified a high correlation between the ESI-55 and Health Assessment Questionnaire-8 for the Physical Function domain (Pearson linear correlation=-0.84), and a moderate correlation for the Pain domain (P=-0.58), but for the other subscales no correlation was detected. Beck Depression Inventory and ESI-55 domains were highly statistically correlated (ANOVA: P<0.005), but there was no association of the Cognitive Function and Role Limitations due to Memory Problems subscales with neuropsychological evaluation (Pearson coefficient: P>0.05). With respect to demographic characteristics, a statistically significant correlation was observed for the variable educational level (Student t, P<0.005) and ESI-55 scores. There was a high correlation between seizure frequency and ESI-55 domains for clinical variables (ANOVA, P<0.005). Surgical treatment in this series improved health-related quality of life in the seizure-free group in three domains--Health Perception (1.24), Emotional Well-Being (1.32), and Energy/Fatigue (1.48)-as reflected by the standard response mean and the effect size of the sample. Our results support the psychometric properties of the Portuguese version of the ESI-55 as a measure of health-related quality of life.

Comparison of PCR/Electron spray Ionization-Time-of-Flight-Mass Spectrometry versus Traditional Clinical Microbiology for active surveillance of organisms contaminating high-use surfaces in a burn intensive care unit, an orthopedic ward and healthcare workers

PubMed Central

2012-01-01

Background Understanding nosocomial pathogen transmission is restricted by culture limitations. Novel platforms, such as PCR-based electron spray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS), may be useful as investigational tools. Methods Traditional clinical microbiology (TCM) and PCR/ESI-TOF-MS were used to recover and detect microorganisms from the hands and personal protective equipment of 10 burn intensive care unit (ICU) healthcare workers providing clinical care at a tertiary care military referral hospital. High-use environmental surfaces were assessed in 9 burn ICU and 10 orthopedic patient rooms. Clinical cultures during the study period were reviewed for pathogen comparison with investigational molecular diagnostic methods. Results From 158 samples, 142 organisms were identified by TCM and 718 by PCR/ESI-TOF-MS. The molecular diagnostic method detected more organisms (4.5 ± 2.1 vs. 0.9 ± 0.8, p < 0.01) from 99% vs. 67% of samples (p < 0.01). TCM detected S. aureus in 13 samples vs. 21 by PCR/ESI-TOF-MS. Gram-negative organisms were less commonly identified than gram-positive by both methods; especially by TCM. Among all detected bacterial species, similar percentages were typical nosocomial pathogens (18-19%) for TCM vs. PCR/ESI-TOF-MS. PCR/ESI-TOF-MS also detected mecA in 112 samples, vanA in 13, and KPC-3 in 2. MecA was associated (p < 0.01) with codetection of coagulase negative staphylococci but not S. aureus. No vanA was codetected with enterococci; one KPC-3 was detected without Klebsiella spp. Conclusions In this pilot study, PCR/ESI-TOF-MS detected more organisms, especially gram-negatives, compared to TCM, but the current assay format is limited by the number of antibiotic resistance determinants it covers. Further large-scale assessments of PCR/ESI-TOF-MS for hospital surveillance are warranted. PMID:23050585

Comparative investigation of low-molecular-weight fulvic acids of different origin by SEC-Q-TOF-ms: new insights into structure and formation.

PubMed

Reemtsma, Thorsten; These, Anja

2005-05-15

Size exclusion chromatography (SEC) coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS) was used to analyze the elemental composition and structure of low-molecular-weight fulvic acid molecules. It is shown that the set of hundreds of individual molecules form a homogeneous and structurally unique class of compounds that can be clearly differentiated from any other class of biogenic matter investigated to date. The molecular composition of low-molecular-weight fulvic acids in isolates of very different origin (surface water, groundwater, peat) is virtually indistinguishable. Significant and characteristic differences are, however, recognized when qualitative information and quantitative information provided by ESI-Q-TOF-MS are linked to each other. The relative frequency of the various molecules in each mixture can differ significantly, with the peat showing higher intensity of the aromatic and less carboxylated molecules of this set, whereas the aquatic fulvic acids show a strong contribution of the molecules with less aromaticity and a higher carboxylate content. The identity of fulvic acid molecules in isolates of different origin implies that no specific source material is required forfulvic acid formation but that they may be formed from different sources by different oxidative processes.

Proceedings of Conference on Variable-Resolution Modeling, Washington, DC, 5-6 May 1992

DTIC Science & Technology

1992-05-01

of powerful new computer architectures for supporting object-oriented computing. Objects, as self -contained data-code packages with orderly...another entity structure. For example, (copy-entstr e:sys- tcm ’ new -system) creates an entity structure named c:new-system that has the same structure...324 Parry, S-H. (1984): A Self -contained Hierarchical Model Construct. In: Systems Analysis and Modeling in Defense (R.K. Huber, Ed.), New York

Improved sensitivity by post-column chemical environment modification of CE-ESI-MS using a flow-through microvial interface.

PubMed

Risley, Jessica May; Chen, David Da Yong

2017-06-01

Post-column chemical environment modification can affect detection sensitivity and signal appearance when capillary electrophoresis is coupled through electrospray ionization to mass spectrometry (CE-ESI-MS). In this study, changes in the signal intensity and peak shape of N-Acetylneuraminic acid (Neu5Ac) were examined when the modifier solution used in a flow-through microvial interface for CE-ESI-MS was prepared using an acidic or basic background electrolyte (BGE) composition. The use of a basic modifier resulted in improved detection compared to the results obtained when an acidic modifier was used in negative ion mode. Increased sensitivity and more symmetrical peak shape were obtained. Using an acidic modifier, the LOD of Neu5Ac was 47.7 nM, whereas for a basic modifier, the LOD of Neu5Ac was 5.20 nM. The calculated asymmetry factor at 100 nM of Neu5Ac ranged from 0.71 to 1.5 when an acidic modifier was used, while the factor ranged from 1.0 to 1.1 when a basic modifier was used. Properly chosen post-column chemical modification can have a significant effect on the performance of the CE-MS system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Top-down approach for the direct characterization of low molecular weight heparins using LC-FT-MS.

PubMed

Li, Lingyun; Zhang, Fuming; Zaia, Joseph; Linhardt, Robert J

2012-10-16

Low molecular heparins (LMWHs) are structurally complex, heterogeneous, polydisperse, and highly negatively charged mixtures of polysaccharides. The direct characterization of LMWH is a major challenge for currently available analytical technologies. Electrospray ionization (ESI) liquid chromatography-mass spectrometry (LC-MS) is a powerful tool for the characterization complex biological samples in the fields of proteomics, metabolomics, and glycomics. LC-MS has been applied to the analysis of heparin oligosaccharides, separated by size exclusion, reversed phase ion-pairing chromatography, and chip-based amide hydrophilic interaction chromatography (HILIC). However, there have been limited applications of ESI-LC-MS for the direct characterization of intact LMWHs (top-down analysis) due to their structural complexity, low ionization efficiency, and sulfate loss. Here we present a simple and reliable HILIC-Fourier transform (FT)-ESI-MS platform to characterize and compare two currently marketed LMWH products using the top-down approach requiring no special sample preparation steps. This HILIC system relies on cross-linked diol rather than amide chemistry, affording highly resolved chromatographic separations using a relatively high percentage of acetonitrile in the mobile phase, resulting in stable and high efficiency ionization. Bioinformatics software (GlycReSoft 1.0) was used to automatically assign structures within 5-ppm mass accuracy.

Post-acquisition data processing for the screening of transformation products of different organic contaminants. Two-year monitoring of river water using LC-ESI-QTOF-MS and GCxGC-EI-TOF-MS.

PubMed

López, S Herrera; Ulaszewska, M M; Hernando, M D; Martínez Bueno, M J; Gómez, M J; Fernández-Alba, A R

2014-11-01

This study describes a comprehensive strategy for detecting and elucidating the chemical structures of expected and unexpected transformation products (TPs) from chemicals found in river water and effluent wastewater samples, using liquid chromatography coupled to electrospray ionization quadrupole-time-of-flight mass spectrometer (LC-ESI-QTOF-MS), with post-acquisition data processing and an automated search using an in-house database. The efficacy of the mass defect filtering (MDF) approach to screen metabolites from common biotransformation pathways was tested, and it was shown to be sufficiently sensitive and applicable for detecting metabolites in environmental samples. Four omeprazole metabolites and two venlafaxine metabolites were identified in river water samples. This paper reports the analytical results obtained during 2 years of monitoring, carried out at eight sampling points along the Henares River (Spain). Multiresidue monitoring, for targeted analysis, includes a group of 122 chemicals, amongst which are pharmaceuticals, personal care products, pesticides and PAHs. For this purpose, two analytical methods were used based on direct injection with a LC-ESI-QTOF-MS system and stir bar sorptive extraction (SBSE) with bi-dimensional gas chromatography coupled with a time-of-flight spectrometer (GCxGC-EI-TOF-MS).

Formation of low charge state ions of synthetic polymers using quaternary ammonium compounds.

PubMed

Nasioudis, Andreas; Joyce, William F; van Velde, Jan W; Heeren, Ron M A; van den Brink, Oscar F

2010-07-01

Factors such as high polymer dispersity and variation in elemental composition (of copolymers) often complicate the electrospray ionization mass spectrometry (ESI-MS) analysis of synthetic polymers with high molar mass. In the experiments described in this study, quaternary ammonium compounds were observed to facilitate the production of low charge state pseudomolecular ions when added to the spray solution for ESI-MS. This approach was then used for the ESI time-of-flight mass spectrometry (TOF-MS) analysis of synthetic polymers. Hexadecyltrimethylammonium chloride permitted the successful analysis of poly(ethylene glycol) of 2-40 kDa, poly(propylene glycol) and poly(tetramethylene glycol) oligomers. Increasing the quaternary ammonium compounds' concentration results in the production of low charge state pseudomolecular ions. A comparison of structurally different quaternary ammonium compounds showed that the best performance is expected from large molecules with specific charge localization, which leaves the charge available for interactions. The applicability of the method for the MS analysis of other polymeric systems was also studied. In the case of poly(tetramethylene glycol), the method not only shifted the distributions to higher m/z values but also allowed the detection of high molecular weight material that was not observed without addition of the modifier to the spray solution.

Cu/Mn bimetallic catalysis enables carbonylative Suzuki–Miyaura coupling with unactivated alkyl electrophiles† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc01170a Click here for additional data file.

PubMed Central

Pye, Dominic R.; Cheng, Li-Jie

2017-01-01

A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C–C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C–C coupling step. PMID:28966784

An easy-to-prepare mini-scaffold for DNA origami

NASA Astrophysics Data System (ADS)

Brown, S.; Majikes, J.; Martínez, A.; Girón, T. M.; Fennell, H.; Samano, E. C.; Labean, T. H.

2015-10-01

The DNA origami strategy for assembling designed supramolecular complexes requires ssDNA as a scaffold strand. A system is described that was designed approximately one third the length of the M13 bacteriophage genome for ease of ssDNA production. Folding of the 2404-base ssDNA scaffold into a variety of origami shapes with high assembly yields is demonstrated.The DNA origami strategy for assembling designed supramolecular complexes requires ssDNA as a scaffold strand. A system is described that was designed approximately one third the length of the M13 bacteriophage genome for ease of ssDNA production. Folding of the 2404-base ssDNA scaffold into a variety of origami shapes with high assembly yields is demonstrated. Electronic supplementary information (ESI) available: Flow chart of the production process, base sequences of the scaffold strand, and synthetic staple strands, as well as caDNAnao files for all three mini-M13 origami structures. See DOI: 10.1039/c5nr04921k

Directed assembly of nanoparticles to isolated diatom valves using the non-wetting characteristics after pyrolysis

NASA Astrophysics Data System (ADS)

Jantschke, A.; Fischer, C.; Hensel, R.; Braun, H.-G.; Brunner, E.

2014-09-01

A novel strategy for a directed nanoparticle coupling to isolated Stephanopyxis turris valves is presented. After pyrolysis, the valves exhibit incomplete wetting due to their characteristic T-shaped profiles as a prerequisite for a regioselective coupling reaction. A micromanipulation system allows for precise handling and their immobilization onto an adhesive substrate and manipulation into arrays.A novel strategy for a directed nanoparticle coupling to isolated Stephanopyxis turris valves is presented. After pyrolysis, the valves exhibit incomplete wetting due to their characteristic T-shaped profiles as a prerequisite for a regioselective coupling reaction. A micromanipulation system allows for precise handling and their immobilization onto an adhesive substrate and manipulation into arrays. Electronic supplementary information (ESI) available: BET surface area, TG/DTA measurements, HIM images and a video of an array of six valves of S. turris in a wetting experiment as well as a 3D animation based on CLSM measurements. See DOI: 10.1039/c4nr02662d

Experimental investigation of the 2D ion beam profile generated by an ESI octopole-QMS system.

PubMed

Syed, Sarfaraz U A H; Eijkel, Gert B; Kistemaker, Piet; Ellis, Shane; Maher, Simon; Smith, Donald F; Heeren, Ron M A

2014-10-01

In this paper, we have employed an ion imaging approach to investigate the behavior of ions exiting from a quadrupole mass spectrometer (QMS) system that employs a radio frequency octopole ion guide before the QMS. An in-vacuum active pixel detector (Timepix) is employed at the exit of the QMS to image the ion patterns. The detector assembly simultaneously records the ion impact position and number of ions per pixel in every measurement frame. The transmission characteristics of the ion beam exiting the QMS are studied using this imaging detector under different operating conditions. Experimental results confirm that the ion spatial distribution exiting the QMS is heavily influenced by ion injection conditions. Furthermore, ion images from Timepix measurements of protein standards demonstrate the capability to enhance the quality of the mass spectral information and provide a detailed insight in the spatial distribution of different charge states (and hence different m/z) ions exiting the QMS.

Facile electrodeposition of reduced graphene oxide hydrogels for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Pham, Viet Hung; Gebre, Tesfaye; Dickerson, James H.

2015-03-01

We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively.We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively. Electronic supplementary information (ESI) available: GO synthesis, characterization, fabrication of ERGO supercapacitor and electrochemical measurement, elemental composition, TGA and XRD of GO and ERGO. See DOI: 10.1039/c4nr07508k

Pneumatic Microvalve-Based Hydrodynamic Sample Injection for High-Throughput, Quantitative Zone Electrophoresis in Capillaries

PubMed Central

2015-01-01

A hybrid microchip/capillary electrophoresis (CE) system was developed to allow unbiased and lossless sample loading and high-throughput repeated injections. This new hybrid CE system consists of a poly(dimethylsiloxane) (PDMS) microchip sample injector featuring a pneumatic microvalve that separates a sample introduction channel from a short sample loading channel, and a fused-silica capillary separation column that connects seamlessly to the sample loading channel. The sample introduction channel is pressurized such that when the pneumatic microvalve opens briefly, a variable-volume sample plug is introduced into the loading channel. A high voltage for CE separation is continuously applied across the loading channel and the fused-silica capillary separation column. Analytes are rapidly separated in the fused-silica capillary, and following separation, high-sensitivity MS detection is accomplished via a sheathless CE/ESI-MS interface. The performance evaluation of the complete CE/ESI-MS platform demonstrated that reproducible sample injection with well controlled sample plug volumes could be achieved by using the PDMS microchip injector. The absence of band broadening from microchip to capillary indicated a minimum dead volume at the junction. The capabilities of the new CE/ESI-MS platform in performing high-throughput and quantitative sample analyses were demonstrated by the repeated sample injection without interrupting an ongoing separation and a linear dependence of the total analyte ion abundance on the sample plug volume using a mixture of peptide standards. The separation efficiency of the new platform was also evaluated systematically at different sample injection times, flow rates, and CE separation voltages. PMID:24865952

Pneumatic Microvalve-Based Hydrodynamic Sample Injection for High-Throughput, Quantitative Zone Electrophoresis in Capillaries

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

Kelly, Ryan T.; Wang, Chenchen; Rausch, Sarah J.

2014-07-01

A hybrid microchip/capillary CE system was developed to allow unbiased and lossless sample loading and high throughput repeated injections. This new hybrid CE system consists of a polydimethylsiloxane (PDMS) microchip sample injector featuring a pneumatic microvalve that separates a sample introduction channel from a short sample loading channel and a fused silica capillary separation column that connects seamlessly to the sample loading channel. The sample introduction channel is pressurized such that when the pneumatic microvalve opens briefly, a variable-volume sample plug is introduced into the loading channel. A high voltage for CE separation is continuously applied across the loading channelmore » and the fused silica capillary separation column. Analytes are rapidly separated in the fused silica capillary with high resolution. High sensitivity MS detection after CE separation is accomplished via a sheathless CE/ESI-MS interface. The performance evaluation of the complete CE/ESI-MS platform demonstrated that reproducible sample injection with well controlled sample plug volumes could be achieved by using the PDMS microchip injector. The absence of band broadening from microchip to capillary indicated a minimum dead volume at the junction. The capabilities of the new CE/ESI-MS platform in performing high throughput and quantitative sample analyses were demonstrated by the repeated sample injection without interrupting an ongoing separation and a good linear dependence of the total analyte ion abundance on the sample plug volume using a mixture of peptide standards. The separation efficiency of the new platform was also evaluated systematically at different sample injection times, flow rates and CE separation voltages.« less

Poly(3,4-ethylenedioxypyrrole) Modified Emitter Electrode for Substitution of Homogeneous Redox Buffer Agent Hydroquinone in Electrospray Ionization Mass Spectrometry

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

Peintler-Krivan, Emese; Van Berkel, Gary J; Kertesz, Vilmos

2010-01-01

The electrolysis inherent to the operation of the electrospray ionization (ESI) source used with mass spectrometry (MS) is a well-known attendant effect of generating unipolar spray droplets and may affect the analysis of the analyte of interest. Undesirable electrolysis of an analyte may be prevented by limiting the emitter electrode current and/or the mass transport characteristics of the system. However, these ways to avoid analyte electrolysis may not be applcable in all ESI-MS experiments. For example, in the case of specific nanospray systems (e.g. the wire-in-a-capillary bulk-loaded or chip-based tip-loaded nanospray configurations), the solution flow rate is fixed in themore » 50-500 nL/min range and the electrode surface to volume ratio is large presenting a very effcient analyte to electrode mass transport configuration. In these situations, control over the interfacial potential of the working electrode via homogeneous or traditional heterogeneous (sacrificial metal) redox buffering is a possible way to prevent analyte electrolysis. However, byproducts of these redox buffering approaches can appear in the mass spectra and/or they can chemically alter the analyte. For example, the main reason for using hydroquinone as a homogeneous redox buffer, in addition to its relatively low oxidation potential, is that neither the original compound nor its oxidation product benzoquinone can be detected directly by ESI-MS. However, benzoquinone can alter analytes with thiol functional groups by reacting with those groups via a 1,4-Michael addition.« less

In the Jungle of Astronomical On--line Data Services

NASA Astrophysics Data System (ADS)

Egret, D.

The author tried to survive in the jungle of astronomical on--line data services. In order to find efficient answers to common scientific data retrieval requests, he had to collect many pieces of information, in order to formulate typical user scenarios, and try them against a number of different data bases, catalogue services, or information systems. He discovered soon how frustrating treasure coffers may be when their keys are not available, but he realized also that nice widgets and gadgets are of no help when the information is not there. And, before long, he knew he would have to navigate through several systems because no one was yet offering a general answer to all his questions. I will present examples of common user scenarios and show how they were tested against a number of services. I will propose some elements of classification which should help the end-user to evaluate how adequate the different services may be for providing satisfying answers to specific queries. For that, many aspects of the user interaction will be considered: documentation, access, query formulation, functionalities, qualification of the data, overall efficiency, etc. I will also suggest possible improvements to the present situation: the first of them being to encourage system managers to increase collaboration between one another, for the benefit of the whole astronomical community. The subjective review I will present, is based on publicly available astronomical on--line services from the U.S. and from Europe, most of which (excepting the newcomers) were described in ``Databases and On-Line Data in Astronomy", (Albrecht & Egret, eds, 1991): this includes databases (such as NED and Simbad ), catalog services ( StarCat , DIRA , XCatScan , etc.), and information systems ( ADS and ESIS ).

MiDAS ENCORE: Randomized Controlled Study Design and Protocol.

PubMed

Benyamin, Ramsin M; Staats, Peter S

2015-01-01

Epidural steroid injections (ESIs) are commonly used for treatment of symptomatic lumbar spinal stenosis (LSS). ESIs are generally administered after failure of conservative therapy. For LSS patients suffering from neurogenic claudication, the mild® procedure provides an alternative to ESIs via minimally invasive lumbar decompression. Both ESIs and mild offer interventional pain treatment options for LSS patients experiencing neurogenic claudication refractory to more conservative therapies. Prospective, multi-center, randomized controlled, clinical study. Twenty-six interventional pain management centers throughout the United States. To compare patient outcomes following treatment with either mild or ESIs in LSS patients with neurogenic claudication and having verified ligamentum flavum hypertrophy. Study participants include Medicare beneficiaries who meet study inclusion/exclusion criteria. Eligible patients will be randomized in a 1:1 ratio to one of 2 treatment arms, mild (treatment group) or ESI (control group). Each study group will include approximately 150 patients who have experienced neurogenic claudication symptoms for ≥ 3 months duration who have failed to respond to physical therapy, home exercise programs, and oral analgesics. Those randomized to mild are prohibited from receiving lumbar ESIs during the study period, while those randomized to ESI may receive ESIs up to 4 times per year. Patient assessments will occur at baseline, 6 months, and one year. An additional assessment will be conducted for the mild patient group at 2 years. The primary efficacy outcome measure is the proportion of Oswestry Disability Index (ODI) responders from baseline to one year follow-up in the treatment group (mild) versus the control group (ESI). ODI responders are defined as those patients achieving the validated Minimal Important Change (MIC) of ≥ 10 point improvement in ODI from baseline to follow-up as a clinically significant efficacy threshold. Secondary efficacy outcome measures include the proportion of Zurich Claudication Questionnaire (ZCQ) and Numeric Pain Rating Scale (NPRS) responders from baseline to follow-up using validated MIC thresholds. Improvement in ZCQ domains of ≥ 0.5 is considered significant, and a Patient Satisfaction score of at least 2.5 represents a satisfied patient. A reduction of ≥ 2 points in NPRS is considered significant pain relief. The primary safety outcome measure is the incidence of device- and/or procedure-related adverse events. Descriptive summaries will be presented by randomized group for all outcome measures at baseline and follow-up time points. Inferential statistical analysis will be conducted to determine significant differences related to functional improvement, pain relief, and safety outcomes. Primary study results will be presented based on one-year follow-up data, with an interim analysis report when 6-month follow-up data become available. Patients are not blinded due to significant differences in treatment protocols between study groups. Also, since neither study arm is focused on treatment of radicular pain, there may be a higher non-responder rate for both groups versus standard of care due to study restrictions on adjunctive pain therapies. This prospective, multi-center, randomized controlled study will provide Level I evidence of the safety and effectiveness of mild versus ESIs in managing neurogenic claudication symptoms in LSS patients.

Examining the Premises Supporting the Empirically Supported Intervention Approach to Social Work Practice

ERIC Educational Resources Information Center

McBeath, Bowen; Briggs, Harold E.; Aisenberg, Eugene

2010-01-01

Federal, state, and local policymakers and funders have increasingly organized human service delivery functions around the selection and implementation of empirically supported interventions (ESIs), under the expectation that service delivery through such intervention frameworks results in improvements in cost-effectiveness and system performance.…

The Theoretical Basis of the Effective School Improvement Model (ESI)

ERIC Educational Resources Information Center

Scheerens, Jaap; Demeuse, Marc

2005-01-01

This article describes the process of theoretical reflection that preceded the development and empirical verification of a model of "effective school improvement". The focus is on basic mechanisms that could be seen as underlying "getting things in motion" and change in education systems. Four mechanisms are distinguished:…

Modeling Positive Behavior Interventions and Supports for Preservice Teachers

ERIC Educational Resources Information Center

Hill, Doris Adams; Flores, Margaret M.

2014-01-01

The authors modeled programwide positive behavior interventions and supports (PBIS) principles to 26 preservice teachers during consolidated yearly extended school year (ESY) services delivered to elementary students from four school districts. While PBIS were in place for preservice teachers to implement with students, a similar system was…

76 FR 58258 - Combined Notice of Filings #1

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-20

... Colorado Wind Energy, LLC, Peetz Table Energy, LLC, NextEtra Energy Power Marketing, LLC. Description: Next... System Cost filing for sales of electric power to the Bonneville Power Administration pursuant to Part 35...-832-011. Applicants: ESI Vansycle Partners, L.P., FPL Energy New Mexico Wind, LLC, FPL Energy...

Sensitive determination of RDX, nitroso-RDX metabolites, and other munitions in ground water by solid-phase extraction and isotope dilution liquid chromatography-atmospheric pressure electro-spray [correction of chemical] ionization mass spectrometry.

PubMed

Cassada, D A; Monson, S J; Snow, D D; Spalding, R F

1999-06-04

Recent improvements in the LC-MS interface have increased the sensitivity and selectivity of this instrument in the analysis of polar and thermally-labile aqueous constituents. Determination of RDX, nitroso-RDX metabolites, and other munitions was enhanced using LC-MS with solid-phase extraction, 15N3-RDX internal standard, and electrospray ionization (ESI) in negative ion mode. ESI produced a five-fold increase in detector response over atmospheric pressure chemical ionization (APCI) for the nitramine compounds, while the more energetic APCI produced more than twenty times the ESI response for nitroaromatics. Method detection limits in ESI for nitramines varied from 0.03 microgram l-1 for MNX to 0.05 microgram l-1 for RDX.

Development of Remote Sampling ESI Mass Spectrometry for the Rapid and Automatic Analysis of Multiple Samples

PubMed Central

Yamada, Yuki; Ninomiya, Satoshi; Hiraoka, Kenzo; Chen, Lee Chuin

2016-01-01

We report on combining a self-aspirated sampling probe and an ESI source using a single metal capillary which is electrically grounded and safe for use by the operator. To generate an electrospray, a negative H.V. is applied to the counter electrode of the ESI emitter to operate in positive ion mode. The sampling/ESI capillary is enclosed within another concentric capillary similar to the arrangement for a standard pneumatically assisted ESI source. The suction of the liquid sample is due to the Venturi effect created by the high-velocity gas flow near the ESI tip. In addition to serving as the mechanism for suction, the high-velocity gas flow also assists in the nebulization of charged droplets, thus producing a stable ion signal. Even though the potential of the ion source counter electrode is more negative than the mass spectrometer in the positive ion mode, the electric field effect is not significant if the ion source and the mass spectrometer are separated by a sufficient distance. Ion transmission is achieved by the viscous flow of the carrier gas. Using the present arrangement, the user can hold the ion source in a bare hand and the ion signal appears almost immediately when the sampling capillary is brought into contact with the liquid sample. The automated analysis of multiple samples can also be achieved by using motorized sample stage and an automated ion source holder. PMID:28616373

Radiation Metabolomics. 4. UPLC-ESI-QTOFMS-Based Metabolomics for Urinary Biomarker Discovery in Gamma-Irradiated Rats

PubMed Central

Johnson, Caroline H.; Patterson, Andrew D.; Krausz, Kristopher W.; Lanz, Christian; Kang, Dong Wook; Luecke, Hans; Gonzalez, Frank J.; Idle, Jeffrey R.

2011-01-01

Radiation metabolomics has aided in the identification of a number of biomarkers in cells and mice by ultra-performance liquid chromatography-coupled time-of-flight mass spectrometry (UPLC-ESI-QTOFMS) and in rats by gas chromatography-coupled mass spectrometry (GCMS). These markers have been shown to be both dose- and time-dependent. Here UPLC-ESI-QTOFMS was used to analyze rat urine samples taken from 12 rats over 7 days; they were either sham-irradiated or γ-irradiated with 3 Gy after 4 days of metabolic cage acclimatization. Using multivariate data analysis, nine urinary biomarkers of γ radiation in rats were identified, including a novel mammalian metabolite, N-acetyltaurine. These upregulated urinary biomarkers were confirmed through tandem mass spectrometry and comparisons with authentic standards. They include thymidine, 2′-deoxyuridine, 2′deoxyxanthosine, N1-acetylspermidine, N-acetylglucosamine/galactosamine-6-sulfate, N-acetyltaurine, N-hexanoylglycine, taurine and, tentatively, isethionic acid. Of these metabolites, 2′-deoxyuridine and thymidine were previously identified in the rat by GCMS (observed as uridine and thymine) and in the mouse by UPLC-ESI-QTOFMS. 2′Deoxyxanthosine, taurine and N-hexanoylglycine were also seen in the mouse by UPLC-ESI-QTOFMS. These are now unequivocal cross-species biomarkers for ionizing radiation exposure. Downregulated biomarkers were shown to be related to food deprivation and starvation mechanisms. The UPLC-ESI-QTOFMS approach has aided in the advance for finding common biomarkers of ionizing radiation exposure. PMID:21309707

Development of Remote Sampling ESI Mass Spectrometry for the Rapid and Automatic Analysis of Multiple Samples.

PubMed

Yamada, Yuki; Ninomiya, Satoshi; Hiraoka, Kenzo; Chen, Lee Chuin

2016-01-01

We report on combining a self-aspirated sampling probe and an ESI source using a single metal capillary which is electrically grounded and safe for use by the operator. To generate an electrospray, a negative H.V. is applied to the counter electrode of the ESI emitter to operate in positive ion mode. The sampling/ESI capillary is enclosed within another concentric capillary similar to the arrangement for a standard pneumatically assisted ESI source. The suction of the liquid sample is due to the Venturi effect created by the high-velocity gas flow near the ESI tip. In addition to serving as the mechanism for suction, the high-velocity gas flow also assists in the nebulization of charged droplets, thus producing a stable ion signal. Even though the potential of the ion source counter electrode is more negative than the mass spectrometer in the positive ion mode, the electric field effect is not significant if the ion source and the mass spectrometer are separated by a sufficient distance. Ion transmission is achieved by the viscous flow of the carrier gas. Using the present arrangement, the user can hold the ion source in a bare hand and the ion signal appears almost immediately when the sampling capillary is brought into contact with the liquid sample. The automated analysis of multiple samples can also be achieved by using motorized sample stage and an automated ion source holder.

CicerTransDB 1.0: a resource for expression and functional study of chickpea transcription factors.

PubMed

Gayali, Saurabh; Acharya, Shankar; Lande, Nilesh Vikram; Pandey, Aarti; Chakraborty, Subhra; Chakraborty, Niranjan

2016-07-29

Transcription factor (TF) databases are major resource for systematic studies of TFs in specific species as well as related family members. Even though there are several publicly available multi-species databases, the information on the amount and diversity of TFs within individual species is fragmented, especially for newly sequenced genomes of non-model species of agricultural significance. We constructed CicerTransDB (Cicer Transcription Factor Database), the first database of its kind, which would provide a centralized putatively complete list of TFs in a food legume, chickpea. CicerTransDB, available at www.cicertransdb.esy.es , is based on chickpea (Cicer arietinum L.) annotation v 1.0. The database is an outcome of genome-wide domain study and manual classification of TF families. This database not only provides information of the gene, but also gene ontology, domain and motif architecture. CicerTransDB v 1.0 comprises information of 1124 genes of chickpea and enables the user to not only search, browse and download sequences but also retrieve sequence features. CicerTransDB also provides several single click interfaces, transconnecting to various other databases to ease further analysis. Several webAPI(s) integrated in the database allow end-users direct access of data. A critical comparison of CicerTransDB with PlantTFDB (Plant Transcription Factor Database) revealed 68 novel TFs in the chickpea genome, hitherto unexplored. Database URL: http://www.cicertransdb.esy.es.

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

The photochemical thiol–ene reaction as a versatile method for the synthesis of glutathione S-conjugates targeting the bacterial potassium efflux system Kef† †Electronic supplementary information (ESI) available: Further experimental details and NMR spectra. See DOI: 10.1039/c5qo00436e Click here for additional data file.

PubMed Central

Rasmussen, Tim; Miller, Samantha; Booth, Ian R.

2016-01-01

The thiol–ene coupling reaction is emerging as an important conjugation reaction that is suitable for use in a biological setting. Here, we explore the utility of this reaction for the synthesis of glutathione-S-conjugates (GSX) and present a general, operationally simple, protocol with a wide substrate scope. The GSX afforded are an important class of compounds and provide invaluable molecular tools to study glutathione-binding proteins. In this study we apply the diverse library of GSX synthesised to further our understanding of the structural requirements for binding to the glutathione-binding protein, Kef, a bacterial K+ efflux system, found in many bacterial pathogens. This system is vital to the survival of bacteria upon exposure to electrophiles, and plays an essential role in the maintenance of intracellular pH and K+ homeostasis. Consequently, Kef is an appealing target for the development of novel antibacterial drugs. PMID:27110363

Identification of phenolic compounds in red wine extract samples and zebrafish embryos by HPLC-ESI-LTQ-Orbitrap-MS.

PubMed

Vallverdú-Queralt, Anna; Boix, Nuria; Piqué, Ester; Gómez-Catalan, Jesús; Medina-Remon, Alexander; Sasot, Gemma; Mercader-Martí, Mercè; Llobet, Juan M; Lamuela-Raventos, Rosa M

2015-08-15

The zebrafish embryo is a highly interesting biological model with applications in different scientific fields, such as biomedicine, pharmacology and toxicology. In this study, we used liquid chromatography/electrospray ionisation-linear ion trap quadrupole-Orbitrap-mass spectrometry (HPLC/ESI-LTQ-Orbitrap-MS) to identify the polyphenol compounds in a red wine extract and zebrafish embryos. Phenolic compounds and anthocyanin metabolites were determined in zebrafish embryos previously exposed to the red wine extract. Compounds were identified by injection in a high-resolution system (LTQ-Orbitrap) using accurate mass measurements in MS, MS(2) and MS(3) modes. To our knowledge, this research constitutes the first comprehensive identification of phenolic compounds in zebrafish by HPLC coupled to high-resolution mass spectrometry. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer System for In-Situ Detection of Organic Compounds

NASA Technical Reports Server (NTRS)

Kanik, I.; Johnson, P. V.; Beegle, L. W.; Cooks, R. G.; Laughlin, B. C.; Hill, H. H.

2003-01-01

The potential of an Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer (ESI/IMS/CIT-MS) as an analytical instrument for analyzing material extracted from rock and soil samples as part of a suite of instruments on the proposed 2009 Mars Science Lander (MSL) will be demonstrated. This instrument will be able to identify volatile compounds as well as resident organic molecules on the parts-per-billion (ppb) level. Also, it will be able to obtain an inventory of chemical species on the surface of Mars which will result in a better understanding of ongoing surface chemistry. Finally, questions relevant to biological processes will be answered with the complete inventory of surface and near surface organic molecules that the ESI/IMS/CIT is capable of performing.

The Design and Implementation of a Relational to Network Query Translator for a Distributed Database Management System.

DTIC Science & Technology

1985-12-01

RELATIONAL TO NETWORK QUERY TRANSLATOR FOR A DISTRIBUTED DATABASE MANAGEMENT SYSTEM TH ESI S .L Kevin H. Mahoney -- Captain, USAF AFIT/GCS/ENG/85D-7...NETWORK QUERY TRANSLATOR FOR A DISTRIBUTED DATABASE MANAGEMENT SYSTEM - THESIS Presented to the Faculty of the School of Engineering of the Air Force...Institute of Technology Air University In Partial Fulfillment of the Requirements for the Degree of Master of Science in Computer Systems - Kevin H. Mahoney

Spirituality as a Scientific Construct: Testing Its Universality across Cultures and Languages

PubMed Central

MacDonald, Douglas A.; Friedman, Harris L.; Brewczynski, Jacek; Holland, Daniel; Salagame, Kiran Kumar K.; Mohan, K. Krishna; Gubrij, Zuzana Ondriasova; Cheong, Hye Wook

2015-01-01

Using data obtained from 4004 participants across eight countries (Canada, India, Japan, Korea, Poland, Slovakia, Uganda, and the U.S.), the factorial reliability, validity and structural/measurement invariance of a 30-item version of Expressions of Spirituality Inventory (ESI-R) was evaluated. The ESI-R measures a five factor model of spirituality developed through the conjoint factor analysis of several extant measures of spiritual constructs. Exploratory factor analyses of pooled data provided evidence that the five ESI-R factors are reliable. Confirmatory analyses comparing four and five factor models revealed that the five dimensional model demonstrates superior goodness-of-fit with all cultural samples and suggest that the ESI-R may be viewed as structurally invariant. Measurement invariance, however, was not supported as manifested in significant differences in item and dimension scores and in significantly poorer fit when factor loadings were constrained to equality across all samples. Exploratory analyses with a second adjective measure of spirituality using American, Indian, and Ugandan samples identified three replicable factors which correlated with ESI-R dimensions in a manner supportive of convergent validity. The paper concludes with a discussion of the meaning of the findings and directions needed for future research. PMID:25734921

Determination of Aspartame and Caffeine in Carbonated Beverages Utilizing Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Bergen, H. Robert, III; Benson, Linda M.; Naylor, Stephen

2000-10-01

Mass spectrometry has undergone considerable changes in the past decade. The advent of "soft ionization" techniques such as electrospray ionization (ESI) affords the direct analysis of very polar molecules without need for the complex inefficient derivatization procedures often required in GC-MS. These ionization techniques make possible the direct mass spectral analysis of polar nonvolatile molecules such as DNA and proteins, which previously were difficult or impossible to analyze by MS. Compounds that readily take on a charge (acids and bases) lend themselves to ESI-MS analysis, whereas compounds that do not readily accept a charge (e.g. sugars) are often not seen or are seen only as inefficient adducts (e.g., M+Na+). To gain exposure to this state-of-the-art analytical procedure, high school students utilize ESI-MS in an analysis of aspartame and caffeine. They dilute a beverage sample and inject the diluted sample into the ESI-MS. The lab is procedurally simple and the results clearly demonstrate the potential and limitations of ESI-coupled mass spectrometry. Depending upon the instructional goals, the outlined procedures can be used to quantify the content of caffeine and aspartame in beverages or to understand the capabilities of electrospray ionization.

Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry

USGS Publications Warehouse

Leenheer, J.A.; Rostad, C.E.; Gates, Paul M.; Furlong, E.T.; Ferrer, I.

2001-01-01

Molecular weight distributions of fulvic acid from the Suwannee River, Georgia, were investigated by electrospray ionization/quadrupole mass spectrometry (ESI/QMS), and fragmentation pathways of specific fulvic acid masses were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/MS). ESI/QMS studies of the free acid form of low molecular weight poly(carboxylic acid) standards in 75% methanol/25% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can be used for molecular weight determinations. However, experiments with poly(acrylic acid) mixtures and specific high molecular weight standards found multiply charged negative ions that gave a low bias to molecular mass distributions. The number of negative charges on a molecule is dependent on the distance between charges. ESI/MST/MS of model compounds found characteristic water loss from alcohol dehydration and anhydride formation, as well as CO2 loss from decarboxylation, and CO loss from ester structures. Application of these fragmentation pathways to specific masses of fulvic acid isolated and fragmented by ESI/MST/MS is indicative of specific structures that can serve as a basis for future structural confirmation after these hypothesized structures are synthesized.

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

PubMed

Santa, Tomofumi

2011-01-01

Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

The measurement of mangrove characteristics in southwest Florida using SPOT multispectral data

NASA Technical Reports Server (NTRS)

Jensen, John R.; Lin, Hongyue; Yang, Xinghe; Ramsey, Elijah, III; Davis, Bruce A.; Thoemke, Chris W.

1991-01-01

An intensive in situ sampling program near Marco Island, Florida during 19-23 October 1988 collected information on mangrove type, maximum canopy height, and percent canopy closure. These data were correlated with selected vegetation index information derived from analysis of SPOT multispectral (XS) data obtained on 21 October 1988. The Normalized Difference (ND) vegetation index information was the most highly correlated index with percent canopy closure (r = 0.91). Percent canopy closure information can be used as a surrogate for mangrove density which is of great value when predicting which parts of the mangrove ecosystem are at greatest risk after an oil spill occurs. Such information is very valuable when constructing oil spill Environmental Sensitivity Index (ESI) Maps for tropical regions of the world.

Quantitative LC-MS of polymers: determining accurate molecular weight distributions by combined size exclusion chromatography and electrospray mass spectrometry with maximum entropy data processing.

PubMed

Gruendling, Till; Guilhaus, Michael; Barner-Kowollik, Christopher

2008-09-15

We report on the successful application of size exclusion chromatography (SEC) combined with electrospray ionization mass spectrometry (ESI-MS) and refractive index (RI) detection for the determination of accurate molecular weight distributions of synthetic polymers, corrected for chromatographic band broadening. The presented method makes use of the ability of ESI-MS to accurately depict the peak profiles and retention volumes of individual oligomers eluting from the SEC column, whereas quantitative information on the absolute concentration of oligomers is obtained from the RI-detector only. A sophisticated computational algorithm based on the maximum entropy principle is used to process the data gained by both detectors, yielding an accurate molecular weight distribution, corrected for chromatographic band broadening. Poly(methyl methacrylate) standards with molecular weights up to 10 kDa serve as model compounds. Molecular weight distributions (MWDs) obtained by the maximum entropy procedure are compared to MWDs, which were calculated by a conventional calibration of the SEC-retention time axis with peak retention data obtained from the mass spectrometer. Comparison showed that for the employed chromatographic system, distributions below 7 kDa were only weakly influenced by chromatographic band broadening. However, the maximum entropy algorithm could successfully correct the MWD of a 10 kDa standard for band broadening effects. Molecular weight averages were between 5 and 14% lower than the manufacturer stated data obtained by classical means of calibration. The presented method demonstrates a consistent approach for analyzing data obtained by coupling mass spectrometric detectors and concentration sensitive detectors to polymer liquid chromatography.

Thermal QST Phenotypes Associated with Response to Lumbar Epidural Steroid Injections: A Pilot Study.

PubMed

Maher, Dermot P; Ding, Weihua; Singh, Sarabdeep; Opalacz, Arissa; Fishman, Claire; Houghton, Mary; Ahmed, Shihab; Chen, Lucy; Mao, Jianren; Zhang, Yi

2017-08-01

Response to lumbar epidural steroid injection in lumbar radicular pain varies. The purpose of this study is to characterize the changes in quantitative sensory testing (QST) phenotypes of subjects and compare the QST characteristics in patients who do respond to treatment of radicular pain with a lumbar epidural steroid injection (ESI). Prospective, observational pilot study. Outpatient pain center. Twenty subjects with a lower extremity (LE) radicular pain who were scheduled to have an ESI were recruited. At the visit prior to and four weeks following an ESI, subjects underwent QST measurements of both the affected LE and the contralateral unaffected UE. Following an ESI, nine subjects reported a greater than 30% reduction in radicular pain and 11 reported a less than 30% reduction in radicular pain. Subjects who had less than 30% pain reduction response (nonresponders) to an ESI had increased pre-injection warm sensation threshold (37.30 °C, SD = 2.51 vs 40.39, SD = 3.36, P = 0.03) and heat pain threshold (47.22 °C, SD = 1.38, vs 48.83 °C, SD = 2.10, P = 0.04). Further, the nonresponders also showed increased pre-injection warm sensation threshold as measured in the difference of warm sensation detection threshold difference in the affected limb and the unaffected arm (2.68 °C, SD = 2.92 vs 5.67 °C, SD = 3.22, P  = 0.045). Other QST parameters were not affected. The results show that the nonresponders to ESIs have increased detection threshold to heat pain and warm sensation, suggesting that a preexisting dysfunction in the C fibers in this group of subjects who can be detected by QST. Such altered QST characteristics may prognosticate the response to ESIs. © 2017 American Academy of Pain Medicine. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com

Metabolic profiling of Vitex agnus castus leaves, fruits and sprouts: analysis by LC/ESI/(QqQ)MS and (HR) LC/ESI/(Orbitrap)/MS n.

PubMed

Mari, Angela; Montoro, Paola; D'Urso, Gilda; Macchia, Mario; Pizza, Cosimo; Piacente, Sonia

2015-01-01

Food supplements based on Vitex agnus castus L. (Verbenaceae) fruits, also known as chasteberry, are routinely used by women against somatic and psychic premenstrual symptoms such as depression, sadness or irritability. With the aim of highlighting the differences in the chemical profiles of cultivated fruits and different parts of wild plants (fruits, leaves and sprouts) of V. agnus castus, a method concerning with the quali-quantitative study of the derived hydroalcoholic extracts was carried out by using high-performance liquid chromatography coupled to electrospray negative ionization Orbitrap multicollisional high resolution mass spectrometry (LC/ESI/(Orbitrap)MS(n)) and high-performance liquid chromatography coupled to electrospray negative ionization triple quadrupole tandem mass spectrometry (LC/ESI/(QqQ)MS) in multiple reaction monitoring (MRM) mode. Copyright © 2014 Elsevier B.V. All rights reserved.

Practical approaches to the ESI-MS analysis of catalytic reactions.

PubMed

Yunker, Lars P E; Stoddard, Rhonda L; McIndoe, J Scott

2014-01-01

Electrospray ionization mass spectrometry (ESI-MS) is a soft ionization technique commonly coupled with liquid or gas chromatography for the identification of compounds in a one-time view of a mixture (for example, the resulting mixture generated by a synthesis). Over the past decade, Scott McIndoe and his research group at the University of Victoria have developed various methodologies to enhance the ability of ESI-MS to continuously monitor catalytic reactions as they proceed. The power, sensitivity and large dynamic range of ESI-MS have allowed for the refinement of several homogenous catalytic mechanisms and could potentially be applied to a wide range of reactions (catalytic or otherwise) for the determination of their mechanistic pathways. In this special feature article, some of the key challenges encountered and the adaptations employed to counter them are briefly reviewed. Copyright © 2014 John Wiley & Sons, Ltd.

Interface contributions to peak broadening in CE-ESI-MS

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

Udseth, H.R.; Barinaga, C.J.; Smith, R.D.

1991-06-01

The applications of capillary electrophoresis (CE) are expanding, and a number of commercial CE instruments are now available. Combining CE with mass spectroscopy (MS), first done with an electrospray ionization (ESI) interface, yields additional advantages. Other interfaces have been proposed, but CE-ESI-MS offers better sensitivity, reduced background, applicability to higher molecular weight (MW) compounds and a better interface design. Our aim has been to exploit the advantages of automated CE coupled to MS for separation of biological materials. Details of our instrument design are provided. Samples used for these studies were a mixture of myoglobin proteins (MW {approximately}17 kilodaltons) andmore » a tryptic digest of tuna cytochrome c. The results show the ESI-MS interface does not broaden bands, and ion dissociation in the mass spectrometer permits the unambiguous identification of fragments in cases where mass alone is insufficient. 2 refs., 2 figs. (MHB)« less

MALDI versus ESI: The Impact of the Ion Source on Peptide Identification.

PubMed

Nadler, Wiebke Maria; Waidelich, Dietmar; Kerner, Alexander; Hanke, Sabrina; Berg, Regina; Trumpp, Andreas; Rösli, Christoph

2017-03-03

For mass spectrometry-based proteomic analyses, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) are the commonly used ionization techniques. To investigate the influence of the ion source on peptide detection in large-scale proteomics, an optimized GeLC/MS workflow was developed and applied either with ESI/MS or with MALDI/MS for the proteomic analysis of different human cell lines of pancreatic origin. Statistical analysis of the resulting data set with more than 72 000 peptides emphasized the complementary character of the two methods, as the percentage of peptides identified with both approaches was as low as 39%. Significant differences between the resulting peptide sets were observed with respect to amino acid composition, charge-related parameters, hydrophobicity, and modifications of the detected peptides and could be linked to factors governing the respective ion yields in ESI and MALDI.

Thiol–ene/oxidation tandem reaction under visible light photocatalysis: synthesis of alkyl sulfoxides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7cc05672a

PubMed Central

Guerrero-Corella, Andrea; María Martinez-Gualda, Ana; Ahmadi, Fereshteh; Ming, Enrique

2017-01-01

The photocatalyzed synthesis of sulfoxides from alkenes and thiols has been carried out using Eosin Y. This is a metal-free method which uses a low catalyst loading, atmospheric oxygen as the oxidant, and visible light conditions (green light). A mechanism has been proposed that is consistent with the experimental results. PMID:28890975

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

PubMed

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

2000-07-21

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

Do Superior or Inferior Interlaminar Approach or Bevel Orientation Predispose to Nonepidural Needle Penetration?

PubMed

Koontz, Nicholas A; Wiggins, Richard H; Stoddard, Gregory J; Shah, Lubdha M

2017-10-01

There is a paucity of evidence-based literature regarding the advantages and disadvantages of the interlaminar approach and needle bevel orientation for performing a lumbar interlaminar epidural steroid injection (ESI). The purpose of this study was to determine if superior versus inferior lamina approach, needle bevel tip orientation, or both may predispose to inadvertent nonepidural penetration during lumbar interlaminar ESI. A prospective study was performed of patients with low back pain with or without radicular pain or neurogenic claudication referred for lumbar interlaminar ESI. Two hundred eleven patients were randomized by interlaminar approach (superior vs inferior) and bevel tip orientation (cranial vs caudal). Lumbar interlaminar ESI was performed by six interventionalists of varying levels of experience using fluoroscopic guidance with curved tip epidural needles, using loss-of-resistance technique and confirmation with contrast opacification. Exact Poisson regression was used to model the study outcome. Two hundred twenty-one lumbar interlaminar ESIs were performed on 211 patients, randomized to a superior (n = 121) or inferior lamina approach (n = 100) and to a cranial (n = 103) or caudal (n = 118) orientation of the bevel tip. Epidural needle placement was confirmed in 96.4% (n = 213) of cases. Nonepidural needle placement was most commonly associated with superior lamina approach and caudal bevel tip orientation, which was marginally significant (adjusted risk ratio, 6.88; 95% CI, 0.93-∞; p = 0.059). Inadvertent nonepidural needle penetration during fluoroscopically guided lumbar interlaminar ESI appears to be affected by approach, with superior lamina approach and caudal bevel tip orientation being the least favorable technique.

ESI-MS measurements for the equilibrium constants of copper(II)-insulin complexes.

PubMed

Gülfen, Mustafa; Özdemir, Abdil; Lin, Jung-Lee; Chen, Chung-Hsuan

2018-06-01

Trace elements regulate many biological reactions in the body. Copper(II) is known as one of trace elements and capable of binding to proteins. Insulin is a blood glucose-lowering peptide hormone and it is secreted by the pancreatic β-cells. In this study, Cu(II)-insulin complexes were investigated by using ESI-MS method. Insulin molecule gives ESI-MS peaks at +4, +5, +6 and +7 charged states. Cu(II)-insulin complexes can be monitored and quantified on the ESI-MS spectra as the shifted peaks according to insulin peaks. The solutions of Cu(II)-insulin complexes at different pHs and mole ratios of Cu(II) ions to insulin molecule were measured on the ESI-MS. The highest complex formation ratio for Cu(II)-insulin were found at pH 7. The multiple bindings of Cu(II) ions to insulin molecule was observed. The formation equilibrium constants of Cu(II)-insulin complexes were calculated as Kf 1 : 3.34 × 10 4 , Kf 2 : 2.99 × 10 4 , Kf 3 : 7.00 × 10 3 and Kf 4 :2.86 × 10 3 . The specific binding property of Cu(II) ions was controlled by using different spray ion sources including electrospray and nano-electrospray. The binding property of Cu(II) also investigated by MS/MS fragmentation. It was concluded from the ESI-MS measurements that Cu(II) ion has a high affinity to insulin molecules to form stable complexes. Copyright © 2018 Elsevier B.V. All rights reserved.

Metabolic profile of naringenin in the stomach and colon using liquid chromatography/electrospray ionization linear ion trap quadrupole-Orbitrap-mass spectrometry (LC-ESI-LTQ-Orbitrap-MS) and LC-ESI-MS/MS.

PubMed

Orrego-Lagarón, Naiara; Vallverdú-Queralt, Anna; Martínez-Huélamo, Miriam; Lamuela-Raventos, Rosa M; Escribano-Ferrer, Elvira

2016-02-20

Several biological activities (antioxidant, anti-inflammatory, anticarcinogenic) are attributed to naringenin (NAR)-a predominant flavonoid of citrus fruit and tomato-despite its low bioavailability after ingestion. NAR undergoes extensive metabolism when crossing the gastrointestinal tract, resulting in enteric, hepatic and microbial metabolites, some of them with recognized beneficial effects on human health. This study sought to provide new insights into the metabolism of NAR in regions of the gastrointestinal tract where it has been less studied: the stomach and colon. With this purpose, liquid chromatography coupled with an electrospray ionization hybrid linear ion trap quadrupole Orbitrap mass spectrometry technique (LC-ESI-LTQ-Orbitrap-MS) was used for an accurate identification of NAR metabolites, and liquid chromatography/electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) on a triple quadrupole was used for their identification and quantification. The combination of both analytical techniques provided a broader metabolic profile of NAR. As far as we know, this is the first in-depth metabolic profiling study of NAR in the stomach of mice. Three of the metabolites determined using the LC-LTQ-Orbitrap could not be identified by LC-ESI-MS/MS in stomach perfusion samples: apigenin, 3-(4-hydroxyphenyl) propionic acid and phloroglucinol. The number of colonic metabolites determined using the LTQ-Orbitrap-MS was more than twice the number identified by LC-ESI-MS/MS. Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid Diagnosis of Bloodstream Infections with PCR Followed by Mass Spectrometry

PubMed Central

Jordana-Lluch, Elena; Carolan, Heather E.; Giménez, Montserrat; Sampath, Rangarajan; Ecker, David J.; Quesada, M. Dolores; Mòdol, Josep M.; Arméstar, Fernando; Blyn, Lawrence B.; Cummins, Lendell L.; Ausina, Vicente; Martró, Elisa

2013-01-01

Achieving a rapid microbiological diagnosis is crucial for decreasing morbidity and mortality of patients with a bloodstream infection, as it leads to the administration of an appropriate empiric antimicrobial therapy. Molecular methods may offer a rapid alternative to conventional microbiological diagnosis involving blood culture. In this study, the performance of a new technology that uses broad-spectrum PCR coupled with mass spectrometry (PCR/ESI-MS) was evaluated for the detection of microorganisms directly from whole blood. A total of 247 whole blood samples and paired blood cultures were prospectively obtained from 175 patients with a suspicion of sepsis. Both sample types were analyzed using the PCR/ESI-MS technology, and the results were compared with those obtained by conventional identification methods. The overall agreement between conventional methods and PCR/ESI-MS performed in blood culture aliquots was 94.2% with 96.8% sensitivity and 98.5% specificity for the molecular method. When comparing conventional methods with PCR/ESI-MS performed in whole blood specimens, the overall agreement was 77.1% with 50% sensitivity and 93.8% specificity for the molecular method. Interestingly, the PCR/ESI-MS technology led to the additional identification of 13 pathogens that were not found by conventional methods. Using the PCR/ESI-MS technology the microbiological diagnosis of bloodstream infections could be anticipated in about half of the patients in our setting, including a small but significant proportion of patients newly diagnosed. Thus, this promising technology could be very useful for the rapid diagnosis of sepsis in combination with traditional methods. PMID:23626775

Implications for Metabolite Quantification by Mass Spectrometry in the Absence of Authentic Standards.

PubMed

Hatsis, Panos; Waters, Nigel J; Argikar, Upendra A

2017-05-01

Quantification of metabolites by mass spectrometry in the absence of authentic reference standards or without a radiolabel is often called "semiquantitative," which acknowledges that mass spectrometric responses are not truly quantitative. For many researchers, it is tempting to pursue this practice of semiquantification in early drug discovery and even preclinical development, when radiolabeled absorption, distribution, metabolism, and excretion studies are being deferred to later stages of drug development. The caveats of quantifying metabolites based on parent drug response are explored in this investigation. A set of 71 clinically relevant drugs/metabolites encompassing common biotransformation pathways was subjected to flow injection analysis coupled with electrospray ionization (ESI) mass spectrometry. The results revealed a large variation in ESI response even for structurally similar parent drug/metabolite pairs. The ESI response of each metabolite was normalized to that of the parent drug to generate an ESI relative response factor. Overall, relative response factors ranged from 0.014 (>70-fold lower response than parent) to 8.6 (8.6-fold higher response than parent). Various two-dimensional molecular descriptors were calculated that describe physicochemical, topological, and structural properties for each drug/metabolite. The molecular descriptors, along with the ESI response factors, were used in univariate analyses as well as a principal components analysis to ascertain which molecular descriptors best account for the observed discrepancies in drug/metabolite ESI response. This investigation has shown that the practice of using parent drug response to quantify metabolites should be used with caution. Copyright © 2017 by The American Society for Pharmacology and Experimental Therapeutics.

Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI-MSMS and ESI-nozzle-skimmer-MSMS.

PubMed

Siegel, Marshall M; Kong, Fangming; Feng, Xidong; Carter, Guy T

2009-12-01

Three lipocyclopeptide antibiotics, aspartocins A (1), B (2), and C (3), were obtained from the aspartocin complex by HPLC separation methodology. Their structures were elucidated using previously published chemical degradation results coupled with spectroscopic studies including ESI-MS, ESI-Nozzle Skimmer-MSMS and NMR. All three aspartocin compounds share the same cyclic decapeptide core of cyclo [Dab2 (Asp1-FA)-Pip3-MeAsp4-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11]. They differ only in the fatty acid side chain moiety (FA) corresponding to (Z)-13-methyltetradec-3-ene-carbonyl, (+,Z)-12-methyltetradec-3-ene-carbonyl and (Z)-12-methyltridec-3-ene-carbonyl for aspartocins A (1), B (2), and C (3), respectively. All of the sequence ions were observed by ESI-MSMS of the doubly charged parent ions. However, a number of the sequence ions observed were of low abundance. To fully sequence the lipocyclopeptide antibiotic structures, these low abundance sequence ions together with complementary sequence ions were confirmed by ESI-Nozzle-Skimmer-MSMS of the singly charged linear peptide parent fragment ions H-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11-Dab2(1+)-Asp1-FA. Cyclization of the aspartocins was demonstrated to occur via the beta-amino group of Dab2 from ions of moderate intensity in the ESI-MSMS spectra. As the fatty acid moieties do not undergo internal fragmentations under the experimental ESI mass spectral conditions used, the 14 Da mass difference between the fatty acid moieties of aspartocins A (1) and B (2) versus aspartocin C (3) was used as an internal mass tag to differentiate fragment ions containing fatty acid moieties and those not containing the fatty acid moieties. The most numerous and abundant fragment ions observed in the tandem mass spectra are due to the cleavage of the tertiary nitrogen amide of the pipecolic acid residue-3 (16 fragment ions) and the proline residue-11 (7 fragment ions). In addition, the neutral loss of ethanimine from alpha,beta-diaminobutyric acid residue 9 was observed for the parent molecular ion and for 7 fragment ions. Copyright 2009 John Wiley & Sons, Ltd.

Biosynthesis of staphylococcal enterotoxin A by genetic engineering technology and determination of staphylococcal enterotoxin A in water by HPLC-ESI-TOF.

PubMed

Li, Hong-Na; Yuan, Fei; Luo, Yun-Jing; Wang, Jian-Feng; Zhang, Chuan-Bin; Zhou, Wei-E; Ren, Zhi-Qin; Wu, Wen-Jie; Zhang, Feng

2017-08-01

Staphylococcal enterotoxin A (SEA) was the major virulence factor of Staphylococcus aureus and a biomarker of S. aureus. To establish a fast, low cost, high accuracy, reliable, and simple method for detecting S. aureus, SEA was analyzed by HPLC-ESI-TOF. SEA was not yet commercially available in universal, so SEA was prepared before it was analyzed by HPLC-ESI-TOF. The result showed that high purified SEA was successfully prepared and SEA has normal distribution in mass spectra. A large amount of recombinant SEA (rSEA) was obtained by engineering technology and was purified by Ni affinity chromatography column, and the expression and purity of rSEA and SEA were analyzed by SDS-PAGE. The factors effected on ionization of SEA were studied, and the qualitative analysis of SEA by HPLC-ESI-TOF. The result showed that large amount of SEs expressed within a short time at 28 °C or thereabouts, and there was no impurity bands in electrophorogram after rSEA was purified by Ni affinity chromatography column. In addition, the SEA which had homologous AA sequence with wild SEA was made by rSEA. The retention of SEA in column and ionization of SEA in ESI-TOF were studied for qualitative analysis of S. aureus. The result showed that the content of formic acid in mobile phase was an important factor for ionization of SEs in ESI-TOF. And the result provided theoretical foundation for qualitative detection of S. aureus. [SEs + nH + + mNH 4 + ] n+m+ was shown on ESI-TOF spectra when SEA was detected by ESI-TOF in positive ion mode, and the numerical value of n+m was less than or equal to the number of basic amino acids in SEs. This method was applied to determine SEA in water samples preliminarily, and the detection limit of SEA in spiked water sample was 3 mg/kg. The limit of detection of 3 mg/kg was low sensitivity for low molecular weight matters, but it was high sensitivity for SEA which had a high molecular weight of 27 kDa. Of SEA, 3 mg/kg was equivalent to 10 -4  mmol/kg of SEA. This study can provide evidence for establishing method to determine SEA in real samples.

Analysis of Arsenicals and Their Sulfur Analogs in Biological Samples Using HPLC with Collision Cell ICP-MS and ESI-MS/MS

EPA Science Inventory

Recent arsenic speciation studies have indicated that the sulfur analogs of the more common arsenic oxides are present in environmental and biological systems. This discovery was previously impeded due to the strong affinity of these arsenic-sulfides for the stationary phases typ...

Dissociation Behavior of a TEMPO-Active Ester Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS) in Negative ESI-MS.

PubMed

Hage, Christoph; Ihling, Christian H; Götze, Michael; Schäfer, Mathias; Sinz, Andrea

2017-01-01

We have synthesized a homobifunctional amine-reactive cross-linking reagent, containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy) and a benzyl group (Bz), termed TEMPO-Bz-linker, to derive three-dimensional structural information of proteins. The aim for designing this novel cross-linker was to facilitate the mass spectrometric analysis of cross-linked products by free radical initiated peptide sequencing (FRIPS). In an initial study, we had investigated the fragmentation behavior of TEMPO-Bz-derivatized peptides upon collision activation in (+)-electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) experiments. In addition to the homolytic NO-C bond cleavage FRIPS pathway delivering the desired odd-electron product ions, an alternative heterolytic NO-C bond cleavage, resulting in even-electron product ions mechanism was found to be relevant. The latter fragmentation route clearly depends on the protonation of the TEMPO-Bz-moiety itself, which motivated us to conduct (-)-ESI-MS, CID-MS/MS, and MS 3 experiments of TEMPO-Bz-cross-linked peptides to further clarify the fragmentation behavior of TEMPO-Bz-peptide molecular ions. We show that the TEMPO-Bz-linker is highly beneficial for conducting FRIPS in negative ionization mode as the desired homolytic cleavage of the NO-C bond is the major fragmentation pathway. Based on characteristic fragments, the isomeric amino acids leucine and isoleucine could be discriminated. Interestingly, we observed pronounced amino acid side chain losses in cross-linked peptides if the cross-linked peptides contain a high number of acidic amino acids. Graphical Abstract ᅟ.

Integrative metabolomics for characterizing unknown low-abundance metabolites by capillary electrophoresis-mass spectrometry with computer simulations.

PubMed

Lee, Richard; Ptolemy, Adam S; Niewczas, Liliana; Britz-McKibbin, Philip

2007-01-15

Characterization of unknown low-abundance metabolites in biological samples is one the most significant challenges in metabolomic research. In this report, an integrative strategy based on capillary electrophoresis-electrospray ionization-ion trap mass spectrometry (CE-ESI-ITMS) with computer simulations is examined as a multiplexed approach for studying the selective nutrient uptake behavior of E. coli within a complex broth medium. On-line sample preconcentration with desalting by CE-ESI-ITMS was performed directly without off-line sample pretreatment in order to improve detector sensitivity over 50-fold for cationic metabolites with nanomolar detection limits. The migration behavior of charged metabolites were also modeled in CE as a qualitative tool to support MS characterization based on two fundamental analyte physicochemical properties, namely, absolute mobility (muo) and acid dissociation constant (pKa). Computer simulations using Simul 5.0 were used to better understand the dynamics of analyte electromigration, as well as aiding de novo identification of unknown nutrients. There was excellent agreement between computer-simulated and experimental electropherograms for several classes of cationic metabolites as reflected by their relative migration times with an average error of <2.0%. Our studies revealed differential uptake of specific amino acids and nucleoside nutrients associated with distinct stages of bacterial growth. Herein, we demonstrate that CE can serve as an effective preconcentrator, desalter, and separator prior to ESI-MS, while providing additional qualitative information for unambiguous identification among isobaric and isomeric metabolites. The proposed strategy is particularly relevant for characterizing unknown yet biologically relevant metabolites that are not readily synthesized or commercially available.

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

PubMed

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Identification and formation mechanism of individual degradation products in lithium-ion batteries studied by liquid chromatography/electrospray ionization mass spectrometry and atmospheric solid analysis probe mass spectrometry.

PubMed

Takeda, Sahori; Morimura, Wataru; Liu, Yi-Hung; Sakai, Tetsuo; Saito, Yuria

2016-08-15

Improvement of lithium ion batteries (LIBs) in terms of performance and robustness requires good understanding of the reaction processes. The analysis of the individual degradation products in LIB electrolytes and on the surface of the electrodes provides vital information in this regard. In this study, mass spectrometric analytical methods were utilized for the identification of the individual degradation products. The degradation products in the electrolytes recovered from cycle-tested cells were separated by liquid chromatography (LC) and their mass spectrometric analysis was conducted by electrospray ionization mass spectrometry (ESI-MS). For identification of degradation products on the surface of electrodes, atmospheric solid analysis probe (ASAP)-MS analysis was conducted by time-of-flight mass spectrometry with an ASAP probe and an atmospheric pressure chemical ionization source. The degradation products in the electrolytes, namely carbonate oligomers and organophosphates, were identified simultaneously by LC/ESI-MS. Their formation mechanisms were estimated, which explain their different compositions at different temperatures. One degradation product was found on the anode surface by ASAP-MS, and its formation mechanism was explained similarly to those in the electrolyte. The results suggest that the electrolyte degradation is correlated with the formation of a solid electrolyte interphase, which is an important factor in the performance of LIBs. We expect that further investigation of the degradation products by LC/ESI-MS and ASAP-MS will be helpful for studying their degradation processes in LIBs. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Profiling of adrenocorticotropic hormone and arginine vasopressin in human pituitary gland and tumor thin tissue sections using droplet-based liquid-microjunction surface-sampling-HPLC-ESI-MS-MS.

PubMed

Kertesz, Vilmos; Calligaris, David; Feldman, Daniel R; Changelian, Armen; Laws, Edward R; Santagata, Sandro; Agar, Nathalie Y R; Van Berkel, Gary J

2015-08-01

Described here are the results from the profiling of the proteins arginine vasopressin (AVP) and adrenocorticotropic hormone (ACTH) from normal human pituitary gland and pituitary adenoma tissue sections, using a fully automated droplet-based liquid-microjunction surface-sampling-HPLC-ESI-MS-MS system for spatially resolved sampling, HPLC separation, and mass spectrometric detection. Excellent correlation was found between the protein distribution data obtained with this method and data obtained with matrix-assisted laser desorption/ionization (MALDI) chemical imaging analyses of serial sections of the same tissue. The protein distributions correlated with the visible anatomic pattern of the pituitary gland. AVP was most abundant in the posterior pituitary gland region (neurohypophysis), and ATCH was dominant in the anterior pituitary gland region (adenohypophysis). The relative amounts of AVP and ACTH sampled from a series of ACTH-secreting and non-secreting pituitary adenomas correlated with histopathological evaluation. ACTH was readily detected at significantly higher levels in regions of ACTH-secreting adenomas and in normal anterior adenohypophysis compared with non-secreting adenoma and neurohypophysis. AVP was mostly detected in normal neurohypophysis, as expected. This work reveals that a fully automated droplet-based liquid-microjunction surface-sampling system coupled to HPLC-ESI-MS-MS can be readily used for spatially resolved sampling, separation, detection, and semi-quantitation of physiologically-relevant peptide and protein hormones, including AVP and ACTH, directly from human tissue. In addition, the relative simplicity, rapidity, and specificity of this method support the potential of this basic technology, with further advancement, for assisting surgical decision-making. Graphical Abstract Mass spectrometry based profiling of hormones in human pituitary gland and tumor thin tissue sections.

[Emergy analysis on different planting patterns of typical watersheds in Loess Plateau.

PubMed

Deng, Jian; Zhao, Fa Zhu; Han, Xin Hui; Feng, Yong Zhong; Yang, Gai He

2016-05-01

To objectively evaluate and compare the stability and sustainability of different planting patterns of typical watersheds in Loess Plateau of China after the Grain for Green Project, this paper used the emergy analysis method to quantify the emergy inputs and outputs of three watersheds with different planting patterns, i.e., both grains and fruit trees (Gaoxigou watershed), mainly grains (Wuliwan watershed) and mainly fruit trees (Miaozuigou watershed). In addition, an emergy analysis system was established to evaluate the suitability of the three patterns from the perspectives of natural resources pressure as well as social and economic development levels. More than 75% of the total emergy inputs of all the three watersheds were purchased, and nonrenewable emergy inputs had a much larger contribution than renewable emergy inputs, indicating the characteristic of low emergy self-sufficient ratio and considerable high environmental loading ratio. The pattern of planting grains had high emergy inputs but low emergy outputs, while the patterns of planting fruit trees and planting both had high emergy inputs and outputs. The energy densities of all three patterns reached two times of the average of agricultural systems in China. Especially, the net emergy of planting grains pattern was the lowest while that of planting both grains and fruit trees was the highest. The environmental sustainability index (ESI) of planting grains pattern was less than 1 and both emergy and ESI were much lower than national averages. The ESI of planting both grains and fruit trees pattern was the highest. In summary, comparison of the three patterns showed that planting both grains and fruit trees had better sustainability and high stability and the emergy production efficiency was high. Thus, it was suggested to change the agricultural development from watershed based units to multi-industry integrated mode.

48 CFR 208.7402 - General.

Code of Federal Regulations, 2010 CFR

2010-10-01

... DEFENSE ACQUISITION PLANNING REQUIRED SOURCES OF SUPPLIES AND SERVICES Enterprise Software Agreements 208... services, such as software maintenance, in accordance with the DoD Enterprise Software Initiative (ESI... software and related services. ESI does not dictate the products or services to be acquired. ...

Detection, characterization and identification of crucifer phytoalexins using high-performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry.

PubMed

Pedras, M Soledade C; Adio, Adewale M; Suchy, Mojmir; Okinyo, Denis P O; Zheng, Qing-An; Jha, Mukund; Sarwar, Mohammed G

2006-11-10

We have analyzed 23 crucifer phytoalexins (e.g. brassinin, dioxibrassinin, cyclobrassinin, brassicanals A and C) by HPLC with diode array detection and electrospray ionization mass spectrometry (HPLC-DAD-ESI-MS) using both negative and positive ion modes. Positive ion mode ESI-MS appeared more sensitive than negative ion mode ESI-MS in detecting this group of compounds. A new HPLC separation method, new LC-MS and LC-MS(2) data and proposed fragmentation pathways, LC retention times, and UV spectra for selected compounds are reported.

Employer-sponsored health insurance coverage continues to decline in a new decade.

PubMed

Gould, Elise

2013-01-01

Most Americans, particularly those under age 65, rely on health insurance offered through the workplace. Given continuing high unemployment, it comes as no surprise that the share of Americans under age 65 covered by employer-sponsored health insurance (ESI) eroded for the 11th year in a row in 2011, falling from 58.6 percent in 2010 to 58.3 percent. The situation started deteriorating long before the Great Recession: the share of Americans under age 65 covered by ESI eroded every year from 2000 to 2011, decreasing by a total of 10.9 percentage points. As many as 29 million more people under age 65 would have had ESI in 2011 if the coverage rate had remained at the 2000 level. The decline in ESI coverage has been accompanied by an overall decline in health insurance coverage. The number of uninsured non-elderly Americans was 47.9 million in 2011--11.7 million higher than in 2000. Increasing public insurance coverage, particularly among children, is the only reason the uninsured rate did not rise one-for-one with losses in ESI. In addition, key components in the Patient Protection and Affordable Care Act took effect in 2010, shielding young adults from further coverage losses.

Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

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

Bateman, Adam P.; Laskin, Julia; Laskin, Alexander

2012-07-02

The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found betweenmore » the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.« less

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents

NASA Astrophysics Data System (ADS)

Susa, Anna C.; Lippens, Jennifer L.; Xia, Zijie; Loo, Joseph A.; Campuzano, Iain D. G.; Williams, Evan R.

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m / z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. [Figure not available: see fulltext.

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents.

PubMed

Susa, Anna C; Lippens, Jennifer L; Xia, Zijie; Loo, Joseph A; Campuzano, Iain D G; Williams, Evan R

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m /z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. Graphical Abstract.

The Tax Exclusion for Employer-Sponsored Insurance Is Not Regressive-But What Is It?

PubMed

White, Joseph

2017-08-01

Conventional wisdom says that the tax exclusion for employer-sponsored health insurance (ESI) is "regressive and therefore unfair." Yet, by the standard definition of regressive tax policy, the conventional view is almost certainly false. It confuses the absolute size of the tax exclusion with its proportional effect on income. The error results from paying attention only to the marginal tax rate applied to ESI benefits as a portion of income and ignoring the fact that benefits are normally a much larger share of income for people with lower wages. This article explains the difference and then considers other distributional effects of ESI. It suggests that ESI-for those who receive it-further redistributes toward those with lesser means or greater need. The most evident effect is by need, favoring employees with families over those without. Yet there is good reason to believe there is also a redistribution by income, with the package of wages plus benefits being less unequal than wages alone would be. Therefore reformers should be much more careful before criticizing either ESI or its subsidy through the tax code as "unfair," especially as the likelihood of enacting something better in the United States seems quite low. Copyright © 2017 by Duke University Press.

A novel molecular microbiologic technique for the rapid diagnosis of microbial invasion of the amniotic cavity and intra-amniotic infection in preterm labor with intact membranes.

PubMed

Romero, Roberto; Miranda, Jezid; Chaiworapongsa, Tinnakorn; Chaemsaithong, Piya; Gotsch, Francesca; Dong, Zhong; Ahmed, Ahmed I; Yoon, Bo Hyun; Hassan, Sonia S; Kim, Chong Jai; Korzeniewski, Steven J; Yeo, Lami

2014-04-01

The diagnosis of microbial invasion of the amniotic cavity (MIAC) has been traditionally performed using traditional cultivation techniques, which require growth of microorganisms in the laboratory. Shortcomings of culture methods include the time required (days) for identification of microorganisms, and that many microbes involved in the genesis of human diseases are difficult to culture. A novel technique combines broad-range real-time polymerase chain reaction with electrospray ionization time-of-flight mass spectrometry (PCR/ESI-MS) to identify and quantify genomic material from bacteria and viruses. AF samples obtained by transabdominal amniocentesis from 142 women with preterm labor and intact membranes (PTL) were analyzed using cultivation techniques (aerobic, anaerobic, and genital mycoplasmas) as well as PCR/ESI-MS. The prevalence and relative magnitude of intra-amniotic inflammation [AF interleukin 6 (IL-6) concentration ≥ 2.6 ng/mL], acute histologic chorioamnionitis, spontaneous preterm delivery, and perinatal mortality were examined. (i) The prevalence of MIAC in patients with PTL was 7% using standard cultivation techniques and 12% using PCR/ESI-MS; (ii) seven of ten patients with positive AF culture also had positive PCR/ESI-MS [≥17 genome equivalents per PCR reaction well (GE/well)]; (iii) patients with positive PCR/ESI-MS (≥17 GE/well) and negative AF cultures had significantly higher rates of intra-amniotic inflammation and acute histologic chorioamnionitis, a shorter interval to delivery [median (interquartile range-IQR)], and offspring at higher risk of perinatal mortality, than women with both tests negative [90% (9/10) versus 32% (39/122) OR: 5.6; 95% CI: 1.4-22; (P < 0.001); 70% (7/10) versus 35% (39/112); (P = 0.04); 1 (IQR: <1-2) days versus 25 (IQR: 5-51) days; (P = 0.002), respectively]; (iv) there were no significant differences in these outcomes between patients with positive PCR/ESI-MS (≥17 GE/well) who had negative AF cultures and those with positive AF cultures; and (v) PCR/ESI-MS detected genomic material from viruses in two patients (1.4%). (i) Rapid diagnosis of intra-amniotic infection is possible using PCR/ESI-MS; (ii) the combined use of biomarkers of inflammation and PCR/ESI-MS allows for the identification of specific bacteria and viruses in women with preterm labor and intra-amniotic infection; and (iii) this approach may allow for administration of timely and specific interventions to reduce morbidity attributed to infection-induced preterm birth. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

A Novel Molecular Microbiologic Technique for the Rapid Diagnosis of Microbial Invasion of the Amniotic Cavity and Intra-Amniotic Infection in Preterm Labor with Intact Membranes

PubMed Central

Romero, Roberto; Miranda, Jezid; Chaiworapongsa, Tinnakorn; Chaemsaithong, Piya; Gotsch, Francesca; Dong, Zhong; Ahmed, Ahmed I.; Yoon, Bo Hyun; Hassan, Sonia; Kim, Chong J.; Korzeniewski, Steven J.; Yeo, Lami

2014-01-01

Objective The major challenges in using amniotic fluid (AF) cultivation techniques to diagnose microbial invasion of the amniotic cavity (MIAC) are: 1) several days are typically required to obtain results, and 2) many organisms implicated in the pathogenesis of human disease are difficult to culture. Here, we compare the performance of AF culture with a novel technique for the diagnosis of MIAC that can provide results within eight hours by combining broad-range real-time polymerase chain reaction with electrospray ionization mass spectrometry (PCR/ESI-MS) to identify and quantify genomic material from bacteria and viruses in AF. Methods AF samples obtained by transabdominal amniocentesis from 142 women with preterm labor (PTL) and intact membranes were analyzed using cultivation techniques (aerobic, anaerobic and genital mycoplasmas) as well as PCR/ESI-MS. The prevalence and relative magnitude of intra-amniotic inflammation [AF Interleukin 6 (IL-6) concentration ≥ 2.6 ng/mL], acute histologic chorioamnionitis, spontaneous preterm delivery, and perinatal mortality were examined according to the results of these two tests. Results 1) The prevalence of MIAC in patients with preterm labor and intact membranes was 7% using standard cultivation techniques and 12% using PCR/ESI-MS; 2) seven of ten patients with positive AF culture also had positive PCR/ESI-MS [≥17 genome equivalents per PCR reaction well (GE/well)] 3) patients with positive PCR/ESI-MS (≥17 GE/well) and negative AF cultures had significantly higher rates of intra-amniotic inflammation and histologic acute chorioamnionitis, shorter intervals to delivery [median (interquartile range-IQR)], and offspring at higher risk of perinatal mortality, than women with both tests negative [90% (9/10) vs. 32% (39/122); (p<0.001); 70% (7/10) vs. 35% (39/112); (p=0.04); 1 (IQR: <1 – 2) days vs. 25 (IQR: 5 – 51) days; (p=0.002); OR: 5.6; 95% CI: 1.4 – 22, respectively]; 5) there were no significant differences in these factors between patients with positive PCR/ESI-MS (≥17 GE/well) who had negative AF cultures compared to those with positive AF cultures; and 6) PCR/ESI-MS detected genomic material from viruses in two patients (1.4%). Conclusion 1) Rapid diagnosis of intra-amniotic infection is possible using PCR/ESI-MS, which can provide results within 8 hours; 2) the combined use of biomarkers of inflammation and PCR/ESI-MS allows for the rapid identification of specific bacteria and viruses in women with preterm labor and intra-amniotic infection; and 3) this approach may allow for administration of timely and specific interventions to reduce morbidity attributed to infection-induced preterm birth. PMID:24417618

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

Liu, Ying

My graduate research has focused on separation science and bioanalytical analysis, which emphasized in method development. It includes three major areas: enantiomeric separations using high performance liquid chromatography (HPLC), Super/subcritical fluid chromatography (SFC), and capillary electrophoresis (CE); drug-protein binding behavior studies using CE; and carbohydrate analysis using liquid chromatograph-electrospray ionization mass spectrometry (LC-ESI-MS). Enantiomeric separations continue to be extremely important in the pharmaceutical industry. An in-depth evaluation of the enantiomeric separation capabilities of macrocyclic glycopeptides CSPs with SFC mobile phases was investigated using a set of over 100 chiral compounds. It was found that the macrocyclic based CSPs were ablemore » to separate enantiomers of various compounds with different polarities and functionalities. Seventy percent of all separations were achieved in less than 4 min due to the high flow rate (4.0 ml/min) that can be used in SFC. Drug-protein binding is an important process in determining the activity and fate of a drug once it enters the body. Two drug/protein systems have been studied using frontal analysis CE method. More sensitive fluorescence detection was introduced in this assay, which overcame the problem of low sensitivity that is common when using UV detection for drug-protein studies. In addition, the first usage of an argon ion laser with 257 nm beam coupled with CCD camera as a frontal analysis detection method enabled the simultaneous observation of drug fluorescence as well as the protein fluorescence. LC-ESI-MS was used for the separation and characterization of underivatized oligosaccharide mixtures. With the limits of detection as low as 50 picograms, all individual components of oligosaccharide mixtures (up to 11 glucose-units long) were baseline resolved on a Cyclobond I 2000 column and detected using ESI-MS. This system is characterized by high chromatographic resolution, high column stability, and high sensitivity. In addition, this method showed potential usefulness for the sensitive and quick analysis of hydrolysis products of polysaccharides, and for trace level analysis of individual oligosaccharides or oligosaccharide isomers from biological systems.« less

Palladium(ii)-catalyzed synthesis of dibenzothiophene derivatives via the cleavage of carbon–sulfur and carbon–hydrogen bonds† †Electronic supplementary information (ESI) available: Experimental procedures and characterization data for all new compounds. See DOI: 10.1039/c5sc04890g Click here for additional data file.

PubMed Central

Masuya, Yoshihiro; Baba, Katsuaki

2016-01-01

A new process has been developed for the palladium(ii)-catalyzed synthesis of dibenzothiophene derivatives via the cleavage of C–H and C–S bonds. In contrast to the existing methods for the synthesis of this scaffold by C–H functionalization, this new catalytic C–H/C–S coupling method does not require the presence of an external stoichiometric oxidant or reactive functionalities such as C–X or S–H, allowing its application to the synthesis of elaborate π-systems. Notably, the product-forming step of this reaction lies in an oxidative addition step rather than a reductive elimination step, making this reaction mechanistically uncommon. PMID:28660030

Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns containing a nanowire-like core† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc00449g Click here for additional data file.

PubMed Central

Guerra, Sebastiano; Iehl, Julien; Holler, Michel; Peterca, Mihai; Wilson, Daniela A.; Partridge, Benjamin E.; Zhang, Shaodong

2015-01-01

Twelve chiral and achiral self-assembling dendrons have been grafted onto a [60]fullerene hexa-adduct core by copper-catalyzed alkyne azide “click” cycloaddition. The structure adopted by these compounds was determined by the self-assembling peripheral dendrons. These twelve dendrons mediate the self-organisation of the dendronized [60]fullerene into a disc-shaped structure containing the [60]fullerene in the centre. The fullerene-containing discs self-organise into helical supramolecular columns with a fullerene nanowire-like core, forming a 2D columnar hexagonal periodic array. These unprecedented supramolecular structures and their assemblies are expected to provide new developments in chiral complex molecular systems and their application to organic electronics and solar cells. PMID:29142695

Protein modification via alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst† †Dedicated to Professor Stuart L. Schreiber on the occasion of his 60th birthday. ‡ ‡Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05313k Click here for additional data file.

PubMed Central

Kwan, Terence T.-L.; Boutureira, Omar; Frye, Elizabeth C.; Walsh, Stephen J.; Gupta, Moni K.; Wallace, Stephen; Wu, Yuteng; Zhang, Fengzhi; Sore, Hannah F.; Galloway, Warren R. J. D.; Chin, Jason W.; Welch, Martin; Bernardes, Gonçalo J. L.

2017-01-01

Transition metal catalysis has emerged as a powerful strategy to expand synthetic flexibility of protein modification. Herein, we report a cationic Ru(ii) system that enables the first example of alkyne hydrosilylation between dimethylarylsilanes and O-propargyl-functionalized proteins using a substoichiometric amount or low-loading of Ru(ii) catalyst to achieve the first C–Si bond formation on full-length substrates. The reaction proceeds under physiological conditions at a rate comparable to other widely used bioorthogonal reactions. Moreover, the resultant gem-disubstituted vinylsilane linkage can be further elaborated through thiol–ene coupling or fluoride-induced protodesilylation, demonstrating its utility in further rounds of targeted modifications. PMID:28966779

Direct characterization of aqueous extract of Hibiscus sabdariffa using HPLC with diode array detection coupled to ESI and ion trap MS.

PubMed

Rodríguez-Medina, Inmaculada C; Beltrán-Debón, Raúl; Molina, Vicente Micol; Alonso-Villaverde, Carlos; Joven, Jorge; Menéndez, Javier A; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

2009-10-01

The phenolic fraction and other polar compounds of the Hibiscus sabdariffa were separated and identified by HPLC with diode array detection coupled to electrospray TOF and IT tandem MS (DAD-HPLC-ESI-TOF-MS and IT-MS). The H. sabdariffa aqueous extract was filtered and directly injected into the LC system. The analysis of the compounds was carried out by RP HPLC coupled to DAD and TOF-MS in order to obtain molecular formula and exact mass. Posterior analyses with IT-MS were performed and the fragmentation pattern and confirmation of the structures were achieved. The H. sabdariffa samples were successfully analyzed in positive and negative ionization modes with two optimized linear gradients. In positive mode, the two most representative anthocyanins and other compounds were identified whereas the phenolic fraction, hydroxycitric acid and its lactone were identified using the negative ionization mode.

Flow Injection Mass Spectral Fingerprints Demonstrate Chemical Differences in Rio Red Grapefruit with Respect to Year, Harvest Time, and Conventional versus Organic Farming

PubMed Central

Chen, Pei; Harnly, James M.; Lester, Gene E.

2013-01-01

Spectral fingerprints were acquired for Rio Red grapefruit using flow injection electrospray ionization with ion trap and time-of-flight mass spectrometry (FI-ESI-IT-MS and FI-ESI-TOF-MS). Rio Red grapefruits were harvested 3 times a year (early, mid, and late harvests) in 2005 and 2006 from conventionally and organically grown trees. Data analysis using analysis of variance principal component analysis (ANOVA-PCA) demonstrated that, for both MS systems, the chemical patterns were different as a function of farming mode (conventional vs organic), as well as growing year and time of harvest. This was visually obvious with PCA and was shown to be statistically significant using ANOVA. The spectral fingerprints provided a more inclusive view of the chemical composition of the grapefruit and extended previous conclusions regarding the chemical differences between conventionally and organically grown Rio Red grapefruit. PMID:20337420

Screening and identification of radical scavengers from Neo-Taraxacum siphonanthum by online rapid screening method and nuclear magnetic resonance experiments.

PubMed

Shi, Shu Yun; Zhang, Yu Ping; Zhou, Hong Hao; Huang, Ke Long; Jiang, Xin Yu

2010-01-01

An online rapid screening method, the high-performance liquid chromatography (HPLC)-diode array detector (DAD)-radical scavenging detection (RSD)-electrospray ionization (ESI)-mass spectroscopy (MS)/MS system, was developed for the screening and identification of radical scavengers from Neo-Taraxacum siphonanthum, a new species found in China in 1989. For further characterization, the target compounds were isolated by silica column chromatography, preparative high-performance liquid chromatography (HPLC), HSCCC, and Sephadex LH-20 column chromatography and elucidated on the basis of ultraviolet (UV), ESI-MS/MS, and nuclear magnetic resonance (NMR) spectroscopy, as well as the chemical analysis. Eighteen antioxidative polyphenols (5 caffeic acid derivatives and 13 flavonoid derivatives) were characterized from Neo-T. siphonanthum. The distribution of all compounds was discussed in a chemosystematic context, which suggested that the genera Neo-Taraxacum and Taraxacum might relate chemosystematically.

Characterization of antioxidant phenolics in Syringa vulgaris L. flowers and fruits by HPLC-DAD-ESI-MS.

PubMed

Tóth, Gergő; Barabás, Csenge; Tóth, Anita; Kéry, Ágnes; Béni, Szabolcs; Boldizsár, Imre; Varga, Erzsébet; Noszál, Béla

2016-06-01

In this study the polyphenolic composition of lilac flowers and fruits was determined for the first time. For the identification of compounds, accurate molecular masses and formulas, acquired by LC and ESI-TOF-MS and fragmentation pattern given by LC-ESI/MS/MS analyses, were used. Our chromatographic system in conjunction with tandem MS was found to be valuable in the rapid separation and determination of the multiple constituents in methanolic extracts of lilac flowers and fruits. Altogether 34 phenolics, comprising 18 secoiridoids, seven phenylpropanoids, four flavonoids and five low-molecular-weight phenols, were identified. As marker compounds two secoiridoids (oleuropein and nuzhenide), two phenylpropanoids (acteoside and echinacoside) and rutin were quantified by validated methods. As a result of quantitative analysis, it was confirmed that flowers contain significant amounts of phenylpropanoids (acteoside, 2.48%; echinacoside, 0.75%) and oleuropein (0.95%), while in fruits secoiridoid oleuropein (1.09%) and nuzhenide (0.42%) are the major secondary metabolites. The radical scavenging activities of the extracts and the constituents were investigated by DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS [2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)] assays. Both extracts show remarkable antioxidant activities. Our results clearly show that lilac flowers and fruits are inexpensive, readily available natural sources of phenolic compounds with pharmacological and cosmetic applications. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Novel methodology for the extraction and identification of natural dyestuffs in historical textiles by HPLC-UV-Vis-ESI MS. Case study: chasubles from the Wawel Cathedral collection.

PubMed

Lech, Katarzyna; Jarosz, Maciej

2011-03-01

High-performance liquid chromatography coupled with spectrophotometric and electrospray mass spectrometric detection (HPLC-UV-Vis-ESI MS) was used for characterization of natural dyes present in historical art works. The gradient program was developed for identification of 29 colorants of various polarities. Dual detection system (UV-Vis and ESI MS) allowed differentiation of all compounds, even if they were not completely separated. This enabled examination of more color compounds over a substantially shorter time in comparison with previously recommended methods. Moreover, for extraction of colorants from historical textiles a two-step sequential procedure was proposed, excluding evaporation used in earlier procedures. The developed method was successfully applied to identification of indigotin, carminic, kermesic, flavokermesic, dcII, dcIV, dcVII, and ellagic acids as well as luteolin, apigenin, and genistein in red, violet, and green fibers taken from three selected historical chasubles which belong to the collection of the Wawel Cathedral treasury (Cracow, Poland). Italian textiles from the fifteenth and sixteenth centuries, of which chasubles were made, were dyed with a limited number of dyestuffs, consistently used for all batches of fabrics. The obtained results also allowed confirmation of the structure of the so-called "dcII" component of cochineal as a C-glucose derivative of flavokermesic acid.

Geographic variations of ecosystem service intensity in Fuzhou City, China.

PubMed

Hu, Xisheng; Hong, Wei; Qiu, Rongzu; Hong, Tao; Chen, Can; Wu, Chengzhen

2015-04-15

Ecosystem services are strongly influenced by the landscape configuration of natural and human systems. So they are heterogeneous across landscapes. However lack of the knowledge of spatial variations of ecosystem services constrains the effective management and conservation of ecosystems. We presented a spatially explicit and quantitative assessment of the geographic variations in ecosystem services for the Fuzhou City in 2009 using exploratory spatial data analysis (ESDA) and semivariance analysis. Results confirmed a significant and positive spatial autocorrelation, and revealed several hot-spots and cold-spots for the spatial distribution of ecosystem service intensity (ESI) in the study area. Also the trend surface analysis indicated that the level of ESI tended to be reduced gradually from north to south and from west to east, with a trough in the urban central area, which was quite in accordance with land-use structure. A more precise cluster map was then developed using the range of lag distance, deriving from semivariance analysis, as neighborhood size instead of default value in the software of ESRI ArcGIS 10.0, and geographical clusters where population growth and land-use pressure varied significantly and positively with ESI across the city were also created by geographically weighted regression (GWR). This study has good policy implications applicable to prioritize areas for conservation or construction, and design ecological corridor to improve ecosystem service delivery to benefiting areas. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of unknown brominated disinfection byproducts during chlorination using ultrahigh resolution mass spectrometry.

PubMed

Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Zheng, Hongdie; Yang, Min

2014-03-18

Brominated disinfection byproducts (Br-DBPs), formed from the reaction of disinfectant(s) with natural organic matter in the presence of bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. To date, only a few Br-DBPs in drinking water have been identified, while a significant portion of Br-DBPs in drinking water is still unknown. In this study, negative ion electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown Br-DBPs in artificial drinking water. In total, 441 formulas for one-bromine-containing products and 37 formulas for two-bromine-containing products, most of which had not been previously reported, were detected in the chlorinated sample. Most Br-DBPs have corresponding chlorine-containing analogues with identical CHO composition. In addition, on-resonance collision-induced dissociation (CID) of single ultrahigh resolved bromine containing mass peaks was performed in the ICR cell to isolate single bromine-containing components in a very complex natural organic matter spectrum and provide structure information. Relatively abundant neutral loss of CO2 was observed in MS-MS spectra, indicating that the unknown Br-DBPs are rich in carboxyl groups. The results demonstrate that the ESI FT-ICR MS method could provide valuable molecular composition and structure information on unknown Br-DBPs.

Evaluation of PCR electrospray-ionization mass spectrometry for rapid molecular diagnosis of bovine mastitis.

PubMed

Perreten, Vincent; Endimiani, Andrea; Thomann, Andreas; Wipf, Juliette R K; Rossano, Alexandra; Bodmer, Michèle; Raemy, Andreas; Sannes-Lowery, Kristin A; Ecker, David J; Sampath, Rangarajan; Bonomo, Robert A; Washington, Cicely

2013-06-01

Bovine mastitis, an inflammatory disease of the mammary gland, is one of the most costly diseases affecting the dairy industry. The treatment and prevention of this disease is linked heavily to the use of antibiotics in agriculture and early detection of the primary pathogen is essential to control the disease. Milk samples (n=67) from cows suffering from mastitis were analyzed for the presence of pathogens using PCR electrospray-ionization mass spectrometry (PCR/ESI-MS) and were compared with standard culture diagnostic methods. Concurrent identification of the primary mastitis pathogens was obtained for 64% of the tested milk samples, whereas divergent results were obtained for 27% of the samples. The PCR/ESI-MS failed to identify some of the primary pathogens in 18% of the samples, but identified other pathogens as well as microorganisms in samples that were negative by culture. The PCR/ESI-MS identified bacteria to the species level as well as yeasts and molds in samples that contained a mixed bacterial culture (9%). The sensitivity of the PCR/ESI-MS for the most common pathogens ranged from 57.1 to 100% and the specificity ranged from 69.8 to 100% using culture as gold standard. The PCR/ESI-MS also revealed the presence of the methicillin-resistant gene mecA in 16.2% of the milk samples, which correlated with the simultaneous detection of staphylococci including Staphylococcus aureus. We demonstrated that PCR/ESI-MS, a more rapid diagnostic platform compared with bacterial culture, has the significant potential to serve as an important screening method in the diagnosis of bovine clinical mastitis and has the capacity to be used in infection control programs for both subclinical and clinical disease. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Ultrahigh-performance liquid chromatography electrospray ionization Q-Orbitrap mass spectrometry for the analysis of 451 pesticide residues in fruits and vegetables: method development and validation.

PubMed

Wang, Jian; Chow, Willis; Chang, James; Wong, Jon W

2014-10-22

This paper presents an application of ultrahigh-performance liquid chromatography electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap MS) for the determination of 451 pesticide residues in fruits and vegetables. Pesticides were extracted from samples using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure. UHPLC/ESI Q-Orbitrap MS in full MS scan mode acquired full MS data for quantification, and UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) (i.e., data-dependent scan mode) obtained product ion spectra for identification. UHPLC/ESI Q-Orbitrap MS quantification was achieved using matrix-matched standard calibration curves along with the use of isotopically labeled standards or a chemical analogue as internal standards to achieve optimal method accuracy. The method performance characteristics include overall recovery, intermediate precision, and measurement uncertainty evaluated according to a nested experimental design. For the 10 matrices studied, 94.5% of the pesticides in fruits and 90.7% in vegetables had recoveries between 81 and 110%; 99.3% of the pesticides in fruits and 99.1% of the pesticides in vegetables had an intermediate precision of ≤20%; and 97.8% of the pesticides in fruits and 96.4% of the pesticides in vegetables showed measurement uncertainty of ≤50%. Overall, the UHPLC/ESI Q-Orbitrap MS demonstrated acceptable performance for the quantification of pesticide residues in fruits and vegetables. The UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) along with library matching showed great potential for identification and is being investigated further for routine practice.

No difference in pain reduction after epidural steroid injections in diabetic versus nondiabetic patients: A retrospective cohort study

PubMed Central

Wong, Francis; Namdari, Bahram; Dupler, Suzanne; Kovac, Mario Farias; Makarova, Natalya; Dalton, Jarrod E.; Turan, Alparslan

2016-01-01

Background and Aims: Diabetes affects peripheral and central neurons causing paresthesia, allodynia, hyperalgesia, and spontaneous pain. However, the effect of diabetes on response to epidural steroid injection (ESI) remains unknown. We hypothesized that diabetic patients receiving ESI will have different pain scores compared to nondiabetic patients. We tested a secondary hypothesis that pain reduction differs at different levels of hemoglobin A1c (HbA1c) for patients with diabetes. Material and Methods: Data from 284 consecutive patients given ESIs for radiculopathy were obtained via a manual review of electronic medical records. We initially compared diabetic and nondiabetic groups with respect to balance on baseline demographic and morphometric characteristics. Next, a linear regression model was developed to evaluate the association between existing diabetes and postinjection reduction in pain scores. And finally, we univariably characterized the association between HbA1c and pain reduction. Results: After exclusion of nine patients, 275 patients were analysed, including 55 (20%) who were diabetic. Pain reduction after ESI was comparable in diabetic and nondiabetic patients (Wald test P = 0.61). The degree of pain reduction generally decreased with the level of HbA1c until reaching HbA1c levels of approximately 7.5%, after which point it stayed fairly constant. Conclusion: There was no difference in pain reduction after ESIs comparing diabetic with nondiabetic patients; however, for diabetic patients, pain reduction may decrease with uncontrolled diabetes determined by high HbA1c values, thus suggesting pain physicians to take an active role in guiding their patients to have their blood glucose levels better regulated to improve outcomes of their ESIs. PMID:27006548

Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides.

PubMed

Lv, Jitao; Zhang, Shuzhen; Wang, Songshan; Luo, Lei; Cao, Dong; Christie, Peter

2016-03-01

Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

LC-ESI-MS/MS profiling of phenolics in the leaves of Eleutherococcus senticosus cultivated in the West Europe and anti-hyaluronidase and anti-acetylcholinestarase activities.

PubMed

Kuźniewski, Rafał; Załuski, Daniel; Olech, Marta; Banaszczak, Piotr; Nowak, Renata

2018-02-01

Neither secondary metabolites of the spring leaves nor the autumn leaves of Eleutherococcus senticosus species cultivated in Poland, or the bioactivity are known. The richest in polyphenols was the autumn leaves (171.1 mg/g DE), while in flavonoids the spring leaves (107.9 mg/g DE). Using LC-ESI-MS/MS, protocatechuic acid has been identified as the most abundant compound in the spring and autumn leaves (200 and 70 μg/g DE, respectively). Amongst flavonoids, naringenin 7-O-glucoside occurred in the largest amount (20 and 10 mg/g DE in the spring and autumn leaves, respectively). The autumn leaves inhibited Hyal the strongest (74.3%), comparing to the spring leaves (33%). A weak inhibition was found towards AChE (0.64 and 5.8% for the autumn and spring leaves, respectively). To our best knowledge, no information was available on the phytochemical composition and activity of the leaves of E. senticosus cultivated in Poland.

Addition of aluminium, zinc and magnesium hydrides to rhodium(iii)† †Electronic supplementary information (ESI) available. CCDC 1047853–1047855 1056989. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01309g Click here for additional data file. Click here for additional data file.

PubMed Central

Ekkert, Olga; White, Andrew J. P.; Toms, Harold

2015-01-01

We report the addition of M–H bonds (M = Al, Zn, Mg) to a Rh(iii) intermediate generated from the reductive elimination of triethylsilane from [Cp*Rh(H)2(SiEt3)2]. A series of new heterobimetallic complexes possessing Rh–M bonds have been isolated and characterised by a number of spectroscopic (1H, 29Si, 13C, 103Rh NMR, infrared, and X-ray diffraction) and computational techniques (NBO and QTAIM analysis). Experimental and computational data are consistent with cleavage of the M–H bond upon addition to rhodium with formation of new Rh–M and Rh–H bonds. Upon photolysis the Al analogue of this series undergoes a further elimination reaction producing triethylsilane and a highly unusual Rh2Al2H4 containing cluster proposed to contain an Al(i) bridging ligand. PMID:28757949

Mass spectrometric techniques for characterizing low-molecular-weight resins used as paint varnishes.

PubMed

Bonaduce, I; Colombini, M P; Degano, I; Di Girolamo, F; La Nasa, J; Modugno, F; Orsini, S

2013-01-01

The molecular structure of three low-molecular-weight resins used as paint varnishes has been characterized by use of an approach based on three different mass spectrometric techniques. We investigated the ketone resin MS2A, the aldehyde resin Laropal A81, and the hydrocarbon resin Regalrez 1094, now commonly used in restoration. To date, the molecular structures of these resins have not been completely elucidated. To improve current knowledge of the chemical composition of these materials, information obtained by gas chromatography-mass spectrometry (GC/MS), pyrolysis-gas chromatography-mass spectrometry (Py/GC/MS), and electrospray ionization mass spectrometry (ESI-Q-ToF) was combined. Analysis, in solution, of the whole polymeric fraction of the resins by flow-injection ESI-Q-ToF, and of the non-polymeric fraction by GC-MS, enabled us to identify previously unreported features of the polymer structures. In addition, the Py-GC/MS profiles that we obtained will help to enhance the databases currently available in the literature. The proposed approach can be extended to other low-molecular-weight resins used as varnishes in conservation.

Dual nickel and Lewis acid catalysis for cross-electrophile coupling: the allylation of aryl halides with allylic alcohols† †Electronic supplementary information (ESI) available. CCDC 1515176. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03140h

PubMed Central

Jia, Xue-Gong; Guo, Peng; Duan, Jicheng

2017-01-01

Controlling the selectivity in cross-electrophile coupling reactions is a significant challenge, particularly when one electrophile is much more reactive. We report a general and practical strategy to address this problem in the reaction between reactive and unreactive electrophiles by a combination of nickel and Lewis acid catalysis. This strategy is used for the coupling of aryl halides with allylic alcohols to form linear allylarenes selectively. The reaction tolerates a wide range of functional groups (e.g. silanes, boronates, anilines, esters, alcohols, and various heterocycles) and works with various allylic alcohols. Complementary to most current routes for the C3 allylation of an unprotected indole, this method provides access to C2 and C4–C7 allylated indoles. Preliminary mechanistic experiments reveal that the reaction might start with an aryl nickel intermediate, which then reacts with Lewis acid activated allylic alcohols in the presence of Mn. PMID:29629130

Structural and electronic studies of metal carbide clusterfullerene Sc2C2@Cs-C72

NASA Astrophysics Data System (ADS)

Feng, Yongqiang; Wang, Taishan; Wu, Jingyi; Feng, Lai; Xiang, Junfeng; Ma, Yihan; Zhang, Zhuxia; Jiang, Li; Shu, Chunying; Wang, Chunru

2013-07-01

We present a metal carbide clusterfullerene Sc2C2@Cs(10528)-C72, whose structure has been baffling for many years. A motional endohedral Sc2C2 cluster, special molecule geometry and electronic structure were found in Sc2C2@Cs(10528)-C72. The paramagnetic Sc2C2@Cs-C72 anion radical was successfully prepared by a chemical reduction method and hyperfine couplings in the ESR spectrum were observed.We present a metal carbide clusterfullerene Sc2C2@Cs(10528)-C72, whose structure has been baffling for many years. A motional endohedral Sc2C2 cluster, special molecule geometry and electronic structure were found in Sc2C2@Cs(10528)-C72. The paramagnetic Sc2C2@Cs-C72 anion radical was successfully prepared by a chemical reduction method and hyperfine couplings in the ESR spectrum were observed. Electronic supplementary information (ESI) available: Experimental details, HPLC chromatogram, and DFT calculations. CCDC 917712. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr01739g

Profiling and Distribution of Metabolites of Procyanidin B2 in Mice by UPLC-DAD-ESI-IT-TOF-MSn Technique

PubMed Central

Xiao, Ying; Hu, Zhongzhi; Yin, Zhiting; Zhou, Yiming; Liu, Taiyi; Zhou, Xiaoli; Chang, Dawei

2017-01-01

The metabolite profiles and distributions of procyanidin B2 were qualitatively described using UPLC-DAD-ESI-IT-TOF-MSn without help of reference standards, and a possible metabolic pathway was proposed in the present study. Summarily, 53 metabolites (24 new metabolites) were detected as metabolites of procyanidin B2, and 45 of them were tentatively identified. Twenty seven metabolites were assigned as similar metabolites of (−)-epicatechin by scission of the flavanol interflavanic bond C4–C8, including 16 aromatic metabolites, 5 conjugated metabolites, 3 ring-cleavage metabolites, and 2 phenylvalerolactone metabolites. Additionally, 14 metabolites were conjugates of free procyanidin B2, comprising 9 methylation metabolites, 8 sulfation metabolites, 5 hydration metabolites, 2 hydroxylation metabolites, 1 hydrogenation metabolites, and 1 glucuronidation metabolites. The results of metabolite distributions in organs indicated that the conjugated reaction of free procyanidin B2 mainly occurred in liver and diversified metabolites forms were observed in small intestine. The metabolic components of procyanidin B2 identified in mice provided useful information for further study of the bioactivity and mechanism of its action. PMID:28522973

Structural origins of broadband emission from layered Pb–Br hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1521053–1521055, 1521057–1521060 and 1521067. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01590a Click here for additional data file. Click here for additional data file.

PubMed Central

Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.; Lindenberg, Aaron M.

2017-01-01

Through structural and optical studies of a series of two-dimensional hybrid perovskites, we show that broadband emission upon near-ultraviolet excitation is common to (001) lead-bromide perovskites. Importantly, we find that the relative intensity of the broad emission correlates with increasing out-of-plane distortion of the Pb–(μ-Br)–Pb angle in the inorganic sheets. Temperature- and power-dependent photoluminescence data obtained on a representative (001) perovskite support an intrinsic origin to the broad emission from the bulk material, where photogenerated carriers cause excited-state lattice distortions mediated through electron–lattice coupling. In contrast, most inorganic phosphors contain extrinsic emissive dopants or emissive surface sites. The design rules established here could allow us to systematically optimize white-light emission from layered hybrid perovskites by fine-tuning the bulk crystal structure. PMID:28970879

Phytochemical characterization of different prickly pear (Opuntia ficus-indica (L.) Mill.) cultivars and botanical parts: UHPLC-ESI-MSn metabolomics profiles and their chemometric analysis.

PubMed

Mena, Pedro; Tassotti, Michele; Andreu, Lucía; Nuncio-Jáuregui, Nallely; Legua, Pilar; Del Rio, Daniele; Hernández, Francisca

2018-06-01

Prickly pear is an important source of bioactive compounds. However, a comprehensive characterization of the phytochemical profile of its aerial botanical parts, considering genotypic differences, has not been conducted. This study evaluated the phytochemical composition of four botanical parts (fruit pulp and skin, and young and adult cladodes) of six cultivars. Analysis was carried out by using two non-targeted UHPLC-ESI-MS n experimental conditions and assisted with multivariate analysis to facilitate data interpretation. Up to 41 compounds, mainly (poly)phenolic molecules, were identified and quantified, 23 compounds being reported for the first time in Opuntia ficus-indica. Phenolic composition varied significantly depending on the part of the plant. Betalains were detected only in the fruit of a red cultivar. This study provided novel insights in terms of identification of bioactives and thorough characterization of botanical parts of prickly pears. This information may be used for the development of prickly pear-derived products with high levels of bioactive compounds. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mass spectrometry characterization for N-glycosylation of immunoglobulin Y from hen egg yolk.

PubMed

Sheng, Long; He, Zhenjiao; Liu, Yaping; Ma, Meihu; Cai, Zhaoxia

2018-03-01

Immunoglobulin Y (IgY) is a new therapeutic antibody that exists in hen egg yolk. It is a glycoprotein, not much is known about its N-glycan structures, site occupancy and site-specific N-glycosylation. In this study, purified protein from hen egg yolk was identified as IgY based on SDS-PAGE and MALDI-TOF/TOF MS. N-glycan was released from IgY using peptide-N4-(N-acetyl-beta-glucosaminyl) asparagine-amidase treatment, and the molecular weight of IgY was calculated using the difference between the molecular weight of IgY and deglycosylated IgY. Two potential N-Glycosylation sites (ASN 308 and ASN 409 ) were detected on IgY by nanoLC-ESI MS. Sugar chains were separated using normal phase liquid chromatography after fluorescence labeling, and 17 N-glycan structures were confirmed using ESI-MS. The sugar chain pattern contained high-mannose oligosaccharide, hybrid oligosaccharide and complex oligosaccharide. These results could lead to other important information regarding IgY glycosylation. Copyright © 2017 Elsevier B.V. All rights reserved.

Versatile control of the submolecular motion of di(acylamino)pyridine-based [2]rotaxanes† †Electronic supplementary information (ESI) available: Experimental procedures, spectroscopic and mass spectrometry data for all new compounds, electrochemical studies, and full crystallographic details of 1c and 2b. CCDC 1051908 and 1051909. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00790a Click here for additional data file. Click here for additional data file.

PubMed Central

Martinez-Cuezva, Alberto; Pastor, Aurelia; Cioncoloni, Giacomo; Orenes, Raul-Angel; Alajarin, Mateo; Symes, Mark D.

2015-01-01

A cyclic network of chemical reactions has been conceived for exchanging the dynamic behaviour of di(acylamino)pyridine-based rotaxanes and surrogates. X-ray diffraction studies revealed the intercomponent interactions in these interlocked compounds and were consistent with those found in solution by dynamic NMR experiments. This particular binding site was incorporated into a molecular shuttle enabled for accessing two states with an outstanding positional discrimination through chemical manipulation. Furthermore, the ability of the di(acylamino)pyridine domain to associate with external binders with a complementary array of HB donor and acceptor sites was exploited for the advance of an unprecedented electrochemical switch operating through a reversible anion radical recognition process. PMID:28706682

Development and validation of a specific and sensitive HPLC-ESI-MS method for quantification of lysophosphatidylinositols and evaluation of their levels in mice tissues.

PubMed

Masquelier, Julien; Muccioli, Giulio G

2016-07-15

Increasing evidence suggests that lysophosphatidylinositols (LPIs), a subspecies of lysophospholipids, are important endogenous mediators. Although LPIs long remained among the less studied lysophospholipids, the identification of GPR55 as their molecular target sparked a renewed interest in the study of these bioactive lipids. Furthermore, increasing evidence points towards a role for LPIs in cancer development. However, a better understanding of the role and functions of LPIs in physiology and disease requires methods that allow for the quantification of LPI levels in cells and tissues. Because dedicated efficient methods for quantifying LPIs were missing, we decided to develop and validate an HPLC-ESI-MS method for the quantification of LPI species from tissues. LPIs are extracted from tissues by liquid/liquid extraction, pre-purified by solid-phase extraction, and finally analyzed by HPLC-ESI-MS. We determined the method's specificity and selectivity, we established calibration curves, determined the carry over (< 2%), LOD and LLOQ (between 0.116-7.82 and 4.62-92.5pmol on column, respectively), linearity (0.988 80%), intermediate precision (CV<20%) as well as the recovery from tissues. We then applied the method to determine the relative abundance of the LPI species in 15 different mouse tissues. Finally, we quantified the absolute LPI levels in six different mouse tissues. We found that while 18:0 LPI represents more than 60% of all the LPI species in the periphery (e.g. liver, gastrointestinal tract, lungs, spleen) it is much less abundant in the central nervous system where the levels of 20:4 LPI are significantly higher. Thus this validated HPLC-ESI-MS method for quantifying LPIs represents a powerful tool that will facilitate the comprehension of the pathophysiological roles of LPIs. Copyright © 2016 Elsevier B.V. All rights reserved.

Fuzzy clustering evaluation of the discrimination power of UV-Vis and (±) ESI-MS detection system in individual or coupled RPLC for characterization of Ginkgo Biloba standardized extracts.

PubMed

Medvedovici, Andrei; Albu, Florin; Naşcu-Briciu, Rodica Domnica; Sârbu, Costel

2014-02-01

Discrimination power evaluation of UV-Vis and (±) electrospray ionization/mass spectrometric techniques, (ESI-MS) individually considered or coupled as detectors to reversed phase liquid chromatography (RPLC) in the characterization of Ginkgo Biloba standardized extracts, is used in herbal medicines and/or dietary supplements with the help of Fuzzy hierarchical clustering (FHC). Seventeen batches of Ginkgo Biloba commercially available standardized extracts from seven manufacturers were measured during experiments. All extracts were within the criteria of the official monograph dedicated to dried refined and quantified Ginkgo extracts, in the European Pharmacopoeia. UV-Vis and (±) ESI-MS spectra of the bulk standardized extracts in methanol were acquired. Additionally, an RPLC separation based on a simple gradient elution profile was applied to the standardized extracts. Detection was made through monitoring UV absorption at 220 nm wavelength or the total ion current (TIC) produced through (±) ESI-MS analysis. FHC was applied to raw, centered and scaled data sets, for evaluating the discrimination power of the method with respect to the origins of the extracts and to the batch to batch variability. The discrimination power increases with the increase of the intrinsic selectivity of the spectral technique being used: UV-Vis

Rapid Screening and Characterization of Acetylcholinesterase Inhibitors from Yinhuang Oral Liquid Using Ultrafiltration-liquid Chromatography-electrospray Ionization Tandem Mass Spectrometry

PubMed Central

Zhang, Haomin; Guo, Yinan; Meng, Lingwen; Sun, Hui; Yang, Yinping; Gao, Ying; Sun, Jiaming

2018-01-01

Background: At present, approximately 17–25 million people in the world suffer from Alzheimer's disease (AD). The most efficacious and acceptable therapeutic drug clinically are the acetylcholinesterase inhibitors (AChEIs). Yinhuang oral liquid is a Chinese medicine preparation which contains AChEIs according to the literatures. However, no strategy has been presented for rapid screening and identification of AChEIs from Yinhuang oral liquid. Objective: To develop a method for rapid screening and identification of AChEIs from Yinhuang oral liquid using ultrafiltration–liquid chromatography–electrospray ionization tandem mass spectrometry (UF-LC-ESI-MS/MS). Materials and Methods: In this study, UF incubation conditions such as enzyme concentration, incubation time, and incubation temperature were optimized so as to get better screening results. The AChEIs from Yinhuang oral liquid were identified by high-performance liquid chromatography-ESI-MS and the improved Ellman method was used for the AChE inhibitory activity test in vitro. Results: The results showed that Yinhuang oral liquid can inhibit the activity of AChE. We screened and identified seven compounds with potential AChE inhibitory activity from Yinhuang oral liquid, which provided experimental basis for the treatment and prevention of AD. Conclusion: The current technique was used to directly screen the active ingredients with acetylcholinesterase inhibition from complex traditional Chinese medicine, which was simple, rapid, accurate, and suitable for high-throughput screening of AChEI from complex systems. SUMMARY A UF-LC-ESI-MS/MS method for rapid screening and identification of AChEIs from Yinhuang oral liquid was developedSeven compounds were screened and identified with potential AChE inhibitory activity from Yinhuang oral liquidIt provided experimental basis of Yinhuang oral liquid for the treating and preventing AD. Abbreviations used: (AD): Alzheimer's disease; (UF-LC-ESI-MS/MS): ultrafiltration–liquid chromatography–electrospray ionization tandem mass spectrometry; (AChEIs): acetylcholinesterase inhibitors. PMID:29720840

Predicting School Performance with the Early Screening Inventory.

ERIC Educational Resources Information Center

Meisels, Samuel J.; And Others

1984-01-01

Proposes criteria for defining and selecting preschool developmental screening instruments and describes the Early Screening Inventory (ESI), a developmental screening instrument designed to satisfy these criteria. Presents results of several studies demonstrating that the ESI predicts school performance with moderate to excellent accuracy through…

Validity of the Externalizing Spectrum Inventory in a Criminal Offender Sample: Relations with Disinhibitory Psychopathology, Personality, and Psychopathic Features

PubMed Central

Venables, Noah C.; Patrick, Christopher J.

2013-01-01

The Externalizing Spectrum Inventory (ESI; Krueger, Markon, Patrick, Benning, & Kramer, 2007) provides a self-report based method for indexing a range of correlated problem behaviors and traits in the domain of deficient impulse control. The ESI organizes lower-order behaviors and traits of this kind around higher-order factors encompassing general disinhibitory proneness, callous-aggression, and substance abuse. The current study used data from a male prisoner sample (N = 235) to evaluate the validity of ESI total and factor scores in relation to external criterion measures consisting of externalizing disorder symptoms (including child and adult antisocial deviance and substance-related problems) assessed via diagnostic interview, personality traits assessed by self-report, and psychopathic features as assessed by both interview and self-report. Results provide evidence for the validity of the ESI measurement model and point to its potential utility as a referent for research on the neurobiological correlates and etiological bases of externalizing proneness. PMID:21787091

Reliable Determinations of Protein-Ligand Interactions by Direct ESI-MS Measurements. Are We There Yet?

NASA Astrophysics Data System (ADS)

Kitova, Elena N.; El-Hawiet, Amr; Schnier, Paul D.; Klassen, John S.

2012-03-01

The association-dissociation of noncovalent interactions between protein and ligands, such as other proteins, carbohydrates, lipids, DNA, or small molecules, are critical events in many biological processes. The discovery and characterization of these interactions is essential to a complete understanding of biochemical reactions and pathways and to the design of novel therapeutic agents that may be used to treat a variety of diseases and infections. Over the last 20 y, electrospray ionization mass spectrometry (ESI-MS) has emerged as a versatile tool for the identification and quantification of protein-ligand interactions in vitro. Here, we describe the implementation of the direct ESI-MS assay for the determination of protein-ligand binding stoichiometry and affinity. Additionally, we outline common sources of error encountered with these measurements and various strategies to overcome them. Finally, we comment on some of the outstanding challenges associated with the implementation of the assay and highlight new areas where direct ESI-MS measurements are expected to make significant contributions in the future.

Validity of the Externalizing Spectrum Inventory in a criminal offender sample: relations with disinhibitory psychopathology, personality, and psychopathic features.

PubMed

Venables, Noah C; Patrick, Christopher J

2012-03-01

The Externalizing Spectrum Inventory (ESI; Krueger, Markon, Patrick, Benning, & Kramer, 2007) provides a self-report based method for indexing a range of correlated problem behaviors and traits in the domain of deficient impulse control. The ESI organizes lower order behaviors and traits of this kind around higher order factors encompassing general disinhibitory proneness, callous-aggression, and substance abuse. In the current study, we used data from a male prisoner sample (N = 235) to evaluate the validity of ESI total and factor scores in relation to external criterion measures consisting of externalizing disorder symptoms (including child and adult antisocial deviance and substance-related problems) assessed via diagnostic interviews, personality traits assessed with self-reports, and psychopathic features as assessed with both interviews and self-reports. Results provide evidence for the validity of the ESI measurement model and point to its potential usefulness as a referent for research on the neurobiological correlates and etiological bases of externalizing proneness.

Analysis of the extracts of Isatis tinctoria by new analytical approaches of HPLC, MS and NMR.

PubMed

Zhou, Jue; Qu, Fan

2011-01-01

The methods of extraction, separation and analysis of alkaloids and indole glucosinolates (GLs) ofIsatis tinctoria were reviewed. Different analytical approaches such as High-pressure Liquid Chromatography (HPLC), Liquid Chromatography with Electrospray Ionization Mass Spectrometry (LC/ESI/MS), Electrospray Ionization Time-Of-Flight Mass Spectrometry (ESI-TOF-MS), and Nuclear Magnetic Resonance (NMR) were used to validate and identity of these constituents. These methods provide rapid separation, identification and quantitative measurements of alkaloids and GLs of Isatis tinctoria. By connection with different detectors to HPLC such as PDA, ELSD, ESI- and APCI-MS in positive and negative ion modes, complicated compounds could be detected with at least two independent detection modes. The molecular formula can be derived in a second step of ESI-TOF-MS data. But for some constituents, UV and MS cannot provide sufficient structure identification. After peak purification, NMR by semi-preparative HPLC can be used as a complementary method.

LC-ESI-MS/MS identification of polar lipids of two thermophilic Anoxybacillus bacteria containing a unique lipid pattern.

PubMed

Rezanka, Tomáš; Kambourova, Margarita; Derekova, Anna; Kolouchová, Irena; Sigler, Karel

2012-07-01

Phospholipids and glycolipids from two recently described species belonging to the thermophilic genus Anoxybacillus were analyzed by liquid chromatography-electrospray tandem mass spectrometry (LC/ESI-MS/MS). Analysis of total lipids from the facultatively anaerobic A. bogrovensis on a HILIC (Hydrophilic Interaction LIquid Chromatography) column succeeded in separating diacyl- and plasmalogen phospholipids. The LC/ESI-MS/MS analysis of the strict aerobe A. rupiensis revealed the presence of different unique polar lipids, predominantly alanyl-, lysyl-, and glucosyl-phosphatidylglycerols and cardiolipins. Each of the classes of polar lipids was then analyzed by means of the ESI-MS/MS and more than 140 molecular species of six lipid classes from A. bogrovensis and nearly 200 molecular species of nine classes of polar lipids from A. rupiensis were identified. Five classes of unidentified polar lipids were detected in both strains. Plasmalogens were thus determined for the first time in a facultatively anaerobic bacterium, i.e. A. bogrovensis.

Risk, benefits and complications of epidural steroid injections: a case report.

PubMed

Snarr, Jared

2007-06-01

Acute low back pain, radiculopathy, and associated disabilities have a prevalence of 2% in the United States, which represents a significant health problem and a major cause of workplace absence. The condition primarily affects 25- to 45-year-old men and women. Epidural steroid injections (ESIs) are commonly administered to relieve this pain and improve mobility without surgery. This case report presents issues related to the treatment of an epidural hematoma in an 87-year-old man receiving long-term anticoagulant therapy. It reviews the risks, benefits, side effects, complications, and contraindications to ESI and the American Society of Regional Anesthesia consensus recommendations for the performance of neuraxial procedures in patients receiving anticoagulant therapy. It is imperative that any provider who performs ESIs know the risks, benefits, complications, and contraindications for this procedure. Practitioners must also be able to recognize and manage or appropriately refer patients having immediate or delayed complications related to the placement of an ESI.

Investigation of the Biotransformation of a DMA in Mouse Cecum Samples Using IC-ICP-MS and LC-ESI-MS/MS Detection

EPA Science Inventory

Recent arsenic metabolism studies have begun to indicate the presence of sulfur analogs of the more common arsenic oxides in biological systems. An emerging area of research is how and where these arsenic species are formed in the metabolic pathway. The authors have previously i...

The diagnostic utility of 3D-ESI rotating and moving dipole methodology in the pre-surgical evaluation of MRI-negative childhood epilepsy due to focal cortical dysplasia.

PubMed

Russo, Angelo; Lallas, Matt; Jayakar, Prasanna; Miller, Ian; Hyslop, Ann; Dunoyer, Catalina; Resnick, Trevor; Duchowny, Michael

2016-09-01

This study investigates whether a combined rotating dipole (RD) and moving dipole (MD) solution enhances three-dimensional electroencephalography (EEG) source imaging (3D-ESI) localization in magnetic resonance imaging (MRI)-negative pediatric patients with focal cortical dysplasia (FCD). We retrospectively selected 14 MRI-negative patients with FCD from a cohort of 60 pediatric patients previously used to evaluate the diagnostic utility of 3D-ESI in epilepsy surgery. Patients were younger than 18 years at time of surgery and had at least 1 year of outcome data. RD and MD models were constructed for each interictal spike or sharp wave, and it was determined whether each inverse algorithm localized within the surgical resection cavity (SRC). We also compared the 3D-ESI findings and surgical outcome with positron emission tomography (PET) and ictal single photon emission computed tomography (iSPECT). RD analyses revealed a high concordance with the SRC (78.6%), particularly for temporal lobe resection (100.0%), and showed superior localization compared to PET and iSPECT, with the highest correlation in FCD type I and temporal lobe resection. Furthermore, the RD method was superior to iSPECT in FCD type II cases and to PET in extratemporal resections. RD and MD results were comparable, but in 18.2% of patients with FCD type I with localizing RDs, the MD solution was only partially within the SRC; in all of these patients 3D-ESI also correlated with superior surgical outcome compared to PET and iSPECT, especially when RD and MD solutions were analyzed together. 3D-ESI in MRI-negative cases showed superior localization compared to iSPECT or PET, especially in FCD type I and temporal lobe epilepsy, and correlated with superior surgical outcome compared to iSPECT and PET at 1 year and 2 years postoperatively, especially when RD and MD solutions were analyzed together. These findings suggest that 3D-ESI based on a combined RD-MD solution improves surgical accuracy in MRI-negative patients with FCD. Wiley Periodicals, Inc. © 2016 International League Against Epilepsy.

Transition of the GOES Evapotranspiration and Drought Product System (GET-D) into Operations at NOAA/NESDIS

NASA Astrophysics Data System (ADS)

Hain, C.; Anderson, M. C.; Fang, L.; Zhan, X.; Otkin, J.

2016-12-01

Abnormally dry conditions can adversely affect the health of agricultural crops if the dryness persists for an extended period of time or if it occurs at a sensitive stage of crop development. Depending on its severity and timing, drought can result in significant yield loss, with impacts on both local and global markets as signified by reduced economic output and higher grain and food prices. Due to changing climate conditions, we are moving into a regime where processes controlling drought evolution are becoming more variable and are shifting in intensity, frequency and duration. The unusually rapid increase in water stress during some of these drought events are not well predicted by standard drought indicators. Different remote sensing indicators sample moisture and vegetation conditions occurring on different time scales during the typical evolution of agricultural drought. It has been shown that the thermal-based Evaporative Stress Index (ESI), based on land surface temperature, has an early warning component where vegetation stress manifested through decreased root-zone soil moisture leads to detectable vegetation stress in the LST signal before degradation in vegetation health is observed in VIS/NIR drought indices (e.g., NDVI). To provide this data to a larger user community and address the needs of our project stakeholders, the GOES Evapotranspiration and Drought Product System (GET-D) has been developed to operationally generate daily ET and ESI maps over the North America. The core model in GET-D is the Atmosphere-Land Exchange Inverse model (ALEXI), which is built on the two-source energy (TSEB) approach and partitions the GOES land surface temperature into characteristic soil and canopy temperatures, based on the fraction of vegetation cover. The primary operational data products of the GET-D system include the daily clear-sky ET and daily 2, 4, 8 and 12 week composites of the Evaporative Stress Index (ESI) computed from the ET daily estimates over North America at a spatial resolution of 8 km. This talk will focus on the evaluation of the operational data products, lessons learned from the transition into operations and the planned global expansion of the GET-D system at NOAA.

Popular pharmaceutical residues in hospital wastewater: quantification and qualification of degradation products by mass spectroscopy after treatment with membrane bioreactor.

PubMed

Chiarello, M; Minetto, L; Giustina, S V Della; Beal, L L; Moura, S

2016-08-01

The occurrence of drugs in wastewater has been considered an imminent risk to the population, for the treatments used are usually ineffective. The presence of four popular drug residues (metformin, paracetamol, tetracycline, and enalapril) in hospital effluents, by using ultra-fast liquid chromatography tandem mass spectrometry (UFLC-MS/MS) with electrospray (ESI) ionization, and removal/degradation by membrane bioreactor (MBR) system are investigated in this study. For analysis method, all standard calibration curves showed satisfactory linearity (R (2) ≥ 0.993) within a relatively wide range. The recovery was between 70.4 and 105.0 %, and the relative standard deviation (RSD) values were within the ranges of 8.2 and 13.5 %. The effluent samples were collected at the end of the process treated in a bench-scale MBR treatment system and preconcentrated on solid-phase extraction (SPE) cartridges. Following that procedure, the chemical analysis demonstrated that the MBR system was effective in enalapril 94.3 ± 7.63 %, tetracycline 99.4 ± 0.02 %, and paracetamol 98.8 ± 0.86 % removal. However, the polar metformin was less effectively removed (35.4 ± 12.49 %). Moreover, the degradation products were investigated using high-resolution mass spectrometry (HRMS) by quadrupole-time of flight (Q-TOF), which has been indicated a tetracycline metabolite. In order to investigate the environmental impact, the wastewater potential risk was evaluated. The risk quotient (RQ) by measure environmental concentration (MEC) and its predicted no effect concentration (PNEC) ratio (RQ = MEC/PNEC) was between 0.003 (enalapril) to 0.815 (paracetamol). Finally, this work demonstrates that UFLC-MS/MS (ESI-Q) is a sensitive and selective method for drug analysis in wastewater and with ESI-Q-TOF has the accuracy required for determining the degradation products of these compounds. Also, it indicated that membrane bioreactor systems represent a new generation of processes that have proved to outperform conventional treatment showing better effluent quality. The removal capacity studied in this work demonstrates the efficiency of this process.

Fluoroscopically Guided Epidural Injections of the Cervical and Lumbar Spine.

PubMed

Shim, Euddeum; Lee, Joon Woo; Lee, Eugene; Ahn, Joong Mo; Kang, Yusuhn; Kang, Heung Sik

2017-01-01

Advances in imaging and the development of injection techniques have enabled spinal intervention to become an important tool in managing chronic spinal pain. Epidural steroid injection (ESI) is one of the most widely used spinal interventions; it directly delivers drugs into the epidural space to relieve pain originating from degenerative spine disorders-central canal stenoses and neural foraminal stenoses-or disk herniations. Knowledge of the normal anatomy of the epidural space is essential to perform an effective and safe ESI and to recognize possible complications. Although computed tomographic (CT) or combined CT-fluoroscopic guidance has been increasingly used in ESI, conventional fluoroscopic guidance is generally performed. In ESI, drugs are delivered into the epidural space by interlaminar or transforaminal routes in the cervical spine or by interlaminar, transforaminal, or caudal routes in the lumbar spine. Epidurography is usually performed before drug delivery to verify the proper position of the needle in the epidural space. A small amount of contrast agent is injected with fluoroscopic guidance. Familiarity with the findings on a typical "true" epidurogram (demonstrating correct needle placement in the epidural space) permits proper performance of ESI. Findings on "false" epidurograms (demonstrating incorrect needle placement) include muscular staining and evidence of intravascular injection, inadvertent facet joint injection, dural puncture, subdural injection, and intraneural or intradiscal injection. © RSNA, 2016 An earlier incorrect version of this article appeared online. This article was corrected on December 22, 2016.

Tissue Localization of Glycosphingolipid Accumulation in a Gaucher Disease Mouse Brain by LC-ESI-MS/MS and High-Resolution MALDI Imaging Mass Spectrometry.

PubMed

Jones, E Ellen; Zhang, Wujuan; Zhao, Xueheng; Quiason, Cristine; Dale, Stephanie; Shahidi-Latham, Sheerin; Grabowski, Gregory A; Setchell, Kenneth D R; Drake, Richard R; Sun, Ying

2017-12-01

To better understand regional brain glycosphingolipid (GSL) accumulation in Gaucher disease (GD) and its relationship to neuropathology, a feasibility study using mass spectrometry and immunohistochemistry was conducted using brains derived from a GD mouse model (4L/PS/NA) homozygous for a mutant GCase (V394L [4L]) and expressing a prosaposin hypomorphic (PS-NA) transgene. Whole brains from GD and control animals were collected using one hemisphere for MALDI FTICR IMS analysis and the other for quantitation by LC-ESI-MS/MS. MALDI IMS detected several HexCers across the brains. Comparison with the brain hematoxylin and eosin (H&E) revealed differential signal distributions in the midbrain, brain stem, and CB of the GD brain versus the control. Quantitation of serial brain sections with LC-ESI-MS/MS supported the imaging results, finding the overall HexCer levels in the 4L/PS-NA brains to be four times higher than the control. LC-ESI-MS/MS also confirmed that the elevated hexosyl isomers were glucosylceramides rather than galactosylceramides. MALDI imaging also detected differential analyte distributions of lactosylceramide species and gangliosides in the 4L/PS-NA brain, which was validated by LC-ESI-MS/MS. Immunohistochemistry revealed regional inflammation, altered autophagy, and defective protein degradation correlating with regions of GSL accumulation, suggesting that specific GSLs may have distinct neuropathological effects.

Assessing the Agreement Between Radiologic and Clinical Measurements of Lumbar and Cervical Epidural Depths in Patients Undergoing Prone Interlaminar Epidural Steroid Injection.

PubMed

Jones, James Harvey; Singh, Naileshni; Nidecker, Anna; Li, Chin-Shang; Fishman, Scott

2017-05-01

Fluoroscopy-guided epidural steroid injection (ESI) commonly is performed to treat radicular pain yet can lead to adverse events if the needle is not advanced with precision. Accurate preoperative assessment of the distance from the skin to the epidural space holds the potential for reducing the risks of adverse effects from ESI. It was hypothesized that the distance from the skin to the epidural space as measured on preoperative magnetic resonance imaging (MRI) would agree with the distance traveled by a Tuohy needle to reach the epidural space during midline, interlaminar ESI. This study compared the final needle depth measurement at the point of loss of resistance (LOR) from cervical or lumbar ESI to the distance from the skin to the anterior and posterior borders of the epidural space on the associated cervical and lumbar preoperative MRI. This retrospective chart review analyzed the procedure notes, MRI, and demographic data of patients who received a prone, interlaminar ESI at an outpatient chronic pain clinic between June 1, 2013, and June 1, 2015. The following data were collected: body mass index (BMI), age, sex, intervertebral level of the ESI, and LOR depth. We then measured the distance from the skin surface to the anterior border of the ligamentum flavum (ligamentum flavum depth [LFD]) and dura (dura depth [DD]) on MRI. A total of 335 patients were categorized into the following patient subgroups: age ≥65 years, age <65 years, BMI ≥30 kg/m (obese), BMI <30 kg/m (nonobese), male, and female. Secondary analyses were then performed to compare the agreement between LOR depth and DD with that between LOR depth and LFD within each patient subgroup. Intraclass correlation coefficient (ICC) and Bland-Altman plot were used to assess the agreement between DD or LFD and LOR depth. Data from 335 ESIs were analyzed, including 147 cervical ESIs and 188 lumbar ESIs. Estimated ICC values for the agreement between LOR depth and LFD for all lumbar and cervical measurements were 0.88 (95% confidence interval [CI], 0.85-0.91) and 0.72 (95% CI, 0.64-0.79), respectively. Estimated ICC values for the agreement between LOR depth and DD for all lumbar and cervical measurements were 0.86 (95% CI, 0.82-0.89) and 0.69 (95% CI, 0.60-0.77), respectively. This study assessed the agreement between MRI-derived measurements of epidural depth and those determined clinically. MRI-derived measurements from the skin to the anterior border of the ligamentum flavum, which represents the most posterior aspect of the epidural space, revealed stronger agreement with LOR depths than did measurements to the dura or the most anterior aspect of the epidural space. These results require further analysis and refinement before supporting clinical application.

Analysis of Chemical Warfare Agents: General Overview, LC-MS Review, In-House LC-ESI-MS Methods and Open Literature Bibliography

DTIC Science & Technology

2006-03-01

Kurdish village. Most recently, sarin was released by the Aum Shinrikyo cult in the Tokyo underground transit system resulting in thousands seeking...a) Nerve (reacts irreversibly with cholinesterase which results in acetylcholine accumulation, continual stimulation of the body’s nervous system ...18]. The specificity of product scanning with moderate sector resolution, as well as the specificity of ammonia CI, were demonstrated with a hybrid

P39-T Analysis of Oligosaccharides by Capillary-Scale High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection (CHPAEC-PAD) and On-Line Electrospray-Ionization Ion-Trap Mass Spectrometry (CHPAEC-ITMS)

PubMed Central

Bruggink, C.; Koeleman, C.; Barreto, V.; Lui, Y.; Pohl, C.; Ingendoh, A.; Wuhrer, M.; Hokke, C.; Deelder, A.

2007-01-01

High-pH anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD) is an established technique for selective separation and analysis of underivatized carbohydrates. The miniaturization of chromatographic techniques by means of capillary columns, and on-line coupling to mass spectrometry are critical to the further development of glycan analysis methods that are compatible with the current requirements in clinical settings. A system has been developed based on the Dionex BioLC equipped with a microbore gradient pump with PEEK flow splitter, a FAMOS micro autosampler, a modified electrochemical cell for on-line capillary PAD, and a capillary column (380 μm i.d.) packed with a new type of anion-exchange resin. This system operates with sensitivity in the low femtomol range. In addition, an on-line capillary desalter has been developed to allow direct coupling to the Bruker Esquire 3000 ion-trap mass spectrometer with electrospray ionization interface (ESI-IT-MS). Both systems have been evaluated using oligosaccharide standards as well as urine samples exhibiting various lysosomal oligosaccharide storage diseases. Initial data indicate that the robust and selective anion-exchange system, in combination with ESI-IT-MS for structure confirmation and analysis, provides a powerful platform that complements existing nano/capillary LC-MS methods for analytical determination of oligosaccharides in biological matrices.

Fundamentals of Biomolecule Analysis by Electrospray Ionization Mass Spectrometry

ERIC Educational Resources Information Center

Weinecke, Andrea; Ryzhov, Victor

2005-01-01

Electrospray ionization (ESI) is a soft ionization technique that allows transfer of fragile biomolecules directly from solution into the gas phase. An instrumental analysis laboratory experiment is designed that would introduce the students to the ESI technique, major parameters of the ion trap mass spectrometers and some caveats in…

LC-PDA-ESI/MS Identification of the Phenolic Components of Three Compositae Spices: Chamomile, Tarragon, and Mexican Arnica

USDA-ARS?s Scientific Manuscript database

Chamomile (Matricaria chamomilla L.), tarragon (Artemisia dracunculus L.) and Mexican arnica (Heterotheca inuoides) are common compositae spices and herbs found in the US market. They contain flavonoids and hydroxycinnamates that are potentially beneficial to human health. A standardized LC-PDA-ESI...

Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

USDA-ARS?s Scientific Manuscript database

Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

Predictors of Eligibility for ESY. Final Report.

ERIC Educational Resources Information Center

Browder, Diane M.; And Others

Evaluation of eligibility for extended school year (ESY) services was made based on informaton contained in school files in a stratified sampling across Pennsylvania. Subjects had been classified as severely and profoundly mentally retarded and were divided into groups based on eligibility for programming in excess of 180 days or ineligibility for…

Contextual Factors and Effective School Improvement

ERIC Educational Resources Information Center

Sun, Hechuan; Creemers, Bert P. M.; de Jong, Rob

2007-01-01

This research provides policy-makers, researchers, and educators at all levels with a glimpse of the contextual influence on effective school improvement (ESI) in 8 European countries. What are the factors at the contextual level, particularly at the national level, which influence ESI? Are there any similarities or differences between the…

RP-HPLC-DAD-ESI-QTOF-MS based metabolic profiling of the potential Olea europaea by-product "wood" and its comparison with leaf counterpart.

PubMed

Ammar, Sonda; Contreras, Maria Del Mar; Gargouri, Boutheina; Segura-Carretero, Antonio; Bouaziz, Mohamed

2017-05-01

Olea europaea L. organs such as leaves, stems and roots have been associated with numerous in vivo and in vitro biological activities and used for traditional medicinal purposes. However, tree wood is an untapped resource with little information about their chemical composition. That is why, the objective of this study is to increase the knowledge about phytochemicals from 'Chemlali' olive wood by means of mass spectrometry-based analyses. Its comparison with by-products derived from leaves was also studied. Hydromethanol extracts from wood and leaves with stems of 'Chemlali' olive cultivar were analysed using reversed-phase (RP) high-performance liquid chromatography (HPLC) coupled to two detection systems: diode-array detection (DAD) and quadrupole time-of-flight (QTOF) mass spectrometry (MS) in negative ion mode. Tandem MS experiments were performed to establish the chemical structure of olive phytochemicals. A total of 85 compounds were characterised in the studied olive parts and classified as: sugars (3), organic acids (5), one phenolic aldehyde, simple phenolic acids (6), simple phenylethanoids (5), flavonoids (14), coumarins (3), caffeoyl phenylethanoid derivatives (6), iridoids (5), secoiridoids (32), and lignans (5). To our knowledge, the major part of these metabolites was not previously reported in olive tree wood, and 10 olive chemical constituents were identified for the first time in the Oleaceae family. The results presented here demonstrated the usefulness of the methodology proposed, based on RP-HPLC-DAD-ESI-QTOF-MS and MS/MS, to develop an exhaustive metabolic profiling and to recover new biologically active compounds in olive wood with pharmacologic and cosmetic potential. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins† †Electronic supplementary information (ESI) available: Procedures for synthetic, spectroscopic, and electrochemical experiments. CCDC 1582750. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04682k

PubMed Central

Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K.; Smith, Peter T.

2018-01-01

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input. Inspired by natural bioinorganic systems that feature precisely positioned hydrogen-bond donors in the secondary coordination sphere to direct chemical transformations occurring at redox-active metal centers, we now report the design, synthesis, and characterization of a series of iron tetraphenylporphyrin (Fe-TPP) derivatives bearing amide pendants at various positions at the periphery of the metal core. Proper positioning of the amide pendants greatly affects the electrocatalytic activity for carbon dioxide reduction to carbon monoxide. In particular, derivatives bearing proximal and distal amide pendants on the ortho position of the phenyl ring exhibit significantly larger turnover frequencies (TOF) compared to the analogous para-functionalized amide isomers or unfunctionalized Fe-TPP. Analysis of TOF as a function of catalyst standard reduction potential enables first-sphere electronic effects to be disentangled from second-sphere through-space interactions, suggesting that the ortho-functionalized porphyrins can utilize the latter second-sphere property to promote CO2 reduction. Indeed, the distally-functionalized ortho-amide isomer shows a significantly larger through-space interaction than its proximal ortho-amide analogue. These data establish that proper positioning of secondary coordination sphere groups is an effective design element for breaking electronic scaling relationships that are often observed in electrochemical CO2 reduction. PMID:29732079

Enantioselective cellular localisation of europium(iii) coordination complexes† †Electronic supplementary information (ESI) available: Complex synthesis and characterisation, selected cell images showing correspondence with commercial lysosomal or mitochondrial stains and spectral imaging profiles. See DOI: 10.1039/c7sc04422d

PubMed Central

Frawley, Andrew T.; Linford, Holly V.; Starck, Matthieu; Pal, Robert

2017-01-01

The selective mitochondrial localisation of the Λ enantiomer of three different emissive europium(iii) complexes in NIH 3T3 and MCF7 cells contrasts with the behaviour of the Δ enantiomer, for which a predominant lysosomal localisation was observed by confocal microscopy. In each case, cell uptake occurs via macropinocytosis. PMID:29675151

Determining rotational dynamics of the guanidino group of arginine side chains in proteins by carbon-detected NMR† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7cc04821a

PubMed Central

Gerecht, Karola; Figueiredo, Angelo Miguel

2017-01-01

Arginine residues are imperative for many active sites and protein-interaction interfaces. A new NMR-based method is presented to determine the rotational dynamics around the Nε–Cζ bond of arginine side chains. An application to a 19 kDa protein shows that the strengths of interactions involving arginine side chains can be characterised. PMID:28840203

A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies† †Electronic supplementary information (ESI) available: For experimental catalytic details and mechanistic procedures, including GC and GC-MS traces, additional figures (Fig. S1–S25), computational data including Cartesian coordinates and energies of all stationary points reported in the text. See DOI: 10.1039/c7sc02898a

PubMed Central

Vilella, Laia; Conde, Ana

2017-01-01

A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu–O moiety prior to the C–O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured. PMID:29619184

Temporal switching of an amphiphilic self-assembly by a chemical fuel-driven conformational response† †Electronic supplementary information (ESI) available: Experimental section, synthetic procedures and supporting figures. See DOI: 10.1039/c7sc01730h Click here for additional data file.

PubMed Central

Jalani, Krishnendu; Dhiman, Shikha

2017-01-01

The spatial and temporal control of self-assemblies is the latest scientific hurdle in supramolecular chemistry which is inspired by the functioning of biological systems fueled by chemical signals. In this study, we work towards alleviating this scenario by employing a unique amphiphilic foldamer that operates under the effect of a chemical fuel. The conformational changes in the foldamer amplify into observable morphological changes in its amphiphilic assembly that are controlled by external molecular cues (fuel). We take advantage of this redox responsive foldamer to affect its conformation in a temporal manner by an enzymatic pathway. The temporal characteristics of the transient conformation/assembly can be modulated by varying the concentrations of the fuel and enzyme. We believe that such a design strategy can have positive consequences in designing molecular and supramolecular systems for future active, adaptive and autonomous materials. PMID:28989632

Immunomodulatory properties of carbon nanotubes are able to compensate immune function dysregulation caused by microgravity conditions

NASA Astrophysics Data System (ADS)

Crescio, Claudia; Orecchioni, Marco; Ménard-Moyon, Cécilia; Sgarrella, Francesco; Pippia, Proto; Manetti, Roberto; Bianco, Alberto; Delogu, Lucia Gemma

2014-07-01

Spaceflights lead to dysregulation of the immune cell functionality affecting the expression of activation markers and cytokine production. Short oxidized multi-walled carbon nanotubes functionalized by 1,3-dipolar cycloaddition have been reported to activate immune cells. In this Communication we have performed surface marker assays and multiplex ELISA on primary monocytes and T cells under microgravity. We have discovered that carbon nanotubes, through their immunostimulatory properties, are able to fight spaceflight immune system dysregulations.Spaceflights lead to dysregulation of the immune cell functionality affecting the expression of activation markers and cytokine production. Short oxidized multi-walled carbon nanotubes functionalized by 1,3-dipolar cycloaddition have been reported to activate immune cells. In this Communication we have performed surface marker assays and multiplex ELISA on primary monocytes and T cells under microgravity. We have discovered that carbon nanotubes, through their immunostimulatory properties, are able to fight spaceflight immune system dysregulations. Electronic supplementary information (ESI) available: Experimental section, structures of f-MWCNTs and uptake by human primary immune cells. See DOI: 10.1039/c4nr02711f

Comprehensive and accurate tracking of carbon origin of LC-tandem mass spectrometry collisional fragments for 13C-MFA.

PubMed

Kappelmann, Jannick; Klein, Bianca; Geilenkirchen, Petra; Noack, Stephan

2017-03-01

In recent years the benefit of measuring positionally resolved 13 C-labeling enrichment from tandem mass spectrometry (MS/MS) collisional fragments for improved precision of 13 C-Metabolic Flux Analysis ( 13 C-MFA) has become evident. However, the usage of positional labeling information for 13 C-MFA faces two challenges: (1) The mass spectrometric acquisition of a large number of potentially interfering mass transitions may hamper accuracy and sensitivity. (2) The positional identity of carbon atoms of product ions needs to be known. The present contribution addresses the latter challenge by deducing the maximal positional labeling information contained in LC-ESI-MS/MS spectra of product anions of central metabolism as well as product cations of amino acids. For this purpose, we draw on accurate mass spectrometry, selectively labeled standards, and published fragmentation pathways to structurally annotate all dominant mass peaks of a large collection of metabolites, some of which with a complete fragmentation pathway. Compiling all available information, we arrive at the most detailed map of carbon atom fate of LC-ESI-MS/MS collisional fragments yet, comprising 170 intense and structurally annotated product ions with unique carbon origin from 76 precursor ions of 72 metabolites. Our 13 C-data proof that heuristic fragmentation rules often fail to yield correct fragment structures and we expose common pitfalls in the structural annotation of product ions. We show that the positionally resolved 13 C-label information contained in the product ions that we structurally annotated allows to infer the entire isotopomer distribution of several central metabolism intermediates, which is experimentally demonstrated for malate using quadrupole-time-of-flight MS technology. Finally, the inclusion of the label information from a subset of these fragments improves flux precision in a Corynebacterium glutamicum model of the central carbon metabolism.

Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometric (LC/ESI-MS/MS) Study for the Identification and Characterization of In Vivo Metabolites of Cisplatin in Rat Kidney Cancer Tissues: Online Hydrogen/Deuterium (H/D) Exchange Study.

PubMed

Bandu, Raju; Ahn, Hyun Soo; Lee, Joon Won; Kim, Yong Woo; Choi, Seon Hee; Kim, Hak Jin; Kim, Kwang Pyo

2015-01-01

In vivo rat kidney tissue metabolites of an anticancer drug, cisplatin (cis-diamminedichloroplatinum [II]) (CP) which is used for the treatment of testicular, ovarian, bladder, cervical, esophageal, small cell lung, head and neck cancers, have been identified and characterized by using liquid chromatography positive ion electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) in combination with on line hydrogen/deuterium exchange (HDX) experiments. To identify in vivo metabolites, kidney tissues were collected after intravenous administration of CP to adult male Sprague-Dawley rats (n = 3 per group). The tissue samples were homogenized and extracted using newly optimized metabolite extraction procedure which involves liquid extraction with phosphate buffer containing ethyl acetate and protein precipitation with mixed solvents of methanol-water-chloroform followed by solid-phase clean-up procedure on Oasis HLB 3cc cartridges and then subjected to LC/ESI-HRMS analysis. A total of thirty one unknown in vivo metabolites have been identified and the structures of metabolites were elucidated using LC-MS/MS experiments combined with accurate mass measurements. Online HDX experiments have been used to further support the structural characterization of metabolites. The results showed that CP undergoes a series of ligand exchange biotransformation reactions with water and other nucleophiles like thio groups of methionine, cysteine, acetylcysteine, glutathione and thioether. This is the first research approach focused on the structure elucidation of biotransformation products of CP in rats, and the identification of metabolites provides essential information for further pharmacological and clinical studies of CP, and may also be useful to develop various effective new anticancer agents.

Quantitative and transformation product analysis of major active physalins from Physalis alkekengi var. franchetii (Chinese lantern) using ultraperformance liquid chromatography with electrospray ionisation tandem mass spectrometry and time-of-flight mass spectrometry.

PubMed

Zheng, Yunliang; Chen, Yong; Ren, Yiping; Luan, Lianjun; Wu, Yongjiang

2012-01-01

Chinese lantern is the calyx or calyx-with-fruit of the plant Physalis alkekengi .var. franchetii (Solanaceae), and is potential material for the food and pharmaceutical industries. Physalins are the most active and representative secondary metabolites of Chinese lantern. A separation and quantification method based on UPLC-ESI-MS/MS was developed for the quantitative analysis of five active physalins. The transformation products were also detected and identified for the first time. To establish a LC-MS/MS method to quantify five physalins in Chinese lantern for the purpose of quality control, and to identify the transformation products of 4,7-didehydrophysalin B. The separation was carried out on an Acquity UPLC BEH Shield RP C₁₈-column with water and acetonitrile as the mobile phase under gradient conditions. ESI-MS/MS was used as the detector to quantify the five physalins. The transformation products of 4,7-didehydroneophysalin B were detected by UPLC-PDA-ESI-MS/MS and identified through comparing their HRMS and MS² ion fragmentations with corresponding references. All the compounds showed good linearity (R²  > 0.998). The recoveries, measured at three concentration levels, varied from 98.8 to 101.4% with RSDs < 4.5%. The total contents of the five physalins in Chinese lantern varied significantly. Three transformation products of 4,7-didehydroneophysalin B were detected and tentatively identified. The present study developed a highly effective analytical method for the quality control of Chinese lantern, and it could provide comprehensive information for quality evaluation and new drug development of Chinese lantern. Copyright © 2011 John Wiley & Sons, Ltd.

Structural characterization by both positive and negative electrospray ion trap mass spectrometry of oligogalacturonates purified by high-performance anion-exchange chromatography.

PubMed

Quéméner, Bernard; Désiré, Cédric; Debrauwer, Laurent; Rathahao, Estelle

2003-01-17

The off-line coupling of high-performance anion-exchange chromatography to electrospray ion trap mass spectrometry (ESI-IT-MS) is described. Two sets of isocratic conditions were optimised for the semi-preparative purification of oligogalacturonates of degree of polymerisation from 4 to 6 by monitoring eluates with either pulsed amperometric detection or evaporative light scattering detection in the presence of an online Dionex Carbohydrate Membrane Desalter (CMD). In these conditions, purified oligogalacturonate solutions were suitable, without further desalting steps, for infusion ESI-IT-MS experiments. This paper provides some interesting features of positive and negative ESI-IT-multiple MS (MSn) of these acidic oligosaccharides. The spectra acquired in both ion modes show characteristic fragments resulting from glycosidic bond and cross-ring cleavages. Under negative ionization conditions, the fragmentation of the singly-charged [M-H]- ions, as well as the Ci-, and Zi-, fragment ions through sequential MSn experiments, was always dominated by product ions from C- and Z-type glycosidic cleavages. All spectra also displayed 0.2 A-type cross-ring cleavage ions which carry linkage information. Collision-induced dissociation (CID) spectra of sodium-cationized species obtained under positive ionization conditions were more complex. Successive MSn experiments also led to the 0.2 A-type cross-ring cleavage ions observed together with B- and Y-type ions. The presence of the 0.2 A ion series was related to Mr 60 (C2H4O2) losses. Combined with the absence of the Mr 30 (CH2O) and the Mr 90 (C3H6O3) ions, these ions were indicative of 1-4 type glycosidic linkage.

Rapid Quantification of Low-Viscosity Acetyl-Triacylglycerols Using Electrospray Ionization Mass Spectrometry.

PubMed

Bansal, Sunil; Durrett, Timothy P

2016-09-01

Acetyl-triacylglycerols (acetyl-TAG) possess an sn-3 acetate group, which confers useful chemical and physical properties to these unusual triacylglycerols (TAG). Current methods for quantification of acetyl-TAG are time consuming and do not provide any information on the molecular species profile. Electrospray ionization mass spectrometry (ESI-MS)-based methods can overcome these drawbacks. However, the ESI-MS signal intensity for TAG depends on the aliphatic chain length and unsaturation index of the molecule. Therefore response factors for different molecular species need to be determined before any quantification. The effects of the chain length and the number of double-bonds of the sn-1/2 acyl groups on the signal intensity for the neutral loss of short chain length sn-3 groups were quantified using a series of synthesized sn-3 specific structured TAG. The signal intensity for the neutral loss of the sn-3 acyl group was found to negatively correlated with the aliphatic chain length and unsaturation index of the sn-1/2 acyl groups. The signal intensity of the neutral loss of the sn-3 acyl group was also negatively correlated with the size of that chain. Further, the position of the group undergoing neutral loss was also important, with the signal from an sn-2 acyl group much lower than that from one located at sn-3. Response factors obtained from these analyses were used to develop a method for the absolute quantification of acetyl-TAG. The increased sensitivity of this ESI-MS-based approach allowed successful quantification of acetyl-TAG in various biological settings, including the products of in vitro enzyme activity assays.