Science.gov

Sample records for positive electrospray ionisation

  1. Multi-residue analysis of drugs of abuse in wastewater and surface water by solid-phase extraction and liquid chromatography-positive electrospray ionisation tandem mass spectrometry.

    PubMed

    Baker, David R; Kasprzyk-Hordern, Barbara

    2011-03-25

    A new-multi residue method was developed for the environmental monitoring of 65 stimulants, opiod and morphine derivatives, benzodiazepines, antidepressants, dissociative anaesthetics, drug precursors, human urine indicators and their metabolites in wastewater and surface water. The proposed analytical methodology offers rapid analysis for a large number of compounds, with low limits of quantification and utilises only one solid-phase extraction-ultra performance liquid chromatography-positive electrospray ionisation tandem mass spectrometry (SPE-LC-MS/MS) method, thus overcoming the drawbacks of previously published procedures. The method employed solid phase extraction with the usage of Oasis MCX sorbent and subsequent ultra performance liquid chromatography-positive electrospray ionisation tandem mass spectrometry. The usage of a 1.7 μm particle size column (1 mm×150 mm) resulted in very low flow rates (0.04 mLmin(-1)), and as a consequence gave good sensitivity, low mobile phase consumption and short retention times for all compounds (from 2.9 to 23.1 min). High SPE recoveries (>60%) were obtained for the majority of compounds. The mean correlation coefficients of the calibration curves were typically higher than 0.997 and showed good linearity in the range 0-1000 μgL(-1). The method limits of detection ranged from 0.1 ngL(-1) for compounds including cocaine, benzoylecgonine, norbenzoylecgonine and 2-oxo-3-hydroxy-LSD to 100 ngL(-1) for caffeine. Method quantification limits ranged from 0.5 to 154.2 ngL(-1). Intra- and inter-day repeatabilities were on average less than 10%. The method accuracy range was within -33.1 to 30.1%. The new multi-residue method was used to analyse drugs of abuse in wastewater and river water in the UK environment. Of the targeted 65 compounds, 46 analytes were detected at levels above the method quantification limit (MQL) in wastewater treatment plant (WWTP) influent, 43 in WWTP effluent and 36 compounds in river water. Copyright

  2. Electrospray Ionisation Mass Spectrometry: Principles and Clinical Applications

    PubMed Central

    Ho, CS; Lam, CWK; Chan, MHM; Cheung, RCK; Law, LK; Lit, LCW; Ng, KF; Suen, MWM; Tai, HL

    2003-01-01

    This mini-review provides a general understanding of electrospray ionisation mass spectrometry (ESI-MS) which has become an increasingly important technique in the clinical laboratory for structural study or quantitative measurement of metabolites in a complex biological sample. The first part of the review explains the electrospray ionisation process, design of mass spectrometers with separation capability, characteristics of the mass spectrum, and practical considerations in quantitative analysis. The second part then focuses on some clinical applications. The capability of ESI-tandem-MS in measuring bio-molecules sharing similar molecular structures makes it particularly useful in screening for inborn errors of amino acid, fatty acid, purine, pyrimidine metabolism and diagnosis of galactosaemia and peroxisomal disorders. Electrospray ionisation is also efficient in generating cluster ions for structural elucidation of macromolecules. This has fostered a new and improved approach (vs electrophoresis) for identification and quantification of haemoglobin variants. With the understanding of glycohaemoglobin structure, an IFCC reference method for glycohaemoglobin assay has been established using ESI-MS. It represents a significant advancement for the standardisation of HbA1c in diabetic monitoring. With its other applications such as in therapeutic drug monitoring, ESI-MS will continue to exert an important influence in the future development and organisation of the clinical laboratory service. PMID:18568044

  3. On-line reaction monitoring by extractive electrospray ionisation.

    PubMed

    McCullough, Bryan J; Bristow, Tony; O'Connor, Gavin; Hopley, Chris

    2011-05-30

    The design and development of a novel extractive electrospray ionisation (EESI) device for on-line reaction monitoring is described. The EESI apparatus uses a secondary, grounded nebuliser to produce an analyte aerosol and a Venturi pump is then used to transfer a sample of the aerosol to an electrospray source where it is ionised. The EESI apparatus was then tested with a variety of small, organic molecules to assess sensitivity, linearity and dynamic range. The performance of the technique will depend on the mass spectrometer used for the experiments; in the configurations used here it has a usable dynamic range of around 3.5 orders of magnitude with a linear range of around 2.5 orders of magnitude and is capable of analysing species present down to low µg/mL with signal-to-noise ratio greater than 2.5. The use of EESI for reaction monitoring was validated using a series of mock reaction mixtures and then used to monitor the base hydrolysis of ethyl salicylate to salicylic acid. Copyright © 2011 John Wiley & Sons, Ltd.

  4. Liquid chromatography with electrospray ionisation mass spectrometric detection of phenolic compounds from Olea europaea.

    PubMed

    Ryan, D; Robards, K; Prenzler, P; Jardine, D; Herlt, T; Antolovich, M

    1999-09-10

    The results demonstrate the potential of electrospray ionisation mass spectrometry for the specific detection of phenolic species in olives. Phenolic compounds were detected with greater sensitivity in the negative ion mode, but results from positive and negative ion modes were complementary with the positive ion mode showing structurally significant fragments. This is demonstrated by the identification of oleuropein and isomers of verbascoside. The structure of the latter were confirmed by retention, mass spectral and nuclear magnetic resonance data. These isomers have not previously been reported in olive.

  5. Differential ionisation of natural antioxidant polyenes in electrospray and nanospray mass spectrometry.

    PubMed

    Guaratini, Thais; Gates, Paul J; Pinto, Ernani; Colepicolo, Pio; Lopes, Norberto P

    2007-01-01

    Carotenoids are natural products with high economic relevance for the pharmaceutical industries and are a common subject for biochemical research. Reported here is a comparative study of the ionisation of carotenoids by electrospray mass spectrometry (ESI-MS) and nanospray mass spectrometry (nanoESI-MS). The results demonstrate that, along with solvent choice, the influence of the different ionisation processes of ESI and nanoESI are fundamental in determining how ionisation is achieved and which ions (molecular ion or protonated molecule) are observed in MS. The increased understanding afforded by this study will help in the development of unequivocal microanalytical methods for carotenoids and related antioxidant polyenes.

  6. Determination of potato glycoalkaloids using high-pressure liquid chromatography-electrospray ionisation/mass spectrometry.

    PubMed

    Matsuda, Fumio; Morino, Keiko; Miyazawa, Haruna; Miyashita, Masahiro; Miyagawa, Hisashi

    2004-01-01

    A method for quantifying two toxic glycoalkaloids, alpha-solanine and alpha-chaconine, in potato (Solanum tuberosum) tuber tissue was developed using HPLC-electrospray ionisation (ESI)/MS. Potato samples were extracted with 5% aqueous acetic acid, and the extracts were subjected directly to HPLC-ESI/MS after filtration. By determining the intensities of the protonated molecules of alpha-solanine (m/z 868) and alpha-chaconine (m/z 852) using selected ion monitoring (positive ion mode), a sensitive assay was attained with detection limits of 38 and 14 ppb for the two glycoalkaloids, respectively. The high sensitivity and selectivity of MS detection effectively reduced the time of analysis thus enabling a high throughput assay of glycoalkaloids in potato tubers.

  7. Electrospray ionisation-cleavable tandem nucleic acid mass tag–peptide nucleic acid conjugates: synthesis and applications to quantitative genomic analysis using electrospray ionisation-MS/MS

    PubMed Central

    Thompson, Andrew; Prescott, Mark; Chelebi, Noorhan; Smith, John; Brown, Tom; Schmidt, Günter

    2007-01-01

    The synthesis and characterization of isotopomer tandem nucleic acid mass tag–peptide nucleic acid (TNT–PNA) conjugates is described along with their use as electrospray ionisation-cleavable (ESI-Cleavable) hybridization probes for the detection and quantification of target DNA sequences by electrospray ionisation tandem mass spectrometry (ESI-MS/MS). ESI-cleavable peptide TNT isotopomers were introduced into PNA oligonucleotide sequences in a total synthesis approach. These conjugates were evaluated as hybridization probes for the detection and quantification of immobilized synthetic target DNAs using ESI-MS/MS. In these experiments, the PNA portion of the conjugate acts as a hybridization probe, whereas the peptide TNT is released in a collision-based process during the ionization of the probe conjugate in the electrospray ion source. The cleaved TNT acts as a uniquely resolvable marker to identify and quantify a unique target DNA sequence. The method should be applicable to a wide variety of assays requiring highly multiplexed, quantitative DNA/RNA analysis, including gene expression monitoring, genetic profiling and the detection of pathogens. PMID:17259215

  8. Forensic applications of desorption electrospray ionisation mass spectrometry (DESI-MS).

    PubMed

    Morelato, Marie; Beavis, Alison; Kirkbride, Paul; Roux, Claude

    2013-03-10

    Desorption electrospray ionisation mass spectrometry (DESI-MS) is an emerging analytical technique that enables in situ mass spectrometric analysis of specimens under ambient conditions. It has been successfully applied to a large range of forensically relevant materials. This review assesses and highlights forensic applications of DESI-MS including the analysis and detection of illicit drugs, explosives, chemical warfare agents, inks and documents, fingermarks, gunshot residues and drugs of abuse in urine and plasma specimens. The minimal specimen preparation required for analysis and the sensitivity of detection achieved offer great advantages, especially in the field of forensic science. Crown Copyright © 2013. Published by Elsevier Ireland Ltd. All rights reserved.

  9. Screening for medium chain acyl-CoA dehydrogenase deficiency using electrospray ionisation tandem mass spectrometry

    PubMed Central

    Clayton, P.; Doig, M.; Ghafari, S.; Meaney, C.; Taylor, C.; Leonard, J.; Morris, M.; Johnson, A.

    1998-01-01

    OBJECTIVE—To establish criteria for the diagnosis of medium chain acyl-CoA dehydrogenase (MCAD) deficiency in the UK population using a method in which carnitine species eluted from blood spots are butylated and analysed by electrospray ionisation tandem mass spectrometry (ESI-MS/MS).
DESIGN—Four groups were studied: (1) 35 children, aged 4 days to 16.2 years, with proven MCAD deficiency (mostly homozygous for the A985G mutation, none receiving carnitine supplements); (2) 2168control children; (3) 482 neonates; and (4) 15 MCAD heterozygotes.
RESULTS—All patients with MCAD deficiency had an octanoylcarnitine concentration ([C8-Cn]) > 0.38 µM and no accumulation of carnitine species > C10 or < C6. Among the patients with MCAD deficiency, the [C8-Cn] was significantly lower in children > 10 weeks old and in children with carnitine depletion (free carnitine < 20 µM). Neonatal blood spots from patients with MCAD deficiency had a [C8-Cn] > 1.5 µM, whereas in heterozygotes and other normal neonates the [C8-Cn] was < 1.0 µM. In contrast, the blood spot [C8-Cn] in eight of 27 patients with MCAD deficiency > 10 weeks old fell within the same range as five of 15 MCAD heterozygotes (0.38-1.0 µM). However, the free carnitine concentrations were reduced (< 20 µM) in the patients with MCAD deficiency but normal in the heterozygotes.
CONCLUSIONS—Criteria for the diagnosis of MCAD deficiency using ESI-MS/MS must take account of age and carnitine depletion. If screening is undertaken at 7-10 days, the number of false positive and negative results should be negligible. Because there have been no instances of death or neurological damage following diagnosis of MCAD deficiency in our patient group, a strong case can be made for neonatal screening for MCAD deficiency in the UK.

 PMID:9797589

  10. Zwitterionic clusters with dianion core produced by electrospray ionisation of Brønsted acidic ionic liquids.

    PubMed

    Li, Jing; Wei, Wei; Nye, Leanne C; Schulz, Peter S; Wasserscheid, Peter; Ivanović-Burmazović, Ivana; Drewello, Thomas

    2012-04-21

    New Brønsted acidic ionic liquids (BAILs) are prepared by treating zwitterions, which are composed of an imidazolium cation and a sulfonate anion, with an alkanedisulfonic acid. Acidification of the zwitterions produces the cation and deprotonation of the alkanedisulfonic acid forms the anion of the new BAILs. Direct laser desorption/ionisation (LDI), matrix-assisted LDI (MALDI) and electrospray ionisation (ESI) are employed to transfer ions into the gas-phase for detection by mass spectrometry and for dissociation studies by tandem mass spectrometry. The components of the BAILs are confirmed by LDI and MALDI by the detection of the respective cation and anion and by ESI by the observation of the cation and the dianion. A prominent feature of ESI is the formation of aggregates (cluster ions). Positively charged cluster ions are formally composed of multiple zwitterions plus one additional proton. In the negative-ion mode the clusters also incorporate the zwitterions which are, however, linked with the alkanedisulfonate dianion. In collision-induced dissociations (CID), the cationic aggregates show the evaporation of zwitterions until the protonated zwitterion is reached. Similarly, the cluster dianions release zwitterions until the free alkane disulfonate dianion is reached. However, the 1:1 adduct of dianion and zwitterion also displays proton transfer and Coulomb explosion into the mono-protonated disulfonic mono-anion and an imidazole-based carbene with sulfonate mono-anion. This journal is © the Owner Societies 2012

  11. Simultaneous Determination of Celecoxib, Erlotinib, and its Metabolite Desmethyl-Erlotinib (OSI-420) in Rat Plasma by Liquid chromatography/Tandem Mass Spectrometry with Positive/Negative Ion-Switching Electrospray Ionisation.

    PubMed

    Thappali, Satheeshmanikandan R S; Varanasi, Kanthikiran; Veeraraghavan, Sridhar; Arla, Rambabu; Chennupati, Sandhya; Rajamanickam, Madheswaran; Vakkalanka, Swaroop; Khagga, Mukkanti

    2012-01-01

    A new method for the simultaneous determination of celecoxib, erlotinib, and its active metabolite desmethyl-erlotinib (OSI-420) in rat plasma, by liquid chromatography/tandem mass spectrometry with positive/negative ion-switching electrospray ionization mode, was developed and validated. Protein precipitation with methanol was selected as the method for preparing the samples. The analytes were separated on a reverse-phase C(18) column (50mm×4.6mm i.d., 3μ) using methanol: 2 mM ammonium acetate buffer, and pH 4.0 as the mobile phase at a flow rate 0.8 mL/min. Sitagliptin and Efervirenz were used as the internal standards for quantification. The determination was carried out on a Theremo Finnigan Quantam ultra triple-quadrupole mass spectrometer, operated in selected reaction monitoring (SRM) mode using the following transitions monitored simultaneously: positive m/z 394.5→278.1 for erlotinib, m/z 380.3→278.1 for desmethyl erlotinib (OSI-420), and negative m/z -380.1→ -316.3 for celecoxib. The limits of quantification (LOQs) were 1.5 ng/mL for Celecoxib, erlotinib, and OSI-420. Within- and between-day accuracy and precision of the validated method were within the acceptable limits of < 15% at all concentrations. The quantitation method was successfully applied for the simultaneous estimation of celecoxib, erlotinib, and desmethyl erlotinib in a pharmacokinetic study in Wistar rats.

  12. Chemical profile of mango (Mangifera indica L.) using electrospray ionisation mass spectrometry (ESI-MS).

    PubMed

    Oliveira, Bruno G; Costa, Helber B; Ventura, José A; Kondratyuk, Tamara P; Barroso, Maria E S; Correia, Radigya M; Pimentel, Elisângela F; Pinto, Fernanda E; Endringer, Denise C; Romão, Wanderson

    2016-08-01

    Mangifera indica L., mango fruit, is consumed as a dietary supplement with purported health benefits; it is widely used in the food industry. Herein, the chemical profile of the Ubá mango at four distinct maturation stages was evaluated during the process of growth and maturity using negative-ion mode electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI(-)FT-ICR MS) and physicochemical characterisation analysis (total titratable acidity (TA), total soluble solids (TSS), TSS/TA ratio, and total polyphenolic content). Primary (organic acids and sugars) and secondary metabolites (polyphenolic compounds) were mostly identified in the third maturation stage, thus indicating the best stage for harvesting and consuming the fruit. In addition, the potential cancer chemoprevention of the secondary metabolites (phenolic extracts obtained from mango samples) was evaluated using the induction of quinone reductase activity, concluding that fruit polyphenols have the potential for cancer chemoprevention.

  13. Ruthenium versus platinum: interactions of anticancer metallodrugs with duplex oligonucleotides characterised by electrospray ionisation mass spectrometry.

    PubMed

    Groessl, Michael; Tsybin, Yury O; Hartinger, Christian G; Keppler, Bernhard K; Dyson, Paul J

    2010-06-01

    The binding of the ruthenium-based anticancer drug candidates KP1019, NAMI-A and RAPTA-T towards different double-stranded oligonucleotides was probed by electrospray ionisation mass spectrometry and compared with that of the widely used platinum-based chemotherapeutics cisplatin, carboplatin and oxaliplatin. It was found that the extent of adduct formation decreased in the following order: cisplatin > oxaliplatin > NAMI-A > RAPTA-T > carboplatin > KP1019. In addition to the characterisation of the adducts formed with the DNA models, the binding sites of the metallodrugs on the oligonucleotides were elucidated employing top-down tandem mass spectrometry and were found to be similar for all the metallodrugs studied, irrespective of the sequence of the oligonucleotide. A strong preference for guanine residues was established.

  14. Multi-residue method for the determination of basic/neutral pharmaceuticals and illicit drugs in surface water by solid-phase extraction and ultra performance liquid chromatography-positive electrospray ionisation tandem mass spectrometry.

    PubMed

    Kasprzyk-Hordern, B; Dinsdale, R M; Guwy, A J

    2007-08-17

    The paper presents the development and validation of a new multi-residue method for the determination of 28 basic/neutral pharmaceuticals (antiepileptics, antibacterial drugs, beta-blockers, analgesics, lipid-regulating agents, bronchodilators, histamine-2-blockers, anti-inflammatory agents, calcium channel blockers, angiotensin-II antagonists and antidepressants) and illicit drugs in surface water with the usage of a new technique: ultra performance liquid chromatography-positive electrospray tandem mass spectrometry (UPLC-MS/MS). The usage of the novel UPLC system with 1.7 microm particle size and 1mm internal diameter column allowed for low mobile phase flow rates (0.07 mL min(-1)) and short retention times (from 1.3 to 15.5 min) for all compounds analysed. As a result, a fast and cost-effective method was developed. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for pharmaceuticals extraction from environmental samples. The influence of matrix-assisted ion suppression and low SPE recovery on the sensitivity of the method was studied. The instrumental limits of quantification varied from 0.2 to 10 microg L(-1). The method limits of quantification were at low nanogram per litre levels and ranged from 0.3 to 50 ng L(-1). The instrumental and method intra- and inter-day repeatabilities were on average less than 10%. The method was applied for the determination of pharmaceuticals in Rivers Taff (UK) and Warta (Poland). Fifteen compounds were determined in river water at levels ranging from single nanograms to single micrograms per litre.

  15. Free energy for blue copper protein unfolding determined by electrospray ionisation mass spectrometry.

    PubMed

    Cunsolo, V; Foti, S; La Rosa, C; Saletti, R; Canters, G W; Verbeet, M P

    2001-01-01

    An electrospray ionisation (ESI) mass spectrometric method for the determination of the free energy (DeltaG) of unfolding of proteins is described. The method was tested using three blue copper proteins: wild type azurin, Cys-3Ala/Cys-26Ala (C3A/C26A) azurin mutant and wild-type amicyanin. The time course of the denaturation process of the proteins dissolved in methanol/water (50:50, v/v, pH 3.5) was followed by recording ESI mass spectra at time intervals. The spectra showed two series of peaks, corresponding to the native holo-protein and the unfolded apo-protein. From the intensity ratio of these two series of peaks at increasing time and at equilibrium, the free energy for the unfolding process for the three proteins could be determined. To evaluate the reliability of the thermodynamic data obtained by the ESI mass spectrometric approach, the denaturation process was followed by UV-VIS spectroscopy. The two sets of data obtained by these independent methods were in good agreement indicating that the ESI-MS approach can be used to obtain reliable quantitative information about the protein unfolding process. In principle, this approach can be applied to other proteins and requires very low amounts of sample, due to the intrinsic sensitivity of mass spectrometry. This may prove particularly useful when the amount of sample available prevents the use of current methods.

  16. Analysis of oilfield produced waters and production chemicals by electrospray ionisation multi-stage mass spectrometry (ESI-MSn).

    PubMed

    McCormack, P; Jones, P; Hetheridge, M J; Rowland, S J

    2001-10-01

    Large quantities of diverse polar organic chemicals are routinely discharged from oil production platforms in so-called produced waters. The environmental fate of many of these is unknown since few methods exist for their characterisation. Preliminary investigations into the use of multistage electrospray ionisation ion trap mass spectrometry (ESI-MSn) show its potential for the identification and quantification of compounds in specialty oilfield chemicals (corrosion inhibitors, scale inhibitors, biocides and demulsifiers) and produced waters. Multiple stage mass spectrometry (MSn) with both positive and negative ion detection allows high specificity detection and characterisation of a wide range of polar and charged molecules. For example, linear alkylbenzenesulfonates (LAS), alkyldimethylbenzylammonium compounds, 2-alkyl-1-ethylamine-2-imidazolines, 2-alkyl-1-[N-ethylalkylamide]-2-imidazolines and a di-[alkyldimethylammonium-ethyl]ether were all identified and characterised in commercial formulations and/or North Sea oilfield produced waters. The technique should allow the marine environmental effects and fates of some of these polar compounds to be studied.

  17. Characterisation of a proposed internet synthesis of N,N-dimethyltryptamine using liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Martins, Cláudia P B; Freeman, Sally; Alder, John F; Brandt, Simon D

    2009-08-14

    The psychoactive properties of N,N-dimethyltryptamine (DMT) are known to induce altered states of consciousness in humans. These properties attract great interest from clinical, neuroscientific, clandestine and forensic communities. The Breath of Hope Synthesis was reported on an internet website as a convenient two-step methodology for the preparation of DMT. The analytical characterisation of the first stage was the subject of previous publications by the authors and involved the thermal decarboxylation of tryptophan and the formation of tryptamine. The present study reports on the characterisation of the second step of this procedure which was based on the methylation of tryptamine. This employed methyl iodide and benzyltriethylammonium chloride/sodium hydroxide as a phase transfer catalyst. The reaction product was characterised by liquid chromatography/electrospray ionisation tandem mass spectrometry and orthogonal acceleration time-of-flight mass spectrometry. Quantitative evaluation was carried out in positive multiple reaction monitoring mode (MRM), which included synthesis of the identified reaction products. MRM screening of the product did not lead to the detection of DMT. Instead, 11.1% tryptamine starting material, 21.0% N,N,N-trimethyltryptammonium iodide (TMT) and 47.4% 1-N-methyl-TMT were detected. A 0.5% trace of the monomethylated N-methyltryptamine was also detected. This study demonstrated the impact on product purity of doubtful synthetic methodologies discussed on the internet.

  18. Gas-phase dissociation of ionic liquid aggregates studied by electrospray ionisation mass spectrometry and energy-variable collision induced dissociation.

    PubMed

    Fernandes, Ana M; Coutinho, João A P; Marrucho, Isabel M

    2009-01-01

    Positive singly charged ionic liquid aggregates [(C(n)mim)(m+1)(BF(4))(m)](+) (mim = 3-methylimidazolium; n = 2, 4, 8 and 10) and [(C(4)mim)(m+1)(A)(m)](+) (A = Cl(-), BF(4) (-), PF(6) (-), CF(3)SO(3) (-) and (CF(3)SO(2))(2)N(-)) were investigated by electrospray ionisation mass spectrometry and energy-variable collision induced dissociation. The electrospray ionisation mass spectra (ESI-MS) showed the formation of an aggregate with extra stability for m = 4 for all the ionic liquids with the exception of [C(4)mim][CF(3)SO(3)]. ESI-MS-MS and breakdown curves of aggregate ions showed that their dissociation occurred by loss of neutral species ([C(n)mim][A])(a) with a >or= 1. Variable-energy collision induced dissociation of each aggregate from m = 1 to m = 8 for all the ionic liquids studied enabled the determination of E(cm, 1/2) values, whose variation with m showed that the monomers were always kinetically much more stable than the larger aggregates, independently of the nature of cation and anion. The centre-of-mass energy values correlate well with literature data on ionic volumes and interaction and hydrogen bond energies.

  19. Capillary electrophoresis with electrospray ionisation-mass spectrometry for the characterisation of degradation products in aged papers.

    PubMed

    Dupont, Anne-Laurence; Seemann, Agathe; Lavédrine, Bertrand

    2012-01-30

    A methodology for capillary electrophoresis/electrospray ionisation mass spectrometry (CE/ESI-MS) was developed for the simultaneous analysis of degradation products from paper among two families of compounds: low molar mass aliphatic organic acids, and aromatic (phenolic and furanic) compounds. The work comprises the optimisation of the CE separation and the ESI-MS parameters for improved sensitivity with model compounds using two successive designs of experiments. The method was applied to the analysis of lignocellulosic paper at different stages of accelerated hygrothermal ageing. The compounds of interest were identified. Most of them could be quantified and several additional analytes were separated.

  20. Identification of phenolic constituents in red chicory salads (Cichorium intybus) by high-performance liquid chromatography with diode array detection and electrospray ionisation tandem mass spectrometry.

    PubMed

    Carazzone, Chiara; Mascherpa, Dora; Gazzani, Gabriella; Papetti, Adele

    2013-06-01

    Phenolic acids and flavonoids extracted from several types of Cichorium intybus var. silvestre salads ("Chioggia", "Treviso", "Treviso tardivo", and "Verona") were characterised by high-performance liquid chromatography-electrospray ionisation/mass spectrometry. Among the 64 compounds detected, several hydroxycinnamic acid derivatives including 8 mono- and dicaffeoylquinic acids, 3 tartaric acid derivatives, 31 flavonol and 2 flavone glycosides, as well as 10 anthocyanins were characterised based on UV spectra and MS(n) fragmentation patterns. Furthermore, several isomers of caffeic acid derivatives were distinguished for the first time by their specific mass spectral data. This is the first study reporting the glycosylation type and position of mono- and diglycosylated flavonoids in red salads.

  1. On-line coupling of a microelectrode array equipped poly(dimethylsiloxane) microchip with an integrated graphite electrospray emitter for electrospray ionisation mass spectrometry.

    PubMed

    Liljegren, Gustav; Dahlin, Andreas; Zettersten, Camilla; Bergquist, Jonas; Nyholm, Leif

    2005-10-01

    A novel method for the manufacturing of microchips for on-chip combinations of electrochemistry (EC) and sheathless electrospray ionisation mass spectrometry (ESI-MS) is described. The technique, which does not require access to clean-room facilities, is based on the incorporation of an array of gold microcoil electrodes into a poly(dimethylsiloxane)(PDMS) microflow channel equipped with an integrated graphite based sheathless ESI emitter. Electrochemical measurements, which were employed to determine the electroactive area of the electrodes and to test the microchips, show that the manufacturing process was reproducible and that the important interelectrode distance in the electrochemical cell could to be adequately controlled. The EC-ESI-MS device was evaluated based on the ESI-MS detection of the oxidation products of dopamine. The results demonstrate that the present on-chip approach enables full potentiostatic control of the electrochemical cell and the attainment of very short transfer times between the electrochemical cell and the electrospray emitter. The transfer times were 0.6 and 1.2 s for flow rates of 1.0 and 0.5 microL min(-1), respectively, while the electrochemical conversion efficiency of the electrochemical cell was found to be 30% at a flow rate of 0.5 microL min(-1). To decouple the electrochemical cell from the ESI-MS high voltage and to increase the user-friendliness, the on-line electrochemistry-ESI-MS experiments were performed using a wireless Bluetooth battery-powered instrument with the chip floating at the potential induced by the ESI high voltage. The described on-chip EC-ESI-MS device can be used for fundamental electrochemical investigations as well as for applications based on the use of electrochemically controlled sample pretreatment, preconcentration and ionisation steps prior to ESI-MS.

  2. The detection of piroxicam, tenoxicam and their metabolites in equine urine by electrospray ionisation ion trap mass spectrometry.

    PubMed

    McKinney, Andrew R; Suann, Craig J; Stenhouse, Allen M

    2004-01-01

    An investigation has been conducted into the metabolism and urinary excretion of orally administered piroxicam and tenoxicam in the horse. The major component detected in urine after the administration of piroxicam was 5'-hydroxypiroxicam, which was detectable up to 24 h post-administration. Unchanged piroxicam was present only as a minor component. In contrast, unchanged tenoxicam was the major component observed after the administration of tenoxicam, being detectable for 72 h post-administration, while 5'-hydroxytenoxicam was a minor component. Phase II beta-glucuronide conjugation in each case was found to be negligible. The ion trap mass spectral characteristics of piroxicam, tenoxicam, 5'-hydroxypiroxicam and 5'-hydroxytenoxicam under electrospray ionisation conditions were examined in some detail.

  3. Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Jahnke, Annika; Gandrass, Juergen; Ruck, Wolfgang

    2004-04-30

    Reversed-phase LC-MS/MS is used to determine major estrogenic alkylphenol ethoxylates (APEOs) and their biotransformation products. It allows the simultaneous analysis of eight APEOs, alkylphenoxy carboxylates (APECs) and alkylphenols (APs) in sewage treatment plant (STP) effluents in the same extract after solid-phase enrichment on polymeric Oasis HLB. As precursor ions, [APEO + NH4]+, [APEC - H]- and [AP - H]- were monitored. Instrumental limits of detection (LOD) were 2-600 pg, corresponding to sample concentrations of 0.04-12 ng l(-1), without correction for overall method recoveries. Matrix-induced signal suppression during electrospray ionisation (ESI) and extraction as well as overall method recoveries were assessed and the suitability of deuterated surrogates as internal standards was evaluated.

  4. The mechanism of alkene elimination from protonated toluenesulphonamides generated by electrospray ionisation.

    PubMed

    Saidykhan, Amie; Ebert, Jenessa; Martin, William H C; Gallagher, Richard T; Bowen, Richard D

    2016-01-01

    The positive ion electrospray mass spectra of a range of sulphonamides of general structure CH3C6H4SO2NHR1 [R1 = CnH2n(+1) (n = 1-7), CnH2n-1 (n = 3, 4), C6H5, C6H5CH2 and C6H5CH(CH3)] and CH3C6H4SO2NR1R(2) [R(1), R(2) = CnH2n+1 (n = 1-8)] are reported and discussed. The protonated sulphonamides derived from saturated primary and secondary aliphatic amines generally fragment to only a limited extent unless energised by collision. Two general fragmentations are observed: firstly, elimination of an alkene, CnH2n, obtained by hydrogen abstraction from one of the CnH2n+1 alkyl groups on nitrogen; secondly, cleavage to form CH3C6H4SO2+. The mechanism by which an alkene is lost has been probed by studying the variation of the intensity of the [M + H - CnH2n](+) signal with the structure of the alkyl substituent(s) on nitrogen and by monitoring the competition between the loss of different alkenes from protonated unsymmetrical sulphonamides in which two different alkyl groups are attached to nitrogen. This fragmentation is favoured by branching of the alkyl group at the carbon atom directly attached to nitrogen, thus suggesting that it involves a mechanism in which the stability of the cation obtained by stretching the bond connecting the nitrogen atom to the alkyl group is critical. This interpretation also explains the competition between alkene elimination and cleavage to form CH3C6H4SO2(+) (and, in some cases, cleavage to form C6H5CH2(+) or [C6H5CHCH3](+)).

  5. Online antioxidant activity and ultra-performance LC-electrospray ionisation-quadrupole time-of-fight mass spectrometry for chemical fingerprinting of Indian polyherbal formulations.

    PubMed

    Bhandari, Pamita; Kumar, Neeraj; Khan, Shahid M; Bhutani, Kamlesh K

    2016-01-01

    A HPLC-DAD-DPPH method was developed for evaluating the 1, 1-diphenyl-2-picryl hydrazyl free radical scavenging activity of ethylacetate extracts of different polyherbal formulations (draksarista, draksava, lohasava and arvindasava) by using RP-18e column. The ethylacetate extract from polyherbal, 'draksarista' exhibited maximum free radical scavenging activity (99.9 ± 0.38%) followed by draksava (99.8 ± 0.34%), lohasava (98.5 ± 0.30%) and arvindasava (42.3 ± 0.34%) at 100 μg mL(-1). Simultaneously, ultra-performance liquid chromatography coupled with electrospray ionisation-quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used to study chemical composition of the ethylacetate extracts of formulations. The characteristic electrospray mass ionisation reveals the dominance of polyphenols and their glycosides in the four polyherbal formulations.

  6. Detection of phenolic oxidation products in cider apple juice by high-performance liquid chromatography electrospray ionisation ion trap mass spectrometry.

    PubMed

    Bernillon, S; Guyot, S; Renard, C M G C

    2004-01-01

    Juice was prepared from cider apples of the cultivar "Kermerrien" under oxidative conditions. After isolation by solid-phase extraction, the phenolic fraction was subjected to high-performance liquid chromatography/electrospray ionisation mass spectrometry. SIM scans were performed at m/z values obtained in model solutions. The oxidation products, resulting from coupling between a molecule of caffeoylquinic acid and caffeoylquinic acid, catechin or dimeric flavan-3-ol, were detected.

  7. Fragmentation of mycosporine-like amino acids by hydrogen/deuterium exchange and electrospray ionisation tandem mass spectrometry.

    PubMed

    Cardozo, Karina H M; Carvalho, Valdemir M; Pinto, Ernani; Colepicolo, Pio

    2006-01-01

    The determination and identification of mycosporine-like amino acids (MAAs) from algae remain a major challenge due to the low concentration. Mass spectrometry (MS) can make an invaluable contribution in the search and identification of MAAs because of its high sensitivity, possibility of coupling with liquid chromatography, and the availability of powerful tandem mass spectrometric techniques. However, the unequivocal determination of the presence and location of important functional groups present on the basic skeleton of the MAAs is often elusive due to their inherent instability under MS conditions. In this study, the use of hydrogen/deuterium (H/D) exchange and electrospray ionisation tandem mass spectrometry (ESI-MS/MS) for characterisation of four MAAs (palythine, asterina, palythinol and shinorine) isolated from the macroalgae Gracilaria tenuistipitata Chang et Xia was investigated. The accurate-mass confirmation of the protonated molecules was performed on a Q-TOF instrument. We demonstrate that employing deuterium labelling in ESI-MS/MS analysis provides a convenient tool for the determination of new MAAs. Although the fragmentation patterns of MAAs were discussed earlier, to our knowledge, this is the first time that mechanisms are proposed.

  8. Confirmation and 3D profiling of anabolic steroid esters in injection sites using imaging desorption electrospray ionisation (DESI) mass spectrometry.

    PubMed

    de Rijke, Eva; Hooijerink, Dick; Sterk, Saskia S; Nielen, Michel W F

    2013-01-01

    In this study, desorption electrospray ionisation (DESI) linear ion trap tandem mass spectrometry (MS(n)) was applied for the confirmation and three-dimensional profiling of anabolic steroid esters in an injection site of bovine muscle. The spatial resolution of the DESI-MS(n) was demonstrated by scanning hormone esters and marker ink lines drawn at various distances on a microscopic slide at set distances, using an x-scanner with manual y and z adjustment. Tissue slices of bovine muscle injected with a hormone cocktail were analysed. All anabolic steroid esters could be directly detected in the sample and confirmed on the basis of identification points awarded for selected MS/MS transitions according to the performance criteria given in Commission Decision 2002/657/EC. Moreover, the injection site could be mapped by two-dimensional and three-dimensional imaging MS, showing a horizontal and vertical distribution through the muscle tissue. This DESI approach offers potential for analysis of injection sites of steroid esters from illegally treated animals; moreover, direct analysis by ambient imaging DESI-MS still allows conventional extraction and analysis of the whole tissue for further confirmatory or contra-analysis afterwards.

  9. Fragmentation mechanisms of protonated benzylamines. Electrospray ionisation-tandem mass spectrometry study and ab initio molecular orbital calculations.

    PubMed

    Bourcier, Sophie; Hoppilliard, Yannik

    2003-01-01

    Our research into neurotransmitters in a biological fluid presented an opportunity to investigate the fragmentations under low collision energy characterising benzyl-amines protonated under electrospray ionisation (ESI) conditions in a triple quadrupole mass spectrometer. In this work we present the breakdown graphs of protonated 3,4-dihydroxybenzylamine, DHBAH(+), and 3-methoxy, 4-hydroxybenzylamine, HMBAH(+), at various source temperatures and various pressures in the collision cell, the collision energy varying from 0 to 46 eV in the laboratory frame. Both parent ions eliminate first NH(3) at very low collision energy. The fragmentations of [MH - NH(3)](+) occur at high collision energy and are quite different for DHBAH(+) and HMBAH(+): formation of [MH - NH(3) - H(2)O - CO](+) for the former; formation of the radical cation [MH - NH(3) - CH(3)](+.) for the latter. These fragmentations are interpreted by means of ab initio calculations up to the B3LYP/6-311+G(2d,2p) level of theory. The successive losses of H(2)O and CO involve first the rearrangement in two steps of benzylic ions formed by loss of NH(3) into tropylium ions. The transition states associated with this rearrangement are very high in energy (about 400 kJ mol(-1) above MH(+)) explaining (i). the absence of an ion corresponding to [DHBAH - NH(3) - H(2)O](+). The determining steps associated with the losses of H(2)O and with H(2)O + CO are located lower in energy than the transition states associated with the isomerisation of benzylic ions into tropylium ions; explaining (ii). the formation of the radical cation [MH - NH(3) - CH(3)](+.). The homolytic cleavage of CH(3)-O requires less energy than does the rearrangement.

  10. Structure elucidation of unsaturated fatty acids after vicinal hydroxylation of the double bonds by negative electrospray ionisation low-energy tandem mass spectrometry.

    PubMed

    Moe, Morten K; Jensen, Einar

    2004-01-01

    A method for determining the positions of double bonds in unsaturated fatty acids by use of negative electrospray ionisation low-energy tandem mass spectrometry is described. First, a vicinal hydroxylation of the double bonds of mono- and poly-unsaturated fatty acids was performed. Low-energy collision activation dissociation of the deprotonated molecules produced structurally informative ions formed by a-cleavages relative to the hydroxyl groups. Abundant fragment ions that confirmed the positions of all hydroxyl groups, and thus the positions of the double bonds in the native fatty acids, were observed in the spectra of derivatised mono-, di-, and tri-unsaturated fatty acids. Two types of ions were observed, called [alpha'(n)](-) and [alpha(n)](-). The letter n indicates the positions of the hydroxyl groups. The structurally diagnostic ions [alpha'(n)](-) were produced by cleavages distal to the hydroxyl-groups with the charge retained on the carboxylate. [alpha'(n)](-) ions originating from all hydroxyl-groups were observed in the spectra of modified mono-, di-, and tri-unsaturated fatty acids. Initial proton transfer of a hydroxyl proton to the carboxylate with subsequent cleavages proximal to the hydroxyl groups, relative to the carboxylate, resulted in the two structurally diagnostic [alpha(n)](-) ions. In hydroxylated fatty acids having two or more double bonds in their native structure, [alpha(n)](-) ions originating only from the two final hydroxyl-groups were observed. The formation of all ions of [alpha'(n)](-) and [alpha(n)](-) type can be rationalised by a six-membered transition state. Hydroxylated deprotonated tetra-, penta-, and hexa-unsaturated fatty acids also produced [alpha'(n)](-) ions indicating the positions of most of the hydroxyl-groups, whereas the [alpha(n)](-) ions were observed as described above. The method described offers a simple approach to the determination of the positions of double bonds in unsaturated fatty acids, and is an

  11. Determination of steroid hormones, hormone conjugates and macrolide antibiotics in influents and effluents of sewage treatment plants utilising high-performance liquid chromatography/tandem mass spectrometry with electrospray and atmospheric pressure chemical ionisation.

    PubMed

    Schlüsener, Michael P; Bester, Kai

    2005-01-01

    In this study we present a high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) method which has been elaborated to analyse steroid hormones, hormone conjugates, oral contraceptives and macrolide antibiotics unchanged in unfiltered influents and effluents of sewage treatment plants (STPs). HPLC separation of the steroid hormones was achieved in 35 min, as well as those of the antibiotics. The analytes were extracted by solid-phase extraction, followed by clean-up using size exclusion chromatography (SEC). For the final quantification HPLC/MS/MS was used. The two ionisation modes, electrospray ionisation (ESI) and atmospheric pressure chemical ionisation (APCI), in HPLC/MS/MS were compared for the analysis of steroid hormones. For quantitative results drastic matrix effects were observed while using ESI. These effects were less pronounced while using APCI. These pitfalls were additionally reduced by clean-up using SEC as well as isotope dilution. Additionally, two multiple reaction monitoring (MRM) transitions per compound were used to prevent false positive results. Recovery experiments with spiked tap water with concentrations varying from 1 to 1000 ng/L gave constant recovery rates: The recovery rates for the hormones and conjugates ranged from 58 to 107%, those of the contraceptives ranged from 83 to 109%. The relative standard deviation was found to be 7 to 24% and the limits of detection were 0.1 to 4.5 ng/L. The recovery rates of the macrolide antibiotics ranged from 76 to 103%, while the relative standard deviation was found to be 7 to 14% and the limits of detection ranged from 0.6 to 1.8 ng/L. The maximum concentrations found in influents of a STP was 470 ng/L for estriol and 1200 ng/L for erythromycin. Copyright (c) 2005 John Wiley & Sons, Ltd.

  12. Rapid characterisation and identification of compounds in Saposhnikoviae Radix by high-performance liquid chromatography coupled with electrospray ionisation quadrupole time-of-flight mass spectrometry.

    PubMed

    Chen, Luxiao; Chen, Xiangyang; Su, Lei; Jiang, Yanyan; Liu, Bin

    2017-08-18

    Saposhnikoviae Radix (SR), the dried root of Saposhnikovia divaricata (Turcz.) Schischk. (Umbelliferae), is commonly used as a traditional Chinese medicine. In this study, a rapid and accurate method was firstly, developed for the qualitative analysis of SR by high-performance liquid chromatography coupled with electrospray ionisation quadrupole time-of-flight mass spectrometry (HPLC-ESI-Q-TOF-MS/MS). A total of 45 compounds were identified or tentatively characterised, including 13 chromones, 28 coumarins and four others. Among them, 16 compounds were identified from SR for the first time. In addition, six chromones reference standards, including two isolated compounds of 3'-O-angeloylhamaudol and norcimifugin from the extraction of SR, were used to study the fragmentation pathways of chromones. The developed method was effective for characterising the compounds of SR, and the results of the study enriched the understanding of the chemical connotation.

  13. The fragmentation pathways of protonated Amiton in the gas phase: towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry.

    PubMed

    Ellis-Steinborner, Simon; Ramachandran, Aravind; Blanksby, Stephen J

    2006-01-01

    Amiton (O,O-diethyl-S-[2-(diethylamino)ethyl] phosphorothiolate), otherwise known as VG, is listed in schedule 2 of the Chemical Weapons Convention (CWC) and has a structure closely related to VX (O-ethyl-S-(2-diisopropylamino)ethylmethylphosphonothiolate). Fragmentation of protonated VG in the gas phase was performed using electrospray ionisation ion trap mass spectrometry (ESI-ITMS) and revealed several characteristic product ions. Quantum chemical calculations provide the most probable structures for these ions as well as the likely unimolecular mechanisms by which they are formed. The decomposition pathways predicted by computation are consistent with deuterium-labeling studies. The combination of experimental and theoretical data suggests that the fragmentation pathways of VG and analogous organophosphorus nerve agents, such as VX and Russian VX, are predictable and thus ESI tandem mass spectrometry is a powerful tool for the verification of unknown compounds listed in the CWC.

  14. Analysis of peptides and protein digests by reversed phase high performance liquid chromatography-electrospray ionisation mass spectrometry using neutral pH elution conditions.

    PubMed

    Yang, Yuanzhong; Boysen, Reinhard I; Chowdhury, Jamil; Alam, Asif; Hearn, Milton T W

    2015-05-04

    In this study, the advantages of carrying out the analysis of peptides and tryptic digests of proteins under gradient elution conditions at pH 6.5 by reversed-phase liquid chromatography (RP-HPLC) and in-line electrospray ionisation mass spectrometry (ESI-MS) are documented. For these RP separations, a double endcapped, bidentate anchored n-octadecyl wide pore silica adsorbent was employed in a capillary column format. Compared to the corresponding analysis of the same peptides and protein tryptic digests using low pH elution conditions for their RP-HPLC separation, this alternative approach provides improved selectivity and more efficient separation of these analytes, thus allowing a more sensitive identification of proteins at different abundance levels, i.e. more tryptic peptides from the same protein could be confidently identified, enabling higher sequence coverage of the protein to be obtained. This approach was further evaluated with very complex tryptic digests derived from a human plasma protein sample using an online two-dimensional (2D) strong cation-exchange (SCX)-RP-HPLC-ESI-MS/MS system. Again, at pH 6.5, with mobile phases of different compositions, improved chromatographic selectivities were obtained, concomitant with more sensitive on-line electrospray ionisation tandem mass spectrometric (ESI-MS/MS) analysis. As a consequence, more plasma proteins could be confidently identified, highlighting the potential of these RP-HPLC methods with elution at pH 6.5 to extend further the scope of proteomic investigations. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Characterisation of poly(alkyl methacrylate)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS)

    NASA Astrophysics Data System (ADS)

    Jackson, Anthony T.; Slade, Susan E.; Scrivens, James H.

    2004-11-01

    Electrospray ionisation-tandem mass spectrometry (ESI-MS/MS) has been employed for the characterisation of two poly(alkyl methacrylate) polymers, namely poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). Collision-induced dissociation (CID) experiments were performed in a quadrupole orthogonal time-of-flight (ToF) tandem mass spectrometer fitted with a nanospray source. Tandem mass spectra from singly, doubly and triply charged precursor ions (with alkali metals used for cationisation of the oligomers) are shown and the data are compared to those previously generated by means of matrix-assisted laser desorption/ionisation-collision-induced dissociation (MALDI-CID). These data indicate that cations with greater ionic radii may yield the most useful structural information as the mass-to-charge ratio of the precursor ion increases, whereas lithium or sodium ions are proposed to be ideal for obtaining spectra from lower molecular weight oligomers. Fragment ions at low mass-to-charge ratios dominate the spectra. Two series of peaks may be used to calculate the masses of the initiating and terminating end groups of the polymer. Ion peaks of greater mass-to-charge ratios form series that may be used to infer sequence information from the polymers.

  16. Identification of N-glycans from Ebola virus glycoproteins by matrix-assisted laser desorption/ionisation time-of-flight and negative ion electrospray tandem mass spectrometry

    PubMed Central

    Ritchie, Gayle; Harvey, David J.; Stroeher, Ute; Feldmann, Friederike; Feldmann, Heinz; Wahl-Jensen, Victoria; Royle, Louise; Dwek, Raymond A.; Rudd, Pauline M.

    2012-01-01

    The larger fragment of the transmembrane glycoprotein (GP1) and the soluble glycoprotein (sGP) of Ebola virus were expressed in human embryonic kidney cells and the secreted products were purified from the supernatant for carbohydrate analysis. The N-glycans were released with PNGase F from within sodium dodecyl sulphate/polyacrylamide gel electrophoresis (SDS-PAGE) gels. Identification of the glycans was made with normal-phase high-performance liquid chromatography (HPLC), matrix-assisted laser desorption/ionisation mass spectrometry, negative ion electrospray ionisation fragmentation mass spectrometry and exoglycosidase digestion. Most glycans were complex bi-, tri-and tetra-antennary compounds with reduced amounts of galactose. No bisected compounds were detected. Triantennary glycans were branched on the 6-antenna; fucose was attached to the core GlcNAc residue. Sialylated glycans were present on sGP but were largely absent from GP1, the larger fragment of the transmembrane glycoprotein. Consistent with this was the generally higher level of processing of carbohydrates found on sGP as evidenced by a higher percentage of galactose and lower levels of high-mannose glycans than were found on GP1. These results confirm and expand previous findings on partial characterisation of the Ebola virus transmembrane glycoprotein. They represent the first detailed data on carbohydrate structures of the Ebola virus sGP. PMID:20131323

  17. Qualitative and quantitative analysis of Potentilla fulgens roots by NMR, matrix-assisted laser desorption/ionisation with time-of-flight MS, electrospray ionisation MS/MS and HPLC/UV.

    PubMed

    Choudhary, Alka; Radhika, Manukonda; Chatterjee, Anupam; Banerjee, Uttam Chand; Singh, Inder Pal

    2015-01-01

    Potentilla fulgens is a commonly used folk medicine by natives of northeast India, Nepal and Bhutan and is rich in polyphenolic and triterpene constituents. To identify chemomarkers in the roots of P. fulgens by an interplay of (13)C-NMR, matrix-assisted laser desorption/ionisation with time-of-flight (MALDI/TOF) MS, electrospray ionisation (ESI) MS/MS and HPLC/UV. The (13)C-NMR spectrum of crude methanolic extract was recorded in deuterated dimethyl sulphoxide. For MALDI/TOF/MS analysis, 2,5-dihydroxybenzoic acid was used as the matrix. For determination of chemical constituents, two independent simple isocratic HPLC/UV methods for monomeric/oligomeric flavanols and triterpene acids were developed and validated. The (13)C-NMR spectrum of the methanolic extract indicated the presence of B-type oligomeric polyphenolics containing mainly epicatechin/catechin (epicat/cat) and epiafzelechin/afzelechin (epiafz/afz) as the monomeric units. Several isobaric monomeric and oligomeric flavanols and triterpenoids were tentatively identified by MALDI/TOF/MS and ESI/MS/MS. Fourteen compounds (four monomeric and five dimeric flavanols and five triterpene acids) were isolated using repeated column chromatography and semi-preparative HPLC, and were quantitated using HPLC/UV. It is evident from these analyses that roots of P. fulgens contain flavans, including oligomeric flavanols, as major constituents followed by triterpene acids. The methods described can be applied to other Potentilla species to identify their constituents. Copyright © 2014 John Wiley & Sons, Ltd.

  18. A study of the analytical behaviour of selected synthetic and naturally occurring quinolines using electrospray ionisation ion trap mass spectrometry, liquid chromatography and gas chromatography and the construction of an appropriate database for quinoline characterisation.

    PubMed

    O'Donnell, F; Ramachandran, V N; Smyth, W F; Hack, C J; Patton, E

    2006-07-14

    Mass spectral fragmentation of quinoline alkaloids of significance in plants has been investigated using electrospray ionisation ion trap mass spectrometry (ESI-MS(n)) with a view to characterisation of molecules of unknown structure isolated from these natural sources. This investigation has led to the generation of an appropriate database incorporating data from ESI-MS(n) and also from gas liquid chromatography (GLC) and liquid chromatography (HPLC) for these low molecular mass quinolines. This has been put to practical application in the identification of quinoline alkaloids in a plant extract. Thus, an acid extraction of the leaves of Choisya ternata containing such tertiary alkaloids was analysed by liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS) and the resulting behaviour of the quinolines was compared with that of the quinoline alkaloids in the database.

  19. Visualisation of abscisic acid and 12-oxo-phytodienoic acid in immature Phaseolus vulgaris L. seeds using desorption electrospray ionisation-imaging mass spectrometry

    NASA Astrophysics Data System (ADS)

    Enomoto, Hirofumi; Sensu, Takuya; Sato, Kei; Sato, Futoshi; Paxton, Thanai; Yumoto, Emi; Miyamoto, Koji; Asahina, Masashi; Yokota, Takao; Yamane, Hisakazu

    2017-02-01

    The plant hormone abscisic acid (ABA) and the jasmonic acid related-compound 12-oxo-phytodienoic acid (OPDA) play crucial roles in seed development, dormancy, and germination. However, a lack of suitable techniques for visualising plant hormones has restricted the investigation of their biological mechanisms. In the present study, desorption electrospray ionisation-imaging mass spectrometry (DESI-IMS), a powerful tool for visualising metabolites in biological tissues, was used to visualise ABA and OPDA in immature Phaseolus vulgaris L. seed sections. The mass spectra, peak values and chemical formulae obtained from the analysis of seed sections were consistent with those determined for ABA and OPDA standards, as were the precursor and major fragment ions observed in tandem mass spectrometry (MS/MS) imaging. Furthermore, the precursor and fragment ion images showed similar distribution patterns. In addition, the localisation of ABA and OPDA using DESI-IMS was confirmed using liquid chromatography-MS/MS (LC-MS/MS). The results indicated that ABA was mainly distributed in the radical and cotyledon of the embryo, whereas OPDA was distributed exclusively in external structures, such as the hilum and seed coat. The present study is the first to report the visualisation of plant hormones using IMS, and demonstrates that DESI-IMS is a promising technique for future plant hormone research.

  20. Visualisation of abscisic acid and 12-oxo-phytodienoic acid in immature Phaseolus vulgaris L. seeds using desorption electrospray ionisation-imaging mass spectrometry

    PubMed Central

    Enomoto, Hirofumi; Sensu, Takuya; Sato, Kei; Sato, Futoshi; Paxton, Thanai; Yumoto, Emi; Miyamoto, Koji; Asahina, Masashi; Yokota, Takao; Yamane, Hisakazu

    2017-01-01

    The plant hormone abscisic acid (ABA) and the jasmonic acid related-compound 12-oxo-phytodienoic acid (OPDA) play crucial roles in seed development, dormancy, and germination. However, a lack of suitable techniques for visualising plant hormones has restricted the investigation of their biological mechanisms. In the present study, desorption electrospray ionisation-imaging mass spectrometry (DESI-IMS), a powerful tool for visualising metabolites in biological tissues, was used to visualise ABA and OPDA in immature Phaseolus vulgaris L. seed sections. The mass spectra, peak values and chemical formulae obtained from the analysis of seed sections were consistent with those determined for ABA and OPDA standards, as were the precursor and major fragment ions observed in tandem mass spectrometry (MS/MS) imaging. Furthermore, the precursor and fragment ion images showed similar distribution patterns. In addition, the localisation of ABA and OPDA using DESI-IMS was confirmed using liquid chromatography-MS/MS (LC-MS/MS). The results indicated that ABA was mainly distributed in the radical and cotyledon of the embryo, whereas OPDA was distributed exclusively in external structures, such as the hilum and seed coat. The present study is the first to report the visualisation of plant hormones using IMS, and demonstrates that DESI-IMS is a promising technique for future plant hormone research. PMID:28211480

  1. A liquid chromatography/electrospray ionisation tandem mass spectrometry method for the simultaneous quantification of salicylic, jasmonic and abscisic acids in Coffea arabica leaves.

    PubMed

    de Sá, Marta; Ferreira, João P; Queiroz, Vagner T; Vilas-Boas, Luís; Silva, Maria C; Almeida, Maria H; Guerra-Guimarães, Leonor; Bronze, Maria R

    2014-02-01

    Plants have developed an efficient system of recognition that induces a complex network of signalling molecules such as salicylic acid (SA), jasmonic acid (JA) and abscisic acid (ABA) in case of a pathogenic infection. The use of specific and sensitive methods is mandatory for the analysis of compounds in these complex samples. In this study a liquid chromatography/electrospray ionisation tandem mass spectrometry method was developed and validated for the simultaneous quantification of SA, JA and ABA in Coffea arabica (L.) leaves in order to understand the role of these phytohormones in the signalling network involved in the coffee defence response against Hemileia vastatrix. The results showed that the method was specific, linear (r ≥ 0.99) in the range 0.125-1.00 µg mL⁻¹ for JA and ABA and 0.125-5.00 µg mL⁻¹ for SA, and precise (relative standard deviation ≤11%), and the limit of detection (0.010 µg g⁻¹ fresh weight) was adequate for quantifying these phytohormones in this type of matrix. In comparison with healthy leaves, those infected with H. vastatrix (resistance reaction) displayed an increase in SA level 24 h after inoculation, suggesting the involvement of an SA-dependent pathway in coffee resistance. © 2013 Society of Chemical Industry.

  2. Characterisation of chemical components for identifying historical Chinese textile dyes by ultra high performance liquid chromatography - photodiode array - electrospray ionisation mass spectrometer.

    PubMed

    Han, Jing; Wanrooij, Jantien; van Bommel, Maarten; Quye, Anita

    2017-01-06

    This research makes the first attempt to apply Ultra High Performance Liquid Chromatography (UHPLC) coupled to both Photodiode Array detection (PDA) and Electrospray Ionisation Mass Spectrometer (ESI-MS) to the chemical characterisation of common textile dyes in ancient China. Three different extraction methods, respectively involving dimethyl sulfoxide (DMSO)-oxalic acid, DMSO and hydrochloric acid, are unprecedentedly applied together to achieve an in-depth understanding of the chemical composition of these dyes. The first LC-PDA-MS database of the chemical composition of common dyes in ancient China has been established. The phenomena of esterification and isomerisation of the dye constituents of gallnut, gardenia and saffron, and the dye composition of acorn cup dyed silk are clarified for the first time. 6-Hydroxyrubiadin and its glycosides are first reported on a dyed sample with Rubia cordifolia from China. UHPLC-PDA-ESI-MS with a C18 BEH shield column shows significant advantages in the separation and identification of similar dye constituents, particularly in the cases of analysing pagoda bud and turmeric dyed sample extracts.

  3. A predictive science approach to aid understanding of electrospray ionisation tandem mass spectrometric fragmentation pathways of small molecules using density functional calculations.

    PubMed

    Galezowska, Angelika; Harrison, Mark W; Herniman, Julie M; Skylaris, Chris-Kriton; Langley, G John

    2013-05-15

    Tandem mass spectrometry (MS/MS) dissociation pathways can vary markedly between compound classes and can result in challenging and time-consuming interpretation of the data. Compound, class and substructure specific fragmentation rules for protonated molecules require refinement to aid the structural elucidation process. The application of a predictive science approach using density functional theory (DFT) calculations has been investigated to estimate the abundances of first-generation product ions observed using an ion trap mass spectrometer. This has been achieved by application of Boltzmann population theory to electrospray ionisation (ESI)-MS and MS/MS data. Tandem ESI-MS data for this preliminary study were used to investigate the internal stabilities of protonated species and their product ions. The calculated relative abundances of 11.3%, 96.5%, and 1.1% for the product ion (m/z 192) of three quinazoline structural isomers are compared with the experimental values of 16%, 90% and 0% observed in the first-generation product ion mass spectra. Close correlation between calculated and experimental data has been demonstrated for these initial data. Applying this approach and establishing fragmentation rules, based on structure specific and common fragmentation behaviour, would improve and expedite the structural elucidation process. Copyright © 2013 John Wiley & Sons, Ltd.

  4. The Spatial Distribution of Alkaloids in Psychotria prunifolia (Kunth) Steyerm and Palicourea coriacea (Cham.) K. Schum Leaves Analysed by Desorption Electrospray Ionisation Mass Spectrometry Imaging.

    PubMed

    Kato, Lucilia; Moraes, Aline Pereira; de Oliveira, Cecília Maria Alves; Vaz, Boniek Gontijo; de Almeida Gonçalves, Letícia; E Silva, Elienai Cândida; Janfelt, Christian

    2017-09-06

    Species of the genera Psychotria and Palicourea are sources of indole alkaloids, however, the distribution of alkaloids within the plants is not known. Analysing the spatial distribution using desorption electrospray ionisation mass spectrometry imaging (DESI-MSI) has become attractive due to its simplicity and high selectivity compared to traditional histochemical techniques. To apply DESI-MSI to visualise the alkaloid distribution on the leaf surface of Psychotria prunifolia and Palicourea coriacea and to compare the distributions with HPLC-MS and histochemical analyses. Based upon previous structure elucidation studies, four alkaloids targeted in this study were identified using high resolution mass spectrometry by direct infusion of plant extracts, and their distributions were imaged by DESI-MSI via tissue imprints on a porous Teflon surface. Relative quantitation of the four alkaloids was obtained by HPLC-MS/MS analysis performed using multiple-reaction monitoring (MRM) mode on a triple quadrupole mass spectrometer. Alkaloids showed distinct distributions on the leaf surfaces. Prunifoleine was mainly present in the midrib, while 10-hydroxyisodeppeaninol was concentrated close to the petiole; a uniform distribution of 10-hydroxyantirhine was observed in the whole leaf of Psychotria prunifolia. The imprinted image from the Palicourea coriacea leaf also showed a homogeneous distribution of calycanthine throughout the leaf surface. Different distributions were found for three alkaloids in Psychotria prunifolia, and the distributions found by MSI were in complete accordance with HPLC-MS analysis and histochemical results. The DESI-MSI technique was therefore demonstrated to provide reliable information about the spatial distribution of metabolites in plants. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  5. Investigation of pyrrolizidine alkaloids including their respective N-oxides in selected food products available in Hong Kong by liquid chromatography electrospray ionisation mass spectrometry.

    PubMed

    Chung, Stephen W C; Lam, Aaron C H

    2017-07-01

    This study determined the levels of pyrrolizidine alkaloids (PAs), including their respective N-oxides, in foodstuffs available in Hong Kong by liquid chromatography-electrospray ionisation tandem mass spectrometry. A total of 234 samples (48 food items) were collected randomly from a local market and analysed. About 50% of samples were found to contain detectable amount of PAs. Amongst the 48 food items, PAs were not detected in 11 food items, including barley flour, beef, cattle liver, pork, pig liver, chicken meat, chicken liver, milk, non-fermented tea, Melissa tea and linden tea. For those found to contain detectable PAs, the summed PA content ranged up to 11,000 µg kg(-1). The highest sum of PA content among the 37 food items calculated with lower bound was cumin seed, then followed by oregano, tarragon and herbs de Provence with ranges of 2.5-11,000, 1.5-5100, 8.0-3300 and 18-1300 µg kg(-1) respectively. Among the samples, the highest sum of PA content was detected in a cumin seed sample (11,000 µg kg(-1)), followed by an oregano (5100 µg kg(-1)), a tarragon (3300 µg kg(-1)) and a herbs de Provence (1300 µg kg(-1)). In general, the results of this study agreed well with other published results in peer-reviewed journals, except that the total PAs in honey and specific tea infusion in this study were comparatively lower.

  6. Identification of prenylated pterocarpans and other isoflavonoids in Rhizopus spp. elicited soya bean seedlings by electrospray ionisation mass spectrometry.

    PubMed

    Simons, Rudy; Vincken, Jean-Paul; Bohin, Maxime C; Kuijpers, Tomas F M; Verbruggen, Marian A; Gruppen, Harry

    2011-01-15

    Phytoalexins from soya are mainly characterised as prenylated pterocarpans, the glyceollins. Extracts of non-soaked and soaked soya beans, as well as that of soya seedlings, grown in the presence of Rhizopus microsporus var. oryzae, were screened for the presence of prenylated flavonoids with a liquid chromatography/mass spectrometry (LC/MS)-based screening method. The glyceollins I-III and glyceollidins I-II, belonging to the isoflavonoid subclass of the pterocarpans, were tentatively assigned. The formation of these prenylated pterocarpans was accompanied by that of other prenylated isoflavonoids of the subclasses of the isoflavones and the coumestans. It was estimated that approx. 40% of the total isoflavonoid content in Rhizopus-challenged soya bean seedlings were prenylated pterocarpans, whereas 7% comprised prenylated isoflavones and prenylated coumestans. The site of prenylation (A-ring or B-ring) of the prenylated isoflavones was tentatively annotated using positive-ion mode MS by comparing the (1,3) A(+) retro-Diels-Alder (RDA) fragments of prenylated and non-prenylated isoflavones. Furthermore, the fragmentation pathways of the five pterocarpans in negative-ion (NI) mode were proposed, which involved the cleavage of the C-ring and/or D-ring. The absence of the ring-closed prenyl (pyran or furan) gave exclusively -H(2) O(x,y) RDA fragments, whereas its presence gave predominantly the common RDA fragments. Copyright © 2010 John Wiley & Sons, Ltd.

  7. The detection of iron protoporphyrin (heme b) in phytoplankton and marine particulate material by electrospray ionisation mass spectrometry - comparison with diode array detection.

    PubMed

    Gledhill, Martha

    2014-09-02

    A mass spectrometric (MS) method for the identification of iron protoporphyrin (IX) (FePTP, heme b) in marine particulate material and phytoplankton is described. Electrospray ionisation of FePTP produced the molecular Fe(III)PTP(+) ion (m/z=616) or the pseudomolecular [Fe(II)PTP + H](+) ion (m/z=617), depending on the oxidation state of the central iron ion. Collision induced dissociation (CID) in the ion trap mass spectrometer resulted in a single detected product ion (m/z=557) indicative of loss of ethanoic acid from a carboxylic acid side chain. Widening the isolation width to 616±3 resulted in production of a mass spectrum demonstrating the distinctive isotopic ratio of the iron containing fragment, further increasing the specificity of the analysis. Selective reactant monitoring (SRM) of the fragment ion (m/z=557) was applied to the detection of FePTP after chromatography of ammoniacal OGP extracts of marine samples. The detection limit for FePTP analysed by SRM after chromatography was 1.2±0.5fmol. For phytoplankton samples, reasonably good agreement was achieved between results obtained with SRM and those obtained by monitoring absorbance at λ=400nm using a diode array detector (DAD). Use of SRM for analysis of particulate material obtained from the high latitude North Atlantic allowed for the analysis of FePTP in the presence of a co-eluting compound that interfered with detection by DAD. Simultaneous collection of mass spectra from m/z=300 to 1500 resulted in identification of the pseudomolecular ion for the interfering compound. The CID fragmentation pattern and UV-visible mass spectra indicated that the interfering compound was a previously unidentified chlorin type compound. Comparison of FePTP determined by SRM and DAD on samples where this compound could not be detected showed that results collected using the two methods correlated. The use of both MS and DAD results in a powerful tool for quantifying this important biogenic component of the

  8. Fast imaging of intermittent electrospraying of water with positive corona discharge

    NASA Astrophysics Data System (ADS)

    Pongrác, B.; Kim, H. H.; Janda, M.; Martišovitš, V.; Machala, Z.

    2014-08-01

    The effect of the electrospraying of water in combination with a positive direct current (dc) streamer corona discharge generated in air was investigated in this paper. We employed high-speed camera visualizations and oscilloscopic discharge current measurements in combination with an intensified charge-coupled device camera for fast time-resolved imaging. The repetitive process of Taylor cone formation and droplet formation from the mass fragments of water during the electrospray was visualized. Depending on the applied voltage, the following intermittent modes of electrospraying typical for water were observed: dripping mode, spindle mode, and oscillating-spindle mode. The observed electrospraying modes were repetitive with a frequency of a few hundreds of Hz, as measured from the fast image sequences. This frequency agreed well with the frequency of the measured streamer current pulses. The presence of filamentary streamer discharges at relatively low voltages probably prevented the establishment of a continuous electrospray in the cone-jet mode. After each streamer, a positive glow corona discharge was established on the water filament tip, and it propagated from the stressed electrode along with the water filament elongation. The results show a reciprocal character of intermittent electrospraying of water, and the presence of corona discharge, where both the electrospray and the discharge affect each other. The generation of a corona discharge from the water cone depended on the repetitive process of the cone formation. Also, the propagation and curvature of the water filament were influenced by the discharge and its resultant space charge. Furthermore, these phenomena were partially influenced by the water conductivity.

  9. Determination and separation of bisphenol A, phthalate metabolites and structural isomers of parabens in human urine with conventional high-pressure liquid chromatography combined with electrospray ionisation tandem mass spectrometry.

    PubMed

    Myridakis, Antonis; Balaska, Eirini; Gkaitatzi, Christina; Kouvarakis, Antonis; Stephanou, Euripides G

    2015-03-01

    Phthalates, bisphenol A (BPA) and parabens (PBs), organic chemicals widely used in everyday products, are considered to be endocrine disruptors. We propose a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of seven phthalate metabolites, six PBs and BPA in human urine. All three categories of the above endocrine disruptors were simultaneously extracted from 1 mL of human urine using solid phase extraction. In addition, with a conventional reversed phase LC column, we achieved for the first time the separation of three pairs of structural isomers, namely iso-/n-butyl paraben, propyl paraben and monobutyl phthalate. LC-MS/MS was operated and tested in both electrospray ionisation (ESI) and atmospheric pressure chemical ionisation (APCI). ESI was selected for the analysis due to its superior stability and repeatability. The method limit of detection (mLOD), achieved for a single set of high-performance LC conditions, ranged from 0.01 to 0.84 ng/mL for phthalate metabolites, from 0.06 to 0.24 ng/mL for PBs and was 2.01 ng/mL for BPA. Derivatisation of BPA with dansyl chloride lowered its mLOD to 0.007 ng/mL. Blank contamination was non-detectable. The present method was successfully applied for the analysis of the above-mentioned compounds in 80 male human urine samples.

  10. Evidence for site-specific intra-ionic hydrogen/deuterium exchange in the low-energy collision-induced dissociation product ion spectra of protonated small molecules generated by electrospray ionisation.

    PubMed

    Holman, Stephen W; Wright, Patricia; Wells, Neil J; Langley, G John

    2010-04-01

    The experimental investigation of site-specific intra-ionic hydrogen/deuterium (H/D) exchange in the low-energy collision-induced dissociation (CID) product ion spectra of protonated small molecules generated by electrospray ionisation (ESI) is presented. The observation of intra-ionic H/D exchange in such ions under low-energy CID conditions has hitherto been rarely reported. The data suggest that the intra-ionic H/D exchange takes place in a site-specific manner between the ionising deuteron, localised at either a tertiary amine or a tertiary amine-N-oxide, and a gamma-hydrogen relative to the nitrogen atom. Nuclear magnetic resonance (NMR) spectroscopy measurements showed that no H/D exchange takes place in solution, indicating that the reaction occurs in the gas phase. The compounds analysed in this study suggested that electron-withdrawing groups bonded to the carbon atom bearing the gamma-hydrogen can preclude exchange. The effect of the electron-withdrawing group appears dependent upon its electronegativity, with lower chi value groups still allowing exchange to take place. However, the limited dataset available in this study prevented robust conclusions being drawn regarding the effect of the electron-withdrawing group. The observation of site-specific intra-ionic H/D exchange has application in the area of structural elucidation, where it could be used to introduce an isotopic label into the carbon skeleton of a molecule containing specific structural features. This could increase the throughput, and minimise the cost, of such studies due to the obviation of the need to produce a deuterium-labelled analogue by synthetic means. Copyright 2010 John Wiley & Sons, Ltd.

  11. High-performance liquid chromatography with electrospray ionisation mass spectrometry and diode array detection in the identification and quantification of the degradation products of calix[4]arene crown-6 under radiolysis.

    PubMed

    Lamouroux, C; Aychet, N; Lelièvre, A; Jankowski, C K; Moulin, C

    2004-01-01

    The extraction of 135Cs from high-activity liquid waste, arising from reprocessing of spent nuclear fuel, can be achieved by using calix[4]arene crown-6 compounds. The radiolytic degradation of di(n-octyloxy)calix[4]arene crown-6 (octMC6), in aliphatic or aromatic solvent in contact with 3 M nitric acid, was studied by high-performance liquid chromatography directly coupled to electrospray ionisation mass spectrometry (LC/ESI-MS). More than 50 distinct degradation products were observed, and about 30 of these were identified. These compounds can be assigned to three categories, namely, products of reactions involving radical cleavage or addition, of oxidation reactions, or of aromatic substitution reactions. The major product, corresponding to substitution by an NO2 group, was quantified by external standard calibration using a purified synthetic sample. Despite the observation of all these degradation compounds, octMC6 appears to be remarkably stable under these drastic conditions, combining hydrolysis (HNO(3) 3 M) and an extreme exposure to radiolysis (10(6) Gy). Less than 35% degradation of octMC6 was observed in aromatic solvent under these conditions.

  12. Characterisation by liquid chromatography coupled to electrospray ionisation ion trap mass spectrometry of phloroglucinol and 4-methylcatechol oxidation products to study the reactivity of epicatechin in an apple juice model system.

    PubMed

    Poupard, Pascal; Guyot, Sylvain; Bernillon, Stephane; Renard, Catherine M G C

    2008-02-01

    The reactivity of the (-)-epicatechin structure towards caffeoylquinic acid o-quinones was studied in an apple juice model solution. The approach consisted in considering separately the reactivities of the two phenolic moieties of an (-)-epicatechin molecule: phloroglucinol and 4-methylcatechol were chosen to represent A- and B-rings, respectively. The oxidation products were characterised by RP-HPLC coupled with electrospray ionisation Mass spectrometry (MS). The reactivities of the A- and B-rings were clearly different on the basis of the oxidation products formed. Both A- and B-rings could be involved in covalent bond formation, but electron transfers only occurred with the B-ring. Most of the (-)-epicatechin oxidation products were linked by A/B-ring linkage ("head-to-tail" intermolecular coupling). After this first dimerisation step, intramolecular reactions seemed to be favoured. Therefore, the complexity of oxidation products in apple juice does not only result from an extensive polymerisation of native phenolic compounds, but also from a multiplicity of small molecules in different oxidation states and isomeric forms.

  13. Two-dimensional HPLC coupled to ICP-MS and electrospray ionisation (ESI)-MS/MS for investigating the bioavailability in vitro of arsenic species from edible seaweed.

    PubMed

    Garcia-Sartal, Cristina; Taebunpakul, Sutthinun; Stokes, Emma; Barciela-Alonso, María del Carmen; Bermejo-Barrera, Pilar; Goenaga-Infante, Heidi

    2012-04-01

    Edible seaweed consumption is a route of exposure to arsenic. However, little attention has been paid to estimate the bioaccessibility and/or bioavailability of arsenosugars in edible seaweed and their possible degradation products during gastrointestinal digestion. This work presents first use of combined inductively coupled plasma mass spectroscopy (ICP-MS) with electrospray ionization tandem mass spectrometry (ESI-MS/MS) with two-dimensional HPLC (size exclusion followed by anion exchange) to compare the qualitative and quantitative arsenosugars speciation of different edible seaweed with that of their bioavailable fraction as obtained using an in vitro gastrointestinal digestion procedure. Optimal extraction conditions for As species from four seaweed namely kombu, wakame, nori and sea lettuce were selected as a compromise between As extraction efficiency and preservation of compound identity. For most investigated samples, the use of ammonium acetate buffer as extractant and 1 h sonication in a water bath followed by HPLC-ICP-MS resulted in 40-61% of the total As to be found in the buffered aqueous extract, of which 86-110% was present as arsenosugars (glycerol sugar, phosphate sugar and sulfonate sugar for wakame and kombu and glycerol sugar and phosphate sugar for nori). The exception was sea lettuce, for which the arsenosugar fraction (glycerol sugar, phosphate sugar) only comprised 44% of the total extracted As. Interestingly, the ratio of arsenobetaine and dimethylarsinic acid to arsenosugars in sea lettuce extracts seemed higher than that for the rest of investigated samples. After in vitro gastrointestinal digestion, approximately 11-16% of the total As in the solid sample was found in the dialyzates with arsenosugars comprising 93-120% and 41% of the dialyzable As fraction for kombu, wakame, nori and sea lettuce, respectively. Moreover, the relative As species distribution in seaweed-buffered extracts and dialyzates was found to be very similar

  14. Rapid separation and identification of anthocyanins from flowers of Viola yedoensis and V. prionantha by high-performance liquid chromatography-photodiode array detection-electrospray ionisation mass spectrometry.

    PubMed

    Zhang, Jie; Wang, Liang-Sheng; Gao, Jin-Ming; Xu, Yan-Jun; Li, Lian-Fang; Li, Chong-Hui

    2012-01-01

    Anthocyanins are important plant secondary metabolites. They show strong antioxidant activities and have potential as anti-cancer agents. Viola yedoensis and V. prionantha are traditional Chinese medicines and ornamental plants. However, the anthocyanin compositions of these two species are still unresolved. To develop a rapid and reliable high-performance liquid chromatography (HPLC) method for the separation and identification of anthocyanins from V. yedoensis and V. prionantha. Samples were extracted in methanol-water-formic acid-TFA (70:27:2:1, v/v). HPLC analysis was done on a C(18) column (TSK-GEL ODS-80Ts: 150 × 4.6 mm i.d.). Four solvent systems were tested to optimise the separation of anthocyanins using different gradient separation systems. HPLC-photodiode array detection (DAD) coupled to electrospray ionisation mass spectrometry (ESI-MS) was used to carry out the comprehensive characterisation of anthocyanins. Fourteen anthocyanins were characterised within 40 min with satisfactory peak resolution by a gradient composed of 10% aqueous formic acid and formic acid-acetonitrile-water (10:40:50, v/v). The calibration curve showed an excellent linear regression (r(2)  = 0.9995) and low intra- and inter-day variations (RSD < 3.67%). The detected anthocyanins derived from Dp, Cy, Pt, Mv and Pn, could be divided into three groups: non-acylated glycosides, acetylglycosides and coumaroylglycosides. Anthocyanins distribution exhibited remarkable differences in aglycone levels and acylation patterns. The optimised method was successfully applied for the analysis of 14 anthocyanins from V. yedoensis and V. prionantha. The identification of anthocyanin constitutions is valuable for breeding and will open up new prospects for their medicinal application. Copyright © 2011 John Wiley & Sons, Ltd.

  15. Identification of amino acids by material enhanced laser desorption/ionisation mass spectrometry (MELDI-MS) in positive- and negative-ion mode

    NASA Astrophysics Data System (ADS)

    Hashir, Muhammad Ahsan; Stecher, Guenther; Mayr, Stefan; Bonn, Guenther K.

    2009-01-01

    In the present study, different silica gel modifications were evaluated for their application as target surface for material enhanced laser desorption/ionisation mass spectrometric (MELDI-MS) investigation of amino acids. 4,4'-Azodianiline (ADA-silica) modified silica gel was successfully employed for the qualitative analysis of amino acids in positive- and in negative-ion mode. Further no derivatisation of amino acids was necessary, as the introduced system allowed the direct analysis of targets and delivered spectra with excellent signal intensity and signal-to-noise ratio within a few minutes. The influence of surface chemistry, ionisation mode and the nature of analytes on signal intensity was studied and discussed. Detection limit of 2.10 pg (10 fmol) was achieved by employing ADA-silica in positive-ion mode. Finally, xylem saps from different types of trees were analysed. This proved the high performance and excellent behaviour of the introduced target surface material.

  16. Positive and negative electrospray LC-MS-MS methods for quantitation of the antiparasitic endectocide drugs, abamectin, doramectin, emamectin, eprinomectin, ivermectin, moxidectin and selamectin in milk.

    PubMed

    Durden, David A

    2007-05-01

    Avermectin endectocides are used for the treatment of cattle against a variety of nematode and arthropod parasites, and consequently may appear in milk after normal or off-label use. The compounds abamectin, doramectin, and ivermectin, contain only C, H and O and may be expected to be detected by LC-MS in negative ion mode. The others contain nitrogen in addition and would be expected to be preferentially ionized in positive mode. The use of positive ion and negative ion methods with electrospray LC-MS-MS were compared. Using negative ion the compounds abamectin, doramectin, ivermectin, emamectin, eprinomectin, and moxidectin gave a curvilinear response and were quantified in raw milk by LC-MS-MS with a triethylamine-acetonitrile buffer over the concentration range 1-60 ppb (microg/kg) using selamectin as the internal standard. The limits of detection (LOD) were between 0.19 ppb (doramectin) and 0.38 ppb (emamectin). The compounds gave maximum sensitivity with positive ionisation from a formic acid-ammonium formate-acetonitrile buffer and were detected in milk (LC-MS-MS) also with a curvilinear response over the range 0.5-60 ppb. Although the positive ion signals were larger, with somewhat lower limits of detection (LOD between 0.06 ppb (doramectin) and 0.32 ppb (moxidectin) the negative ion procedure gave a more linear response and more consistent results. Comparison of spiked samples in the range 2-50 ppb showed a high degree of correlation between the two methods.

  17. Gas-phase intramolecular elimination reaction studies of steviol glycosides in positive electrospray and tandem mass spectrometry.

    PubMed

    Upreti, Mani; Clos, John F; Somayajula, Kasi V; Milanowski, Dennis J; Mocek, Ulla; Dubois, Grant E; Prakash, Indra

    2009-01-01

    This paper reports the first study of the gas-phase intramolecular elimination reaction of steviol glycosides in positive electrospray mass spectrometry. The observed glycosylated product ions are proposed to be formed via an intramolecular elimination of sugar units from the parent molecule ion. It was further proven by MS/MS studies and deuterium labeling experiments with one of the steviol glycosides, rebaudioside A. These mass spectrometric results confirmed that the new glycosylated product ions observed are most likely formed by the combination of glucose moieties (Glu) II-IV and Glu I via a gas-phase intramolecular elimination reaction.

  18. Electrospray device

    NASA Technical Reports Server (NTRS)

    Demmons, Nathaniel (Inventor); Martin, Roy (Inventor); Hruby, Vladimir (Inventor); Roy, Thomas (Inventor); Spence, Douglas (Inventor); Ehrbar, Eric (Inventor); Zwahlen, Jurg (Inventor)

    2011-01-01

    An electrospray device includes an electrospray emitter adapted to receive electrospray fluid; an extractor plate spaced from the electrospray emitter and having at least one aperture; and a power supply for applying a first voltage between the extractor plate and emitter for generating at least one Taylor cone emission through the aperture to create an electrospray plume from the electrospray fluid, the extractor plate as well as accelerator and shaping plates may include a porous, conductive medium for transporting and storing excess, accumulated electrospray fluid away from the aperture.

  19. Positive mode electrospray tandem mass spectrometry of poly(methacrylic acid) oligomers.

    PubMed

    Giordanengo, Rémi; Viel, Stéphane; Allard-Breton, Béatrice; Thévand, André; Charles, Laurence

    2009-06-01

    The dissociation of small poly(methacrylic acid) (PMAA) cations produced by electrospray was characterized by tandem mass spectrometry. Similarly to PMAA ions produced in the negative ion mode, the two electrosprayed cationic forms, namely [PMAA+Na](+) and [PMAA-H+2Na](+), were shown to fragment via a major pathway consisting of successive dehydration steps. Elimination of a water molecule would occur between two consecutive acid groups in a charged-remote mechanism and was shown to proceed as many times as pairs of acidic pendant groups were available. As a result, comparing the number of dehydration steps observed in the MS/MS spectrum of two consecutive oligomers from the polymeric distribution reveals the degree of polymerization of the molecule. Secondary less informative reactions were shown to consist of losses of CO and/or CO(2), depending on the nature of the precursor ion. These fragmentation rules could be used to characterize PMAA-based copolymers, as successfully demonstrated for a polymeric impurity in the tested PMAA sample.

  20. Method validation for the analysis of 169 pesticides in soya grain, without clean up, by liquid chromatography-tandem mass spectrometry using positive and negative electrospray ionization.

    PubMed

    Pizzutti, Ionara R; de Kok, André; Zanella, Renato; Adaime, Martha B; Hiemstra, Maurice; Wickert, Cristine; Prestes, Osmar D

    2007-02-23

    Part of a comprehensive study on the comparison of different extraction methods, GC-MS(/MS) and LC-MS/MS detection methods and modes, for the analysis of soya samples is described in this paper. The validation of an acetone-based extraction method for analysis of 169 pesticides in soya, using LC-MS/MS positive and negative electrospray ionisation (ESI) mode, is reported. Samples (5 g) were soaked with 10 g water and subsequently extracted with 100 mL of a mixture of acetone, dichloromethane and light petroleum (1:1:1), in the presence of 15 g anhydrous sodium sulphate. After centrifugation, aliquots of the extract were evaporated and reconstituted in 1.0 mL of methanol, before direct injection of the final extract (corresponding with 0.05 g soya mL(-1)) into the LC-MS/MS system. Linearity, r(2) of calibration curves, instrument limit of detection/quantitation (LOD/LOQ) and matrix effect were evaluated, based on seven concentrations measured in 6-fold. Good linearity (at least r(2)> or =0.99) of the calibration curves was obtained over the range from 0.1 or 0.25 to 10.0 ng mL(-1), corresponding with pesticide concentrations in soya bean extract of 2 or 5-200 microg kg(-1). Instrument LOD values generally were 0.1 or 0.25 ng mL(-1). Matrix effects were negligible for approximately 90% of the pesticides. The accuracy, precision and method LOQ were determined via recovery experiments, spiking soya at 10, 50, 100 microg kg(-1), six replicates per level. In both ESI modes, method LOQ values were mostly 10 or 50 microg kg(-1) and more than 70% of pesticides analysed by each mode met the acceptability criteria of recovery (70-120%) and RSD (< or =20%), at one or more of the three levels studied. A fast, easy and efficient method with acceptable performance was achieved for a difficult matrix as soya, without cleanup.

  1. Direct Identification of Bacteria in Positive Blood Culture Bottles by Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry

    PubMed Central

    La Scola, Bernard; Raoult, Didier

    2009-01-01

    Background With long delays observed between sampling and availability of results, the usefulness of blood cultures in the context of emergency infectious diseases has recently been questioned. Among methods that allow quicker bacterial identification from growing colonies, matrix-assisted laser desorption ionisation time-of-flight (MALDI-TOF) mass spectrometry was demonstrated to accurately identify bacteria routinely isolated in a clinical biology laboratory. In order to speed up the identification process, in the present work we attempted bacterial identification directly from blood culture bottles detected positive by the automate. Methodology/Principal Findings We prospectively analysed routine MALDI-TOF identification of bacteria detected in blood culture by two different protocols involving successive centrifugations and then lysis by trifluoroacetic acid or formic acid. Of the 562 blood culture broths detected as positive by the automate and containing one bacterial species, 370 (66%) were correctly identified. Changing the protocol from trifluoroacetic acid to formic acid improved identification of Staphylococci, and overall correct identification increased from 59% to 76%. Lack of identification was observed mostly with viridans streptococci, and only one false positive was observed. In the 22 positive blood culture broths that contained two or more different species, only one of the species was identified in 18 samples, no species were identified in two samples and false species identifications were obtained in two cases. The positive predictive value of bacterial identification using this procedure was 99.2%. Conclusions/Significance MALDI-TOF MS is an efficient method for direct routine identification of bacterial isolates in blood culture, with the exception of polymicrobial samples and viridans streptococci. It may replace routine identification performed on colonies, provided improvement for the specificity of blood culture broths growing viridans

  2. Direct identification of bacteria in positive blood culture bottles by matrix-assisted laser desorption ionisation time-of-flight mass spectrometry.

    PubMed

    La Scola, Bernard; Raoult, Didier

    2009-11-25

    With long delays observed between sampling and availability of results, the usefulness of blood cultures in the context of emergency infectious diseases has recently been questioned. Among methods that allow quicker bacterial identification from growing colonies, matrix-assisted laser desorption ionisation time-of-flight (MALDI-TOF) mass spectrometry was demonstrated to accurately identify bacteria routinely isolated in a clinical biology laboratory. In order to speed up the identification process, in the present work we attempted bacterial identification directly from blood culture bottles detected positive by the automate. We prospectively analysed routine MALDI-TOF identification of bacteria detected in blood culture by two different protocols involving successive centrifugations and then lysis by trifluoroacetic acid or formic acid. Of the 562 blood culture broths detected as positive by the automate and containing one bacterial species, 370 (66%) were correctly identified. Changing the protocol from trifluoroacetic acid to formic acid improved identification of Staphylococci, and overall correct identification increased from 59% to 76%. Lack of identification was observed mostly with viridans streptococci, and only one false positive was observed. In the 22 positive blood culture broths that contained two or more different species, only one of the species was identified in 18 samples, no species were identified in two samples and false species identifications were obtained in two cases. The positive predictive value of bacterial identification using this procedure was 99.2%. MALDI-TOF MS is an efficient method for direct routine identification of bacterial isolates in blood culture, with the exception of polymicrobial samples and viridans streptococci. It may replace routine identification performed on colonies, provided improvement for the specificity of blood culture broths growing viridans streptococci is obtained in the near future.

  3. Unexpected Reduction of Iminoquinone and Quinone Derivatives in Positive Electrospray Ionization Mass Spectrometry and Possible Mechanism Exploration

    NASA Astrophysics Data System (ADS)

    Pei, Jiying; Hsu, Cheng-Chih; Zhang, Ruijie; Wang, Yinghui; Yu, Kefu; Huang, Guangming

    2017-08-01

    Unexpected reduction of iminoquinone (IQ) and quinone derivatives was first reported during positive electrospray ionization mass spectrometry. Upon increasing spray voltage, the intensities of IQ and quinone derivatives decreased drastically, accompanying the increase of the intensities of the reduction products, amodiaquine (AQ) and phenol derivatives. To gain more insight into the mechanism of such reduction, we explored the experimental factors that are influential to corona discharge (CD). The results show that experimental parameters that favor severe CD, including metal spray emitter, using water as spray solvent, sheath gas with low dielectric strength (e.g., nitrogen), and shorter spray tip-to-mass spectrometer inlet distance, facilitated the reduction of IQ and quinone derivatives, implying that the reduction should be closely related to CD in the gas phase. [Figure not available: see fulltext.

  4. A comparative study of primary secondary amino (PSA) and multi-walled carbon nanotubes (MWCNTs) as QuEChERS absorbents for the rapid determination of diazepam and its major metabolites in fish samples by high-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry.

    PubMed

    Li, Jincheng; Zhang, Jing; Liu, Huan; Wu, Lidong

    2016-01-30

    A simple and fast modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method is presented for the determination of diazepam and its three major metabolites, nordiazepam, temazepam and oxazepam (benzodiazepines) in fish samples by liquid chromatography-electrospray ionisation-tandem mass spectrometry. Muscle tissues were extracted with acetonitrile, and then cleaned with primary secondary amino (PSA) adsorbents. The cleanup effect of PSA was compared with that of multi-walled carbon nanotubes (MWCNTs) in term of extraction efficiency. The better results were obtained when PSA was used. The chromatography separation was achieved within 5.0 min on a C18 column. The limit of detection was 0.5 µg kg(-1) and the limit of quantification was 2.5 µg kg(-1). Average recoveries of diazepam and its main metabolites were in the range of 88.5-110.1%, with a relative standard deviation lower than 10.0%. The proposed method for fish samples gives good recoveries, linearity, precision and accuracy. © 2015 Society of Chemical Industry.

  5. Simultaneous characterisation of fifty coumarins from the roots of Angelica dahurica by off-line two-dimensional high-performance liquid chromatography coupled with electrospray ionisation tandem mass spectrometry.

    PubMed

    Li, Bin; Zhang, Xu; Wang, Juan; Zhang, Le; Gao, Bowen; Shi, Shepo; Wang, Xiaohui; Li, Jun; Tu, Pengfei

    2014-01-01

    The root of Angelica dahurica is a traditional Chinese medicine that used for the treatment of headache, toothache, abscess, furunculosis and acne. Coumarins were the major bioactive constituents of A. dahurica, hence it is worthwhile developing a method to simultaneously characterise them, especially those in trace amounts. To develop an efficient method for the simultaneous characterisation of coumarins in A. dahurica. A method using off-line two-dimensional high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (off-line 2D-HPLC-ESI/MS(n) ) was developed. In total 50 coumarins, including 32 linear furanocoumarins, 16 bifuranocoumarins and two non-furanocoumarins, were identified from the roots of A. dahurica. The possible MS fragmentations of these coumarins are also proposed. The method described here allows rapid and convenient identification of the coumarins in A. dahurica, and may be applied to other herbal medicines containing linear furanocoumarins. Copyright © 2014 John Wiley & Sons, Ltd.

  6. Determination of ramipril in human plasma and its fragmentation by UPLC-Q-TOF-MS with positive electrospray ionization.

    PubMed

    Szpot, Paweł; Buszewicz, Grzegorz

    2015-06-01

    This report presents the application of ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry with positive electrospray ionization, to determine ramipril in human plasma. First, the proteins in human plasma were precipitated using acetonitrile, then the supernatant was extracted by ethyl acetate at pH 3 and finally, the extract was analyzed using a UPLC-QTOF- MS system. The method was validated and the coefficient of determination (R2) was >0.999, the lower limit of quantification (LLOQ) was 0.5 ng mL(-1). Precision, recovery and stability were determined for three different concentrations of ramipril. RSD for this method ranged from 3.3 to 8.6%. The intra-day mean recovery was from 65.3 to 97.3%. In addition, the fragmentation of ramipril was studied. Due to high resolution of the spectrometer, it was possible to measure fragment masses accurately and determine their molecular and chemical formulas with high accuracy.

  7. Application of positive ion chemical ionisation and tandem mass spectrometry combined with gas chromatography to the trace level analysis of ethyl carbamate in bread.

    PubMed

    Hamlet, Colin G; Jayaratne, Sanal M; Morrison, Carol

    2005-01-01

    A rapid, sensitive and selective method has been developed and validated for the analysis of the contaminant ethyl carbamate (EC) in bread products at the part-per-billion level. The new procedure uses positive ion chemical ionisation (PICI) and tandem mass spectrometry (MS/MS), combined with gas chromatography (GC), on a 'bench-top' triple-quadrupole mass spectrometer. Ammonia was the PICI reagent gas of choice because of its ability to produce abundant [M+H]+ and [M+NH4]+ ions from EC and deuterium-labelled EC (LEC) used as an internal standard. For identification and quantification, selected reaction monitoring (SRM) was used to follow the precursor-to-product ion transitions of m/z 107 --> 90, m/z 107 --> 62 and m/z 90 --> 62 for EC, as well as m/z 112 --> 63 for the LEC internal standard. The limits of detection and quantification were 0.6 and 1.2 microg kg(-1), respectively, and the recovery of the method was 101 +/- 10% at 10 microg kg(-1) and 98 +/- 5% at 100 microg kg(-1). The precision of the method, established under conditions of intermediate reproducibility, did not exceed a relative standard deviation of 7%. The quantitative performance of the new GC/PICI-SRM procedure compared favourably with that of a reference method based on GC/MS and selected ion monitoring (correlation coefficient, r = 0.997). However, the new method had the advantages of reduced sample preparation time, improved sensitivity and unambiguous identification of EC at all concentrations. Application of the new method to the analysis of 50 UK breads showed that levels of EC ranged from 0.6 to 2.3 microg kg(-1) in retail products and from 3.1 to 12.2 microg kg(-1) for breads prepared using domestic breadmaking machines (dry weight basis). Toasting bread in a domestic toaster led to increases of between two- and three-fold in mean EC concentrations. Copyright (c) 2005 John Wiley & Sons, Ltd.

  8. Rapid and sensitive quantification of levoglucosan in aerosols by high-performance anion-exchange chromatography with positive electrospray ionization mass spectrometry (HPAEC-positive ESI-MS)

    NASA Astrophysics Data System (ADS)

    Asakawa, Daichi; Furuichi, Yuko; Yamamoto, Atsushi; Oku, Yuichiro; Funasaka, Kunihiro

    2015-12-01

    A convenient quantification method for underivatized levoglucosan, which is a tracer for biomass burning influenced particulate matter (PM), has been established using high-performance anion-exchange chromatography (HPAEC) coupled to positive electrospray ionization mass spectrometry ((+)ESI-MS). Levoglucosan was chromatographically separated from its isomers (mannosan and galactosan) and detected selectively with positive ESI-MS. Limits of detection and quantification for this method were 0.40 and 1.3 ng mL-1, respectively. A comparison of simultaneous measurements by this method and conventional derivatization gas chromatography/mass spectrometry showed a good linearity with a slope of 1.008 and a determination coefficient of 0.9932. The developed method was applied to ambient suspended particulate matter hourly collected by continuous particulate monitors at 10 stations. The hourly concentration of levoglucosan during August 9-11, 2011, was 1.7-918 ng m-3 and its distribution indicated the transportation of biomass burning aerosols of a forest fire. This is the first report of horizontal distribution of the hourly levoglucosan concentration in Japan.

  9. Electrospray ionization mass spectrometry of pyrimidine base-rubidium complexes.

    PubMed

    Frańska, Magdalena

    2005-01-01

    Nucleobases and alkali metal cations, under electrospray ionisation conditions, tend to form the so-called magic number clusters (unusually stable clusters in comparison with the neighbouring ones). The effect of the ion source parameters, namely cone voltage and desolvation temperature and relative concentrations of thymine and RbCl on the [T5+Rb]+ ion abundance has been studied.

  10. The effect of small cations on the positive electrospray responses of proteins at low pH.

    PubMed

    Pan, Peng; McLuckey, Scott A

    2003-10-15

    Solutions consisting of protein and small molecule mixtures have been subjected to electrospray ionization to study the influence of small molecule/cation components at high concentrations on the electrospray responses of proteins. Emphasis was placed on solutions consisting of equal parts methanol and water and containing 1 vol % acetic acid. The results, therefore, are relevant to low pH solutions with significant organic content, a commonly used set of conditions in electrospray ionization mass spectrometry that tends to denature proteins. A variety of small cations/molecules were selected to sample a range of chemical characteristics. For example, sodium and cesium cations were studied to represent metal ions, tetrabutylammonium and tetramethylammonium cations were studied to represent quaternary ammonium compounds with different surface activities, and octadecylamine and glycine were studied to represent species that compete for protons but have different surface activities. A methodology for measuring relative ion suppression efficiencies was developed and applied for protein ions derived from bovine cytochrome c. The form of the small cation (i.e., metal ion, quaternary ammonium ion, or protonated molecule) did not appear to be a factor in determining the efficiency with which protein ion signals were suppressed. The extent to which ions are expected to concentrate on the surface, however, was the major factor in determining the ion suppression efficiency. Itwas found that the ion suppression efficiency of the most surface active species in this study was comparable to that of a protein on another protein after normalization by charge. These results are particularly relevant to the development of mixture analysis strategies based on ionization and tandem mass spectrometry applied to mixtures of whole proteins.

  11. The significance of monoisotopic and carbon-13 isobars for the identification of a 19-component dodecapeptide library by positive ion electrospray Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Ramjit, H G; Kruppa, G H; Spier, J P; Ross, C W; Garsky, V M

    2000-01-01

    Harnessing the ultra high resolution capabilities of Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and positive ion electrospray, we have demonstrated the significance and utility of cumulative mass defect high resolution mass separation stable isotope distribution, exact mass measurement and elemental formula as a means of simultaneously identifying 19 components of the dodecapeptide library Ac-ANKISYQS[X]STE-NH(2). With an instrument resolution of 275 000 (average), isobaric multiplets attributed to monoisotopic and carbon-13 components of peptides: Ac approximately SLS approximately NH(2); Ac approximately SNS approximately NH(2); Ac approximately SOS approximately NH(2); Ac approximately SDS approximately NH(2); within the mass window of 1380-1385 Da, and Ac approximately SQS approximately NH(2); Ac approximately SKS approximately NH(2); Ac approximately SES approximately NH(2); Ac approximately SMS approximately NH(2), within the mass window 1395-1400 Da, were mass resolved, accurately mass measured and identified from the computed molecular formulas. This experimental procedure enabled the separation of monoisotopic and carbon-13 isobars yielding enhanced selectivity and specificity and serves to illustrate the significance of monoisotopic and carbon-13 isobars in final product analysis. Chromatographic separation (HPLC) was of limited utility except for monitoring the overall extent of reaction and apparent product distribution. Positive ion electrospray-FTICR-MS and fast atom bombardment (FAB) MS were used to assess final product quality and apparent component distribution.

  12. MONO- AND DIGALACTOSYLDIACYLGLYCEROL COMPOSITION OF RAPHIDOPHYTES (RAPHIDOPHYCEAE): A MODERN INTERPRETATION USING POSITIVE-ION ELECTROSPRAY/MASS SPECTROMETRY/MASS SPECTROMETRY(1).

    PubMed

    Roche, Shannon A; Leblond, Jeffrey D

    2011-02-01

    Raphidophyte algae (Raphidophyceae) can be divided according to pigment composition and plastid ancestry into two categories, brown- and green-pigmented taxa. We sought to examine if there are any biochemical differences in plastid lipid composition between the two groups. To this end, the composition and positional distribution of fatty acids of the chloroplast lipids, mono- and digalactosyldiacylglycerol (MGDG and DGDG, respectively), were examined using positive-ion electrospray/mass spectrometry (ESI/MS) and electrospray/mass spectrometry/mass spectrometry (ESI/MS/MS). Brown-pigmented strains from the genera Chattonella, Fibrocapsa, and Heterosigma primarily consisted of 20:5/18:4 (sn-1/sn-2) MGDG and 20:5/18:4 DGDG, while isolates of the green-pigmented raphidophyte Gonyostomum semen (Ehrenb.) Diesing contained these as well as 18:3/18:4 MGDG and DGDG, thus underscoring its green algal plastid lineage. Although previously unseen without the regiochemical information provided by ESI/MS/MS, Chattonella subsalsa Biecheler possessed 20:5/18:3 DGDG as a major form, a potential biosynthetic intermediate in the production of 20:5/18:4 DGDG. These results provide a modern interpretation of the fatty acid regiochemistry of MGDG and DGDG.

  13. Direct correlation of the crystal structure of proteins with the maximum positive and negative charge states of gaseous protein ions produced by electrospray ionization.

    PubMed

    Prakash, Halan; Mazumdar, Shyamalava

    2005-09-01

    Electrospray mass spectrometric studies in native folded forms of several proteins in aqueous solution have been performed in the positive and negative ion modes. The mass spectra of the proteins show peaks corresponding to multiple charge states of the gaseous protein ions. The results have been analyzed using the known crystal structures of these proteins. Crystal structure analysis shows that among the surface exposed residues some are involved in hydrogen-bonding or salt-bridge interactions while some are free. The maximum positive charge state of the gaseous protein ions was directly related to the number of free surface exposed basic groups whereas the maximum negative charge state was related to the number of free surface exposed acidic groups of the proteins. The surface exposed basic groups, which are involved in hydrogen bonding, have lower propensity to contribute to the positive charge of the protein. Similarly, the surface exposed acidic groups involved in salt bridges have lower propensity to contribute to the negative charge of the protein. Analysis of the crystal structure to determine the maximum charge state of protein in the electrospray mass spectrum was also used to interpret the reported mass spectra of several proteins. The results show that both the positive and the negative ion mass spectra of the proteins could be interpreted by simple consideration of the crystal structure of the folded proteins. Moreover, unfolding of the protein was shown to increase the positive charge-state because of the availability of larger number of free basic groups at the surface of the unfolded protein.

  14. Hydrophilic interaction liquid chromatography/positive ion electrospray ionization mass spectrometry method for the quantification of alprazolam and α-hydroxy-alprazolam in human plasma.

    PubMed

    Kalogria, Eleni; Pistos, Constantinos; Panderi, Irene

    2013-12-30

    A hydrophilic interaction liquid chromatography/positive ion electrospray-mass spectrometry (HILIC-ESI/MS) has been developed and fully validated for the quantification of alprazolam and its main metabolite, α-hydroxy-alprazolam, in human plasma. The assay is based on 50μL plasma samples, following liquid-liquid extraction. All analytes and the internal standard (tiamulin) were separated by hydrophilic interaction liquid chromatography using an X-Bridge-HILIC analytical column (150.0mm×2.1mm i.d., particle size 3.5μm) under isoscratic elution. The mobile phase was composed of a 7% 10mM ammonium formate water solution in acetonitrile and pumped at a flow rate of 0.20mLmin(-1). Running in positive electrospray ionization and selected ion monitoring (SIM) the mass spectrometer was set to analyze the protonated molecules [M+H](+) at m/z 309, 325 and 494 for alprazolam, α-hydroxy-alprazolam and tiamulin (ISTD) respectively. The assay was linear over the concentration range of 2.5-250ngmL(-1) for alprazolam and 2.5-50ngmL(-1) for α-hydroxy alprazolam. Intermediate precision was less than 4.1% over the tested concentration ranges. The method is the first reported application of HILIC in the analysis benzodiazepines in human plasma. With a small sample size (50μL human plasma) and a run time less than 10.0min for each sample the method can be used to support a wide range of clinical studies concerning alprazolam quantification.

  15. Differential Lipid Profiles of Normal Human Brain Matter and Gliomas by Positive and Negative Mode Desorption Electrospray Ionization – Mass Spectrometry Imaging

    PubMed Central

    Pirro, Valentina; Hattab, Eyas M.; Cohen-Gadol, Aaron A.; Cooks, R. Graham

    2016-01-01

    Desorption electrospray ionization—mass spectrometry (DESI-MS) imaging was used to analyze unmodified human brain tissue sections from 39 subjects sequentially in the positive and negative ionization modes. Acquisition of both MS polarities allowed more complete analysis of the human brain tumor lipidome as some phospholipids ionize preferentially in the positive and others in the negative ion mode. Normal brain parenchyma, comprised of grey matter and white matter, was differentiated from glioma using positive and negative ion mode DESI-MS lipid profiles with the aid of principal component analysis along with linear discriminant analysis. Principal component–linear discriminant analyses of the positive mode lipid profiles was able to distinguish grey matter, white matter, and glioma with an average sensitivity of 93.2% and specificity of 96.6%, while the negative mode lipid profiles had an average sensitivity of 94.1% and specificity of 97.4%. The positive and negative mode lipid profiles provided complementary information. Principal component–linear discriminant analysis of the combined positive and negative mode lipid profiles, via data fusion, resulted in approximately the same average sensitivity (94.7%) and specificity (97.6%) of the positive and negative modes when used individually. However, they complemented each other by improving the sensitivity and specificity of all classes (grey matter, white matter, and glioma) beyond 90% when used in combination. Further principal component analysis using the fused data resulted in the subgrouping of glioma into two groups associated with grey and white matter, respectively, a separation not apparent in the principal component analysis scores plots of the separate positive and negative mode data. The interrelationship of tumor cell percentage and the lipid profiles is discussed, and how such a measure could be used to measure residual tumor at surgical margins. PMID:27658243

  16. Highly sensitive derivatization reagents possessing positively charged structures for the determination of oligosaccharides in glycoproteins by high-performance liquid chromatography electrospray ionization tandem mass spectrometry.

    PubMed

    Min, Jun Zhe; Nagai, Keisuke; Shi, Qing; Zhou, Wenjun; Todoroki, Kenichiro; Inoue, Koichi; Lee, Yong-Ill; Toyo'oka, Toshimasa

    2016-09-23

    We have developed three kinds of novel derivatization reagents (4-CEBTPP, 4-CBBTPP, 5-COTPP) with triphenylphosphine (TPP) as a basic structure carrying a permanent positive charge for resolution of the oligosaccharides in glycoprotein using high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The synthesized reagents reacted with the sialylglycosylamine of the sialylglycopeptide after treatment by PNGase F. The final derivatives were analyzed by ESI-MS and sensitively detected in the selected reaction monitoring (SRM) mode. Furthermore, the limits of detection (S/N=3) on the SRM chromatograms were at the fmol level (30fmol). Therefore, we used the limit of detection of the reagent products detected by the SRM and evaluated the utility of each reagent. Among the reagents, the positively charged 4-CEBTPP derivative's peak area was the highest; 4-CEBTPP with a positively charged structure showed about a 20 times greater sensitivity for the glycosylamine of the SGP product compared to the conventional fluorescence reagent, Fmoc-Cl. In addition, various fragment ions based on the carbohydrate units also appeared in the MS/MS spectra. Among the fragment ions, m/z 627.37 (CE=40eV) corresponding to 4-CEBTPP-GlcNAc and m/z 120.09 (CE=100eV) corresponding to 4-CEBTPP are the most important ones for identifying the oligosaccharide. 4-CEBTPP-SGA was easily identified by the selected-ion chromatogram in the product ion scan (m/z 120.09) and in the precursor ion scan (m/z 627.37) by MS/MS detection. The derivatized analytes have a high ionization efficiency and they are detected with a high sensitivity in the electrospray ionization. The novel derivatization reagent with a multi-function provided a higher sensitivity for the oligosaccharide analysis, as well as a better specificity and feasibility. Furthermore, several oligosaccharides in fetuin and ribonuclease B were successfully identified by the proposed procedure

  17. Ballpoint pen inks: characterization by positive and negative ion-electrospray ionization mass spectrometry for the forensic examination of writing inks.

    PubMed

    Ng, Lay-Keow; Lafontaine, Pierre; Brazeau, Luc

    2002-11-01

    A method based on profiling of dye components by electrospray ionization mass spectrometry (ESI/MS) is described for the characterization of ballpoint pen inks. The method involves benzyl alcohol (30 microL) extraction of ink from paper. The extracts of ink lines 1 and 5 mm in length are used for direct ESI/MS analysis in positive and negative modes, respectively. The instrumental analysis takes 3 min. Basic and acid dyes in the inks are detected in the positive and negative modes, respectively, with each dye yielding one or two characteristic ion peaks. The mass spectrum, which is mainly a compositional signature of the dyes in the ink, was not affected by the type of paper from which the ink was extracted, or by natural ageing of the ink on document in the absence of light. However, exposure to fluorescent illumination caused dealkylation of polyalkylated basic dyes and resulted in changes in the homologous distribution of the dyes. In this study, a total of 44 blue inks, 23 black inks, and 10 red inks have been analyzed, and the mass spectra were used to establish a searchable library. ESI/MS analysis provides a simple and fast way to compare ink specimens and in combination with on-line library search permits rapid screening of inks for forensic document investigations.

  18. Simultaneous identification of nine carcinogenic dyes from textiles by liquid chromatography/electrospray ionization mass spectrometry via negative/positive ion switching mode.

    PubMed

    Ding, Youchao; Sun, Cheng; Xu, Xinhua

    2009-01-01

    A method has been established by using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI/MS/MS) for simultaneous separation and identification of nine carcinogenic dyes (Acid Red 26, Direct Blue 6, Direct Black 38, Direct Red 28, Basic Red 9, Basic Violet 14, Disperse Blue 1, Disperse Orange 11 and Disperse Yellow 3) prohibited in textile materials under EU 2002/371/EC decision. Three selected reaction monitoring (SRM) transitions and negative/positive ion switching mode in one single analysis was applied to differentiate between the dyes of different classes. A lower limit of detection was achieved at 0.025-0.25 mg kg(-1) of positive ESI dyes and 0.005-0.025 mg kg(-1) of negative ESI dyes. The accurate and sensitive identification of the nine dissimilar analytes was achieved by combining the characterized ions and retention time of the standards, for example, the characterized ions of [M - xNa](x-), [M -Cl](+) and [M + H](+), respectively were detected for the the sulfonated (acid and direct), basic and disperse dyes. The chromophore groups of azo, triphenylmethane and anthraquinone in precursor ions were found to have fragmented in SRM mode. These results demonstrated a sensitive, accurate and rapid identification.

  19. Electron ionisation of sulfur dioxide.

    PubMed

    Fletcher, James D; Parkes, Michael A; Price, Stephen D

    2013-05-14

    Relative precursor-specific partial ionisation cross sections for the fragment ions formed following electron ionisation of sulfur dioxide (SO2) have been measured for the first time, from 30 to 200 eV, using time-of-flight mass spectrometry coupled with two-dimensional ion coincidence detection. These data quantify the yields of O(2+), O(+), SO(2+), S(+), O2(+), and SO(+) ions, relative to the formation of SO2(+), via single, double, and triple electron ionisation of SO2. Formation of O(2+), following electron-SO2 collisions, has been quantified for the first time. The data allow a first experimental estimate of the triple ionisation potential of SO2 (69.0 ± 3.6 eV), an energy in good agreement with a value derived in this study via computational chemistry. The triple ion combination S(+) + O(+) + O(+) is clearly detected following electron collisions with SO2 at electron energies markedly below the vertical energy for forming SO2(3 +). This observation is accounted for by the operation of a stepwise pathway to the formation of S(+) + 2O(+) which does not involve the formation of a molecular trication.

  20. Derivatization of the tricarboxylic acid cycle intermediates and analysis by online solid-phase extraction-liquid chromatography-mass spectrometry with positive-ion electrospray ionization.

    PubMed

    Kloos, D; Derks, R J E; Wijtmans, M; Lingeman, H; Mayboroda, O A; Deelder, A M; Niessen, W M A; Giera, M

    2012-04-06

    The analysis of cellular metabolic processes is of fundamental biological interest. Cellular metabolites, such as the intermediates of the tricarboxylic acid (TCA) cycle, provide essential information about the metabolic state of the cell. Not only is the TCA cycle a key factor in the energy regulation within aerobic cells, it possibly also plays a role in cell signaling. This paper describes a novel derivatization strategy, using the empirically selected N-methyl-2-phenylethanamine as derivatization reagent with a carbodiimide as co-reagent, for the selective derivatization of carboxylic acids, such as the di- and tri-carboxylic acids of the TCA cycle. Optimization of the derivatization protocol is described. This procedure enables analysis of the derivatives using on-line solid-phase extraction and reversed-phase liquid chromatography in combination with sensitive positive-ion electrospray ionization mass spectrometry. The complete procedure, involving the use of core-shell silica column material, allows the rapid analysis of TCA cycle intermediates in sample matrices, here shown for pig heart tissue extracts, with a good linearity over 3-4 orders of magnitude. Detection limits range from 12 to 1000 nM, depending on the analyte. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Chromatographic enrichment and subsequent separation of nickel and vanadyl porphyrins from natural seeps and molecular characterization by positive electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Putman, Jonathan C; Rowland, Steven M; Corilo, Yuri E; McKenna, Amy M

    2014-11-04

    We report a novel chromatographic method to enrich and separate nickel and vanadyl porphyrins from a natural seep sample and combine molecular level characterization by positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Vanadyl and nickel porphyrin model compound elution from primary secondary amine (PSA) stationary phase combined with UV-vis spectroscopy confirms enrichment and subsequent fractionation of nickel and vanadyl porphyrins into polarity-based subfractions. A more than 100-fold increase in signal-to-noise ratio for nickel porphyrins enables unequivocal elemental composition assignment confirmed by isotopic fine structure for all isotopes >1% relative abundance, and the first mass spectral identification of (61)Ni porphyrin isotopologues derived from natural seeps. Oxygen-containing vanadyl porphyrins and sulfur-containing vanadyl porphyrins are isolated in the same fraction simultaneously from the same sample. We provide the first chromatographic evidence of carboxylic acid functionalities peripheral to the porphyrin core, in agreement with previous studies.

  2. Influence of water vapour on the height distribution of positive ions, effective recombination coefficient and ionisation balance in the quiet lower ionosphere

    NASA Astrophysics Data System (ADS)

    Barabash, V.; Osepian, A.; Dalin, P.

    2014-03-01

    Mesospheric water vapour concentration effects on the ion composition and electron density in the lower ionosphere under quiet geophysical conditions were examined. Water vapour is an important compound in the mesosphere and the lower thermosphere that affects ion composition due to hydrogen radical production and consequently modifies the electron number density. Recent lower-ionosphere investigations have primarily concentrated on the geomagnetic disturbance periods. Meanwhile, studies on the electron density under quiet conditions are quite rare. The goal of this study is to contribute to a better understanding of the ionospheric parameter responses to water vapour variability in the quiet lower ionosphere. By applying a numerical D region ion chemistry model, we evaluated efficiencies for the channels forming hydrated cluster ions from the NO+ and O2+ primary ions (i.e. NO+.H2O and O2+.H2O, respectively), and the channel forming H+(H2O)n proton hydrates from water clusters at different altitudes using profiles with low and high water vapour concentrations. Profiles for positive ions, effective recombination coefficients and electrons were modelled for three particular cases using electron density measurements obtained during rocket campaigns. It was found that the water vapour concentration variations in the mesosphere affect the position of both the Cl2+ proton hydrate layer upper border, comprising the NO+(H2O)n and O2+(H2O)n hydrated cluster ions, and the Cl1+ hydrate cluster layer lower border, comprising the H+(H2O)n pure proton hydrates, as well as the numerical cluster densities. The water variations caused large changes in the effective recombination coefficient and electron density between altitudes of 75 and 87 km. However, the effective recombination coefficient, αeff, and electron number density did not respond even to large water vapour concentration variations occurring at other altitudes in the mesosphere. We determined the water vapour

  3. Electrospray ionization tandem mass spectrometric study of protonated and alkali- cationized α/ε-hybrid peptides: differentiation of a pair of dipeptide positional isomers.

    PubMed

    Ramesh Babu, A; Raju, G; Purna Chander, C; Shoban Babu, B; Srinivas, R; Sharma, G V M

    2016-01-01

    A new class of Boc-N-protected hybrid peptides derived from L- Ala and ε(6)-Caa (L-Ala = L-Alanine, Caa = C-linked carboamino acid derived from D-xylose) have been studied by positive ion electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS). MS(n) spectra of protonated and alkali-cationized hybrid peptides produce characteristic fragmentation involving the peptide backbone, the tert-butyloxycarbonyl (Boc) group, and the side chain. The dipeptide positional isomers are differentiated by the collision-induced dissociation (CID) of the protonated and alkali-cationized peptides. The CID of [M + H](+) ion of Boc-NH-L-Ala-ε-Caa- OCH3 (1) shows a prominent [M + H - C4H8](+) ion, which is totally absent for its positional isomer Boc-NH-ε-Caa-L-Ala-OCH3 (6), which instead shows significant loss of t-butanol. The formation of the [M + Cat - C4H8](+) ion is totally absent and [M + Cat - Boc + H](+) is prominent in the CID of the [M + Cat](+) ion of Boc-NH-L-Ala-ε-Caa- OCH3 (1), whereas the former is highly abundant and the latter is of low abundance for its positional isomer Boc-NH-ε-Caa-L-Ala-OCH3 (6). It is observed that 'b' ions are abundant when oxazolone structures are formed through a five-membered cyclic transition state in tetra-, penta-, and hexapeptides and the cyclization process for larger 'b' ions led to an insignificant abundance. However, the significant 'b' ion is formed in ε,α-dipeptide, which may have a seven-membered substituted 2-oxoazepanium ion structure. The MS(n) spectra of [M + Cat - Boc + H](+) ions of these peptides are found to be significantly different to those of [M + H - Boc + H](+) ions. The CID spectra of [M + Cat - Boc + H](+) ions of peptide acids containing L-Ala at the C-terminus show an abundant N-terminal rearrangement ion, [b(n) + 17 + Cat](+), which is absent for the peptide acids containing ε-Caa at the C-terminus. Thus, the results of these hybrid peptides

  4. Electrospray tandem mass spectrometry of alkali-cationized BocN-carbo-alpha,beta- and -beta,alpha-peptides: Differentiation of positional isomers.

    PubMed

    Reddy, P Nagi; Srikanth, R; Srinivas, R; Sharma, V U M; Sharma, G V M; Nagendar, P

    2006-01-01

    Dissociation pathways of a series of alkali-cationized hybrid peptides, viz., Boc-alpha,beta- and -beta,alpha-carbopeptides, synthesized from C-linked carbo-beta3-amino acids [Caa (S)] and alpha-alanine (L-Ala), have been investigated by electrospray ionization tandem mass spectrometry. The positional isomers (six pairs) of the cationized alpha,beta- and beta,alpha-peptides can be differentiated by the collision-induced dissociation (CID) spectra of their [M + Cat-Boc + H]+ ions which give characteristic series of alkali-cationized C- (x(n)+, y(n)+, z(n)+) and N-terminal (a(n)+, b(n)+, c(n)+) ions. Another noteworthy difference is cationized beta,alpha-peptides eliminate a molecule of ammonia whereas this pathway is absent for alpha,beta-peptides. This is useful for identifying the presence of a beta-amino acid at the N-terminus. The CID spectra of [M + Cat-Boc + H]+ ions of these peptide acids show abundant rearrangement [b(n) + 17 + Cat]+ (n = 1 to n-1) ions which is diagnostic for distinguishing between alpha- and beta-amino acid at the C-terminus. MS(n) experiments of [b(n) + Li-H]+ ions from these hybrid peptides showed the loss of CO and 72 u giving rise to [a(n) + Li-H]+ and cationized nitrile product ions which render support to earlier proposals that b(n)+ or [b(n) + Cat-H]+ ions have protonated or cationized oxazolinone structures, respectively.

  5. Residue analysis of thyreostats in baby foods via matrix solid phase dispersion and liquid chromatography - dual-polarity electrospray - tandem mass spectrometry.

    PubMed

    Gentili, Alessandra; De Pratti, Valeria; Caretti, Fulvia; Pérez-Fernández, Virginia; Tomai, Pierpaolo; Curini, Roberta; Mainero Rocca, Lucia

    2016-12-01

    This paper describes a rapid method for confirming residues of thyreostats in meat-based baby foods by using liquid chromatography - dual polarity electrospray - tandem mass spectrometry (LC-ES(±)-MS/MS). Six thioureylenes, belonging to the group of thiouracil and imidazole, were selected for this work: thiouracil (TU), methylthiouracil (MTU), propylthiouracil (PTU), phenylthiouracil (PhTU), mercaptobenzimidazole (MBI) and tapazole (TAP). The amphoteric nature of these compounds allows their electrospray detection in both positive and negative ionisation. Nevertheless, MS detection is not favoured by their low molecular weights, while their chromatographic retention is also thwarted by their high polarity. A pentafluorophenyl (PFP) core-shell phase column was selected to avoid peak asymmetry or peak splitting, and a dual-polarity ionisation method was optimised to obtain a sensitivity as high as possible. The method was validated according to the Commission Decision 657/2002/EC. A simple and fast procedure based on matrix solid phase dispersion (MSPD) was optimised to extract analytes from baby foods with recoveries exceeding 82%. Limit of decision (CCα) and detection capability (CCβ) were lower than the permissible maximum concentration (10 ng g(-1)). The validated method was then applied to assess the potential occurrence of the six selected thyreostats in nine commercial products. All the samples were found free of contamination.

  6. Ionisers in the management of bronchial asthma.

    PubMed Central

    Nogrady, S G; Furnass, S B

    1983-01-01

    Because of recent interest in the possible benefits to asthmatic patients of negative ion generators and the largely uncontrolled and inconclusive nature of earlier studies a double blind crossover study of this treatment was carried out in 20 subjects with stable asthma over six months. After an initial two week period without an ioniser, active or placebo ionisers were installed in subjects' bedrooms for two eight week periods separated by a four week "washout" period when no ioniser was present. The study was completed by a final four week period when no ioniser was present. Subjects were randomly allocated to receive an active or a placebo ioniser first. Subjects recorded their peak expiratory flow rate (PEFR) twice daily, completed a daily symptom score questionnaire, and noted any treatment they took on a diary card. Recordings were completed throughout the trial. Ion counts and dust concentrations were measured in subjects' bedrooms during the study. Mean ion counts rose considerably when ionisers were activated (p less than 0.001). There were no significant differences in PEFR, symptom score, or consumption of medication between the periods that active ionisers and either no ionisers or placebo ionisers were in operation. This study has failed to show a statistically significant benefit in asthmatic subjects from the use of negative ion generators. PMID:6364442

  7. Ionisation Chambers and Secondary Emission Monitors at the PROSCAN Beam Lines

    NASA Astrophysics Data System (ADS)

    Dölling, Rudolf

    2006-11-01

    PROSCAN, the dedicated new medical facility at PSI using proton beams for the treatment of deep seated tumours and eye melanoma, is now in the commissioning phase. Air filled ionisation chambers in several configurations are used as current monitors, profile monitors, halo, position and loss monitors at the PROSCAN beam lines. Similar monitors based on secondary emission are used for profile and current measurements in the regime where saturation deteriorates the accuracy of the ionisation chambers.

  8. Selective laser ionisation of radionuclide 63Ni

    NASA Astrophysics Data System (ADS)

    Tsvetkov, G. O.; D'yachkov, A. B.; Gorkunov, A. A.; Labozin, A. V.; Mironov, S. M.; Firsov, V. A.; Panchenko, V. Ya.

    2017-02-01

    We report a search for a scheme of selective laser stepwise ionisation of radionuclide 63Ni by radiation of a dye laser pumped by a copper vapour laser. A three-stage scheme is found with ionisation through an autoionising state (AIS): 3d 84s2 3F4(E = 0) → 3d 94p 1Fo3(31030.99 cm-1) → 3d 94d 2[7/2]4(49322.56 cm-1) → AIS(67707.61 cm-1) which, by employing saturated radiation intensities provides the ionisation selectivity of above 1200 for 63Ni.

  9. Bacterial Spores Survive Electrospray Charging and Desolvation

    NASA Astrophysics Data System (ADS)

    Pratt, Sara N.; Austin, Daniel E.

    2014-05-01

    The survivability of Bacillus subtilis spores and vegetative Escherichia coli cells after electrospray from aqueous suspension was tested using mobility experiments at atmospheric pressure. E. coli did not survive electrospray charging and desolvation, but B. subtilis did. Experimental conditions ensured that any surviving bacteria were de-agglomerated, desolvated, and electrically charged. Based on mobility measurements, B. subtilis spores survived even with 2,000-20,000 positive charges. B. subtilis was also found to survive introduction into vacuum after either positive or negative electrospray. Attempts to measure the charge distribution of viable B. subtilis spores using electrostatic deflection in vacuum were inconclusive; however, viable spores with low charge states (less than 42 positive or less than 26 negative charges) were observed.

  10. Serum ionised calcium concentration: measurement versus calculation.

    PubMed Central

    Conceicao, S C; Weightman, D; Smith, P A; Luno, J; Ward, M K; Kerr, D N

    1978-01-01

    Four hundred and eighteen measurements of serum ionised calcium, total calcium, and protein concentrations were made from 47 normal volunteers, 104 patients with chronic renal failure (33 being treated conservatively and 71 with regular haemodialysis), and 83 renal transplant recipients. The serum ionised calcium concentration was measured with an Orion SS-20 meter and calculated from the total serum calcium and protein concentrations by using three formulae and a nomogram. In the normal subjects and patients undergoing regular haemodialysis, whose serum calcium concentrations were in or near the normal range, three of the calculations gave results similar to those obtained by direct measurement. In patients with conservatively treated chronic renal failure and those who had received renal transplants, however, there was poor aggrement between the methods. When patients with hypercalcaemia and hypocalcaemia from all the groups were considered separately there was again poor agreement between calculated and measured concentrations of serum ionised calcium. Of the patients whose measured concentrations of serum ionised calcium were high, 69-76% were classified as normal by the four indirect methods. We conclude that calculation of the serum ionised calcium concentrations is not an adequate substitute for direct measurement. PMID:346162

  11. New features on the fragmentation and differentiation of C-glycosidic flavone isomers by positive electrospray ionization and triple quadrupole mass spectrometry.

    PubMed

    Abad-García, Beatriz; Garmón-Lobato, Sergio; Berrueta, Luis A; Gallo, Blanca; Vicente, Francisca

    2008-06-01

    Six flavone mono-C-glucosides, four standards (beta-D-glucopyranosyl-(1 --> C-6)- and -(1 --> C-8)- apigenin and luteolin) and two others from lemon juice (beta-D-glucopyranosyl-(1 --> C-6)- and -(1 --> C-8)-diosmetin) have been studied in order to analyze their fragmentation patterns. Initial separation was carried out using high-performance liquid chromatography with diode-array detection (HPLC/DAD) coupled to an electrospray ionization (ESI) interface and a triple quadrupole mass spectrometer. Several systematic differences between collision-induced dissociation tandem mass (CID-MS/MS) spectra of C-6- and C-8-isomers have been found and some general guidelines and two new diagnostic product ions have been proposed for the differentiation of C-6- and C-8-flavonoid glycosides. These results have been successfully applied to the characterization of two flavone C-glycosides found in lemon juice, and mass spectra of a flavone di-C-glycoside detected in lemon juice have been studied and interpreted.

  12. Tunnelling time in strong field ionisation

    NASA Astrophysics Data System (ADS)

    Landsman, Alexandra S.; Keller, Ursula

    2014-10-01

    We revisit the common approaches to tunnelling time in the context of attoclock experiments. These experiments measure tunnelling time using close-to-circularly polarised light of the infrared ultrashort laser pulse. We test the sensitivity of the attoclock measurements of tunnelling time to non-adiabatic effects, as described by a well-known theoretical model first developed by Perelomov, Popov, and Terent'ev. We find that in the case of ionisation of helium, both adiabatic and non-adiabatic theories give very similar predictions for ionisations times over a wide intensity range typical of ultrafast experiments.

  13. Metal cation detection in positive ion mode electrospray ionization mass spectrometry using a tetracationic salt as a gas-phase ion-pairing agent: evaluation of the effect of chelating agents on detection sensitivity.

    PubMed

    Xu, Chengdong; Dodbiba, Edra; Padivitage, Nilusha L T; Breitbach, Zachary S; Armstrong, Daniel W

    2012-12-30

    The detection of metal cations continues to be essential in many scientific and industrial areas of interest. The most common electrospray ionization mass spectrometry (ESI-MS) approach involves chelating the metal ions and detecting the organometallic complex in the negative ion mode. However, it is well known that negative ion mode ESI-MS is generally less sensitive than the positive ion mode. To achieve greater sensitivity, it is necessary to examine the feasibility of detecting the chelated metal cations in positive ion mode ESI-MS. Since highly solvated native metal cations have relatively low ionization efficiency in ESI-MS, and can be difficult to detect in the positive ion mode, a tetracationic ion-pairing agent was added to form a complex with the negatively charged metal chelate. The use of the ion-pairing agent leads to the generation of an overall positively charged complex, which can be detected at higher m/z values in the positive ion mode by electrospray ionization linear quadrupole ion trap mass spectrometry. Thirteen chelating agents with diverse structures were evaluated in this study. The nature of the chelating agent played as important a role as was previously determined for cationic pairing agents. The detection limits of six metal cations reached sub-picogram levels and significant improvements were observed when compared to negative ion mode detection where the metal-chelates were monitored without adding the ion-pairing reagent (IPR). Also, selective reaction monitoring (SRM) analyses were performed on the ternary complexes, which improved detection limits by one to three orders of magnitude. With this method it was possible to analyze the metal cations in the positive ion mode ESI-MS with the advantage of speed, sensitivity and selectivity. The optimum solution pH for this type of analysis is 5-7. Tandem mass spectrometry (MS/MS) further increases the sensitivity. Speciation is straightforward making this a broadly useful approach for the

  14. A systematic review of matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry compared to routine microbiological methods for the time taken to identify microbial organisms from positive blood cultures.

    PubMed

    Dixon, P; Davies, P; Hollingworth, W; Stoddart, M; MacGowan, A

    2015-05-01

    Bloodstream infections are a significant source of mortality and morbidity. Patient outcomes are improved by rapid identification of the causative pathogen and administration of appropriate antimicrobial therapy. Matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) mass spectrometry has recently emerged as an alternative to microbiological identification. It is important to establish whether the costs of MALDI-TOF are justified by more timely identification and appropriate therapy, reduced length of stay and reduced hospital costs. We undertook a systematic review of the literature comparing MALDI-TOF and routine methods for the identification of the aetiological agent in patients with known or suspected bloodstream infection. The primary outcome of the review was the 'time to identify' organisms. Information on related measures such as 'time to appropriate antimicrobial treatment' and downstream hospital cost was also collected where reported. Ten of 775 articles identified met the inclusion criteria. All included studies were observational. MALDI-TOF identification was at least 24 h faster than routine methods in most circumstances. MADLI-TOF was associated with a reduction in downstream hospital costs and length of stay in studies reporting these outcomes. The observational studies reviewed provide evidence of potentially substantial time savings of MALDI-TOF in pathogen identification and instigation of appropriate therapy, which may also reduce hospital stay. Due to the small number of studies, all at relatively high risk of bias, this cannot be considered as definitive evidence of the impact of MALDI-TOF. More and better evidence, including impact on patient health and cost-effectiveness, is required.

  15. NICIL: Non-Ideal magnetohydrodynamics Coefficients and Ionisation Library

    NASA Astrophysics Data System (ADS)

    Wurster, James

    2016-08-01

    NICIL (Non-Ideal magnetohydrodynamics Coefficients and Ionisation Library) calculates the ionization values and the coefficients of the non-ideal magnetohydrodynamics terms of Ohmic resistivity, the Hall effect, and ambipolar diffusion. Written as a standalone Fortran90 module that can be implemented in existing codes, NICIL is fully parameterizable, allowing the user to choose which processes to include and decide the values of the free parameters. The module includes both cosmic ray and thermal ionization; the former includes two ion species and three species of dust grains (positively charged, negatively charged and neutral), and the latter includes five elements which can be doubly ionized.

  16. Application of atmospheric pressure chemical ionisation mass spectrometry in the analysis of barbiturates by high-speed analytical countercurrent chromatography.

    PubMed

    Jones, Jonathan J; Kidwell, Huw; Games, David E

    2003-01-01

    Four barbiturates (barbital, allobarbital, phenobarbital and butalbital) were analysed using high-speed analytical countercurrent chromatography (HSACCC) and high-performance liquid chromatography (HPLC) interfaced with mass spectrometry, using negative mode atmospheric pressure chemical ionisation (APCI). The polar biphasic solvent system of butyronitrile/acetonitrile/water (1:1:1) was used, in the upper-stationary, lower-mobile mode of operation, at a flow rate of 1 mL/min and a rotational speed of 1200 rpm, equating to an applied "g"-field of 177 g. The fractional stationary phase retention (S(F)) was 0.58. Representative mass spectral data are presented from the HPLC and the HSACCC analyses. Structural information was obtained using source-induced fragmentation at increased source block voltages. The effect of increasing g-field on chromatographic resolution is illustrated using the binary base system of butyronitrile/water (1:1), under electrospray ionisation. Copyright 2003 John Wiley & Sons, Ltd.

  17. Ionisation en couche K et effet biologique

    NASA Astrophysics Data System (ADS)

    L'Hoir, A.; Herve Du Penhoat, M. A.; Champion, C.; Fayard, B.; Touati, A.; Abel, F.; Politis, M. F.; Despiney-Bailly, I.; Sabatier, L.; Chetioui, A.

    1998-04-01

    Initial steps of radiation action mechanism on biological targets are still undnown. The strong correlation observed between inactivation cross sections by heavy ions and K-vacancy production cross sections has drawn the attention on this process. Although quite minor in the energy deposition of these particles, the K-ionization process gives rise to quite efficient ionization clusters. Values of K-ionization biological effectivenesses extracted from measured relative biological efficiencies of ultra soft X-rays support the idea of a major -may be a dominant- contribution of the K-vacancy process to the biological effect of heavy ions. Les étapes initiales des mécanismes d'effet biologique des radiations sont encore mal connues. La forte corrélation observée entre sections efficaces d'inactivation par ions lourds et sections efficaces d'ionisation K a attiré l'attention sur ce processus. Bien que de faible probabilité, l'ionisation K engendre des grappes d'ionisation très efficaces. Les valeurs de rendement létal extraites des efficacités biologiques relatives mesurées pour les rayonnements X ultra-mous suggèrent une contribution majeure -peut-être dominante- de l'ionisation K à l'effet biologique des ions.

  18. Effect of radiation-induced charge accumulation on build-up cap on the signal current from an ionisation chamber.

    PubMed

    Takata, N; Morishita, Y

    2011-04-01

    The signal current from a thimble ionisation chamber with a build-up cap made of an insulator decreases by about 0.41 % after being irradiated for 17 h at an air kerma rate of 41 Gy h(-1) by a collimated (60)Co gamma-ray beam in air. In contrast, the signal current remains constant when the thimble ionisation chamber is irradiated in a water phantom. During irradiation, positive charge is considered to accumulate near the outer surface of the build-up cap where electron equilibrium is not achieved. Secondary electrons travelling in the build-up cap and the chamber wall toward the ionisation volume are decelerated by the electric field generated by the positive charge. Consequently, the signal current decreases with increasing charge accumulation because some secondary electrons are prevented from entering the ionisation volume. In the water phantom, electron equilibrium is established in and around the ionisation chamber and charge does not accumulate. To confirm this hypothesis, the signal current was measured for an ionisation chamber in air with a build-up cap wrapped with Al foil and covered with PMMA tubes. Electron equilibrium was established over the build-up cap because the tubes were thicker than the secondary electron range. The signal current decreased with increasing positive voltage applied to the Al foil. It was estimated from the results that positive charges equivalent to a voltage of over 6 kV applied to the Al foil accumulated during irradiation. The signal current was also measured for an ionisation chamber with a metal build-up cap and for an ionisation chamber with a wall and build-up cap made of conductive plastic.

  19. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    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.

  20. Electrospray Droplet Impact/SIMS

    NASA Astrophysics Data System (ADS)

    Hiraoka, Kenzo

    A new type of cluster SIMS, named as electrospray droplet impact (EDI), has been developed in our laboratory. It was found that peptides deposited on the stainless steel substrate were ionized/desorbed without the accumulation of radiation products. The organic samples with film thickness thinner than 10 monolayers are desorbed/ionized with little damage underneath the surface. In general, rather strong negative ions as well as positive ions are generated. The mechanism for the ionization/desorption in EDI is much less complicated than those for MALDI and SIMS due to the fact that only very thin sample layers take part in the shock-wave excited selvedge and higher-order side reactions are largely suppressed.

  1. Electrospraying from nanofluidic capillary slot

    NASA Astrophysics Data System (ADS)

    Arscott, Steve; Troadec, David

    2005-09-01

    We present here an original electrospray emitter tip based on a nanofluidic capillary slot. The nanofabrication involves focused ion beam etching to form the slot which has a cross-section of 50×300nm and a length of 4μm. The liquid is deformed into the nanofluidic capillary slot by capillary action; the electrospray is produced by the application of a low voltage. Using a water-methanol-formic acid solution, we have observed an electrospray onset voltage of 125V. At a measured electrospray current of 1nA, the unforced flow-rate is estimated to be 110pLmin-1.

  2. Background ionising radiation: a pictorial perspective.

    PubMed

    Bibbo, Giovanni; Piotto, Lino

    2014-09-01

    Ionising radiation from natural sources, known as background radiation, has existed on earth since the earth's formation. The exposure of humans and other living creatures to this radiation is a feature of the earth's environment which is continuing and inescapable. The word "radiation" brings fear to many people: a fear of the unknown, as human's senses cannot detect the presence of ionising radiation. In this study, a catalogue of images of the distribution of radioactivity in every day objects and foods has been produced using an imaging plate from a computed radiography cassette. The aim of the study is that by visually demonstrating that every day objects and foods are radioactive would alleviate the fear of "radiation" by becoming aware that we live in a radioactive environment and even our body is radioactive.

  3. Multi-mycotoxin Analysis of Finished Grain and Nut Products Using Ultrahigh-Performance Liquid Chromatography and Positive Electrospray Ionization-Quadrupole Orbital Ion Trap High-Resolution Mass Spectrometry.

    PubMed

    Liao, Chia-Ding; Wong, Jon W; Zhang, Kai; Yang, Paul; Wittenberg, James B; Trucksess, Mary W; Hayward, Douglas G; Lee, Nathaniel S; Chang, James S

    2015-09-23

    Ultrahigh-performance liquid chromatography using positive electrospray ionization and quadrupole orbital ion trap high-resolution mass spectrometry was evaluated for analyzing mycotoxins in finished cereal and nut products. Optimizing the orbital ion trap mass analyzer in full-scan mode using mycotoxin-fortified matrix extracts gave mass accuracies, δM, of < ± 2.0 ppm at 70,000 full width at half maximum (FWHM) mass resolution (RFWHM). The limits of quantitation were matrix- and mycotoxin-dependent, ranging from 0.02 to 11.6 μg/kg. Mean recoveries and standard deviations for mycotoxins from acetonitrile/water extraction at their relevant fortification levels were 91 ± 10, 94 ± 10, 98 ± 12, 91 ± 13, 99 ± 15, and 93 ± 17% for corn, rice, wheat, almond, peanut, and pistachio, respectively. Nineteen mycotoxins with concentrations ranging from 0.3 (aflatoxin B1 in peanut and almond) to 1175 μg/kg (fumonisin B1 in corn flour) were found in 35 of the 70 commercial grain and nut samples surveyed. Mycotoxins could be identified at δM < ± 5 ppm by identifying the precursor and product ions in full-scan MS and data-dependent MS/MS modes. This method demonstrates a new analytical approach for monitoring mycotoxins in finished grain and nut products.

  4. Effects of ionised or chelated water-soluble mineral mixture supplementation on growth performance, nutrient digestibility, blood characteristics, meat quality and intestinal microbiota in broilers.

    PubMed

    Upadhaya, S D; Lee, B R; Kim, I H

    2016-04-01

    An experiment was conducted to study the effects of dietary supplementation of water-soluble ionised or chelated mineral mixture on growth performance, nutrient digestibility, blood characteristics, relative organ weight, meat quality and excreta microflora in broilers. A total of 408 Arbor Acres broilers (17 birds in 8 replicate pens) were randomly allocated into one of the following three treatments: (1) Control/basal diet (CON), (2) T1 (basal diet + 0.5% ionised mineral mixture solution, pH 3.0) and (3) T2 (basal diet + 0.5% chelated mineral mixture solution, pH 3.0). The body weight gain was greater and feed conversion ratio was lower in broilers supplemented with ionised or chelated mineral liquid complex compared to CON during the grower and overall phase of the experiment. No significant effect in the concentration of Ca and P in the blood was observed in birds supplemented with ionised or chelated mineral mixture solution. No adverse effects were observed in organ weight and meat quality with ionised or chelated mineral mixture supplementation. Regarding intestinal microbiota counts there was a reduction of Escherichia coli counts in the small intestine in ionised mineral supplemented birds. In the large intestine, E. coli as well as Salmonella populations were reduced in ionised mineral supplemented birds. In conclusion, ionised or chelated minerals have partial positive effects in improving growth performance and reducing pathogenic bacteria load in the gastro-intestinal tract.

  5. European Code against Cancer 4th Edition: Ionising and non-ionising radiation and cancer.

    PubMed

    McColl, Neil; Auvinen, Anssi; Kesminiene, Ausrele; Espina, Carolina; Erdmann, Friederike; de Vries, Esther; Greinert, Rüdiger; Harrison, John; Schüz, Joachim

    2015-12-01

    Ionising radiation can transfer sufficient energy to ionise molecules, and this can lead to chemical changes, including DNA damage in cells. Key evidence for the carcinogenicity of ionising radiation comes from: follow-up studies of the survivors of the atomic bombings in Japan; other epidemiological studies of groups that have been exposed to radiation from medical, occupational or environmental sources; experimental animal studies; and studies of cellular responses to radiation. Considering exposure to environmental ionising radiation, inhalation of naturally occurring radon is the major source of radiation in the population - in doses orders of magnitude higher than those from nuclear power production or nuclear fallout. Indoor exposure to radon and its decay products is an important cause of lung cancer; radon may cause approximately one in ten lung cancers in Europe. Exposures to radon in buildings can be reduced via a three-step process of identifying those with potentially elevated radon levels, measuring radon levels, and reducing exposure by installation of remediation systems. In the 4th Edition of the European Code against Cancer it is therefore recommended to: "Find out if you are exposed to radiation from naturally high radon levels in your home. Take action to reduce high radon levels". Non-ionising types of radiation (those with insufficient energy to ionise molecules) - including extremely low-frequency electric and magnetic fields as well as radiofrequency electromagnetic fields - are not an established cause of cancer and are therefore not addressed in the recommendations to reduce cancer risk. Copyright © 2015 International Agency for Research on Cancer. Published by Elsevier Ltd. All rights reserved.

  6. Simultaneous determination of phentermine and topiramate in human plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application in pharmacokinetic study.

    PubMed

    Ni, Yang; Zhou, Ying; Xu, Mingzhen; He, Xiaomeng; Li, Huqun; Haseeb, Satter; Chen, Hui; Li, Weiyong

    2015-03-25

    A new method for simultaneous determination of phentermine and topiramate by liquid chromatography/electrospray tandem mass spectrometry (LC/MS/MS) operated in positive and negative ionization switching modes was developed and validated. Protein precipitation with acetonitrile was selected for sample preparation. Analyses were performed on a liquid chromatography system employing a Kromasil 60-5CN column (2.1 mm × 100 mm, 5 μm) and an isocratic elution with mixed solution of acetonitrile-20mM ammonium formate containing 0.3% formic acid (40:60, v/v), at a flow rate of 0.35 mL/min. Doxazosin mesylate and pioglitazone were used as the internal standard (IS) respectively for quantification. The determination was carried out on an API 4000 triple-quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode using the following transitions monitored simultaneously: positive m/z 150.0/91.0 for phentermine, m/z 452.1/344.3 for doxazosin, and negative m/z 338.3/77.9 for topiramate, m/z 355.0/41.9 for pioglitazone. The method was validated to be linear over the concentration range of 1-800 ng mL(-1) for phentermine, 1-1000 ng mL(-1) for topiramate. Within- and between-day accuracy and precision of the validated method at three different concentration levels were within the acceptable limits of <15% at all concentrations. Blood samples were collected into heparinized tubes before and after administration. The simple and robust LC/MS/MS method was successfully applied for the simultaneous determination of phentermine and topiramate in a pharmacokinetic study in healthy male Chinese volunteers.

  7. Quantitative determination of saroglitazar, a predominantly PPAR alpha agonist, in human plasma by a LC-MS/MS method utilizing electrospray ionization in a positive mode.

    PubMed

    Ghoghari, Ashok; Dash, Ranjeet; Bhatt, Chandrakant; Singh, Kanchan; Jha, Anil; Patel, Harilal; Gupta, Rahul; Kansagra, Kevinkumar; Srinivas, Nuggehally R

    2016-12-01

    A sensitive LC-MS/MS method was developed and validated for quantitation of saroglitazar using turboion spray interface with positive ion mode. A liquid-liquid extraction, with a mixture of dichloromethane and diethyl ether, was employed for the extraction of saroglitazar and glimepiride (IS) from human plasma. The chromatographic separation was achieved using an ACE-5, C18 (4.6 × 100 mm) column with a gradient mobile phase comprising acetonitrile and ammonium acetate buffer with trifluoracetic acid in purified water. Both analytes were separated within 10 min with retention times of 4.52 and 2.57 min for saroglitazar and IS, respectively. Saroglitazar quantitation was achieved by the summation of two MRM transition pairs (m/z 440.2 to m/z 366.0 and m/z 440.2 to m/z 183.1), while that of IS was achieved using transition pair m/z 491.3 to m/z 352.0. The calibration standards of saroglitazar showed linearity from 0.2 to 500 ng/mL, with a lower limit of quantitation of 0.2 ng/mL. The biases for inter- and intra-batch assays were -7.51-1.15% and -11.21 to -3.25%, respectively, while the corresponding precisions were 5.04-8.06% and 1.53-7.68%, respectively. The developed method was used to monitor the plasma concentrations of saroglitazar in clinical samples.

  8. Students' Conceptions of Ionisation Energy: A Cross-Cultural Study

    ERIC Educational Resources Information Center

    Tan, Kim Chwee Daniel; Taber, Keith S.; Liu, Xiufeng; Coll, Richard K.; Lorenzo, Mercedes; Li, Jia; Goh, Ngoh Khang; Chia, Lian Sai

    2008-01-01

    Previous studies have indicated that A-level students in the UK and Singapore have difficulty learning the topic of ionisation energy. A two-tier multiple-choice instrument developed in Singapore in an earlier study, the Ionisation Energy Diagnostic Instrument, was administered to A-level students in the UK, advanced placement high school students…

  9. Students' Conceptions of Ionisation Energy: A Cross-Cultural Study

    ERIC Educational Resources Information Center

    Tan, Kim Chwee Daniel; Taber, Keith S.; Liu, Xiufeng; Coll, Richard K.; Lorenzo, Mercedes; Li, Jia; Goh, Ngoh Khang; Chia, Lian Sai

    2008-01-01

    Previous studies have indicated that A-level students in the UK and Singapore have difficulty learning the topic of ionisation energy. A two-tier multiple-choice instrument developed in Singapore in an earlier study, the Ionisation Energy Diagnostic Instrument, was administered to A-level students in the UK, advanced placement high school students…

  10. Determination of structure parameters in molecular tunnelling ionisation model

    NASA Astrophysics Data System (ADS)

    Wang, Jun-Ping; Zhao, Song-Feng; Zhang, Cai-Rong; Li, Wei; Zhou, Xiao-Xin

    2014-04-01

    We extracted the accurate structure parameters in a molecular tunnelling ionisation model (the so-called MO-ADK model) for 23 selected linear molecules including some inner orbitals. The molecular wave functions with the correct asymptotic behaviour are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials numerically constructed using the modified Leeuwen-Baerends (LBα) model. We show that the orientation-dependent ionisation rate reflects the shape of the ionising orbitals in general. The influences of the Stark shifts of the energy levels on the orientation-dependent ionisation rates of the polar molecules are studied. We also examine the angle-dependent ionisation rates (or probabilities) based on the MO-ADK model by comparing with the molecular strong-field approximation calculations and with recent experimental measurements.

  11. Simultaneous determination of lovastatin and its metabolite lovastatin acid in rat plasma using UPLC-MS/MS with positive/negative ion-switching electrospray ionization: Application to a pharmacokinetic study of lovastatin nanosuspension.

    PubMed

    Guo, Mengran; Zhao, Longshan; Li, Mo; Fu, Qiang; Pu, Xiaohui; Liu, Bingyang; He, Zhonggui; Yang, Li

    2016-06-15

    Lovastatin (LOV) is an antihyperlipidemic agent which exhibits low bioavailability due to its poor solubility. Therefore, a nanosuspension (NS) was developed as an efficient strategy to improve its oral bioavailability. To evaluate the pharmacokinetics of LOV-NS, a novel, sensitive, and rapid UPLC-MS/MS method was developed and validated for the simultaneous determination of LOV and its metabolite lovastatin acid (LOVA) in rat plasma. Simvastatin (IS) was chosen as the internal standard, and a liquid-liquid extraction method was used to isolate LOV and LOVA from biological matrices. The analytes were analyzed on an Acquity UPLC BEH C18 column, and a gradient program was applied at a flow rate of 0.2mL/min. Then, a tandem quadrupole mass spectrometer coupled with a positive/negative ion-switching electrospray ionization interface was employed to detect the analytes. Quantitation of the analytes was performed in the multiple reaction monitoring mode to monitor the transitions of m/z 427.1→325.0 for LOV and m/z 441.1→325.0 for IS in the positive ion mode and m/z 421.0→101.0 for LOVA in the negative ion mode, respectively. The method was validated over the concentration range 0.25-500ng/mL (r(2)≥0.99) for both LOV and LOVA. The intra-day and inter-day precision (RSD%) of LOV and LOVA were less than 12.87% and the accuracy (RE%) was less than 5.22%. The average extraction recoveries were 90.1% and 91.9% for LOV and LOVA, and the matrix effects were found to be between 85% and 115%. The stability study showed that both analytes were stable during the experiment. Finally, this method has been successfully applied to a pharmacokinetic study in rats following a single oral dose of 10mg/kg LOV-NS. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Derivatisation and gas chromatography-chemical ionisation mass spectrometry of selected synthetic and natural endocrine disruptive chemicals.

    PubMed

    Lerch, Oliver; Zinn, Peter

    2003-03-28

    Methods for ultra trace detection of endocrine disruptive chemicals (EDCs) are needed because of their low levels of impact. Twenty-one EDCs were selected, including 17beta-estradiol, 17alpha-ethinylestradiol, 17beta-testosterone and bisphenol A. Derivatisation with eight different fluorine containing compounds was examined. All EDCs could be derivatised automatedly (autosampler) with heptafluorobutyric acid (HFB) anhydride and trifluoroacetic acid (TFA) anhydride, respectively. The detection of these HFB and TFA derivatives in different chemical ionisation modes was studied. Fourteen different reagent gases, including methane, ammonia, acetone and water, were tested with the HFB and TFA derivatives in the negative chemical ionisation mode. Furthermore both types of derivatives were measured in positive chemical ionisation mode. Methane or water provide a good detection of all 21 TFA derivatives and create mass spectra with few fragmentation and characteristic mass peaks. This could serve as a basis for tandem or multiple mass spectrometric measurements.

  13. Incorporation of a venturi device in electrospray ionization.

    PubMed

    Zhou, Li; Yue, Bingfang; Dearden, David V; Lee, Edgar D; Rockwood, Alan L; Lee, Milton L

    2003-11-01

    Electrospray ionization has grown to be one of the most commonly used ionization techniques for mass spectrometry, and efforts continue to improve its performance. Typically, the sprayer tip must be very close to the entrance orifice of the mass spectrometer in order to maximize the conduction of ions from the sprayer into the mass spectrometer. However, because of space-charge repulsion, most ions never reach the sampling orifice. In this work, an industrial air amplifier, for which the working mechanism is based on venturi and coanda effects, was added between an electrospray ionization source and a time-of-flight mass spectrometer. When a series of reserpine solutions (0.5, 1.0, 5.0, and 10.0 microM) were monitored using mass spectrometry, an over 5-fold increase in m/z 609.3 ion intensity was measured for a separation distance of 14 mm between the electrospray tip and interface capillary inlet, as compared to when the electrospray tip was in its normal position 1 mm in front of the inlet without the amplifier. When a voltage was applied to the air amplifier to further assist in focusing the electrosprayed ions, an approximately 18-fold increase in m/z 609.3 ion intensity was obtained. In addition, a 34-fold reduction in method detection limit was observed.

  14. High pressure (>1 atm) electrospray ionization mass spectrometry.

    PubMed

    Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2011-03-01

    High pressure electrospray ionization mass spectrometry has been performed by pressurizing a custom made ion source chamber with compressed air to a pressure higher than the atmospheric pressure. The ion source was coupled to a commercial time-of-flight mass spectrometer using a nozzle-skimmer arrangement. The onset voltage for the electrospray of aqueous solution was found to be independent on the operating pressure. The onset voltage for the corona discharge, however, increased with the rise of pressure following the Paschen's law. Thus, besides having more working gas for the desolvation process, gaseous breakdown could also be avoided by pressurizing the ESI ion source with air to an appropriate level. Stable electrospray ionization has been achieved for the sample solution with high surface tension such as pure water in both positive and negative ion modes. Fragmentation of labile compounds during the ionization process could also be reduced by optimizing the operating pressure of the ion source.

  15. Desorption electrospray ionization mass spectrometry of intact bacteria

    USDA-ARS?s Scientific Manuscript database

    Desorption electrospray ionization (DESI) mass spectrometry (MS) was used to differentiate 7 bacterial species based on their measured DESI-mass spectral profile. Both Gram positive and Gram negative bacteria were tested and included Escherichia coli, Staphyloccocus aureus, Enterococcus sp., Bordete...

  16. Electrospray Collection of Lunar Dust

    NASA Technical Reports Server (NTRS)

    Dziekan, Michael

    2012-01-01

    A report describes ElectroSpray Ionization based Electrostatic Precipitation (ESIEP) for collecting lunar dust particles. While some HEPA filtration processes may remove a higher fraction (>99.9 percent) of the particles, the high efficiency may not be appropriate from an overall system standpoint, especially in light of the relatively large power requirement that such systems demand. The new electrospray particle capture technology is described as a variant of electrostatic precipitation that eliminates the current drawbacks of electrostatic precipitation. The new approach replaces corona prone field with a mist of highly charged micro-droplets generated by electrospray ionization (ESI) as the mechanism by which incoming particles are attracted and captured. In electrospray, a miniscule flow rate (microliters/minute) of liquid (typically water and a small amount of salt to enhance conductivity) is fed from the tip of a needle held at a high voltage potential relative to an opposite counter electrode. At sufficient field strength, a sharp liquid meniscus forms , which emits a jet of highly charged droplets that drift through the surrounding gas and are collected on the walls of a conductive tube. Particles in the gas have a high probability of contact with the droplets either by adhering to the droplets or otherwise acquiring a high level of charge, causing them to be captured on the collecting electrode as well. The spray acts as a filtration material that is continuously introduced and removed from the gas flow, and thus can never become clogged.

  17. Identification and quantification of five macrolide antibiotics in several tissues, eggs and milk by liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Dubois, M; Fluchard, D; Sior, E; Delahaut, P

    2001-04-05

    We present an electrospray high-performance liquid chromatographic tandem mass spectrometric (HPLC-MS-MS) method capable of determining in several tissues (muscle, kidney, liver), eggs and milk the following five macrolides: tylosin, tilmicosin, spiramycin, josamycin, erythromycin. Roxithromycin was used as an internal standard. The method uses extraction in a Tris buffer at pH 10.5, followed by protein precipitation with sodium tungstate and clean-up on an Oasis solid-phase extraction column. The HPLC separation was performed on a Purospher C18 column (125 x 3 mm I.D.) protected by a guard column, with a gradient of aqueous 0.1 M ammonium acetate-acetonitrile as the mobile phase at a flow-rate of 0.7 ml min(-1). Protonated molecules served as precursor ions for electrospray ionisation in the positive ion mode and four product ions were chosen for each analyte for multiple reaction monitoring (MRM). A validation study was conducted to confirm the five macrolides by MRM HPLC-MS-MS analysis of a negative control and fortified samples. All of the samples analysed were confirmed with four ions. The ion ratio reproducibility limit ranged from 2.4 to 15%. All compounds could be detected and quantified at half-maximum residue limits (MRLs). The method is specific, quantitative and reproducible enough to conform to European Union recommendations within the concentration range 0.5 MRL-2 MRL (accuracy: 80 to 110%, relative standard deviation: 2 to 13%). This whole method allows extraction and analysis of up to 50 samples per day.

  18. Radial arrays of nano-electrospray ionization emitters and methods of forming electrosprays

    DOEpatents

    Kelly, Ryan T [West Richland, WA; Tang, Keqi [Richland, WA; Smith, Richard D [Richland, WA

    2010-10-19

    Electrospray ionization emitter arrays, as well as methods for forming electrosprays, are described. The arrays are characterized by a radial configuration of three or more nano-electrospray ionization emitters without an extractor electrode. The methods are characterized by distributing fluid flow of the liquid sample among three or more nano-electrospray ionization emitters, forming an electrospray at outlets of the emitters without utilizing an extractor electrode, and directing the electrosprays into an entrance to a mass spectrometry device. Each of the nano-electrospray ionization emitters can have a discrete channel for fluid flow. The nano-electrospray ionization emitters are circularly arranged such that each is shielded substantially equally from an electrospray-inducing electric field.

  19. Hyphenation of atmospheric pressure chemical ionisation mass spectrometry to supercritical fluid chromatography for polar car lubricant additives analysis.

    PubMed

    Lavison-Bompard, Gwenaelle; Thiébaut, Didier; Beziau, Jean-François; Carrazé, Bernadette; Valette, Pascale; Duteurtre, Xavier; Tabet, Jean-Claude

    2009-01-30

    Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming. In a previous paper, it was demonstrated that supercritical fluid chromatography (SFC) allows the elution of common low-molecular-weight additives. Since their total resolution could not be achieved owing to the limited peak capacity of packed columns, the hyphenation of selective and informative detection methods such as atomic emission detection (AED) was required. Further to results obtained in SFC-AED, this work describes the hyphenation of SFC to atmospheric pressure chemical ionisation ion trap mass spectrometry (MS). SFC-MS hyphenation is detailed: temperature, flow rates of gas and mobile phase introduced in the source, position of the restrictor, ionisation additives and conditions of autotune are studied. Car lubricant monitoring requires negative and positive ionisation modes with or without the addition of ionisation auxiliary solvent according to the nature of additives. Moreover, when sensitivity is of major concern for a selected additive, the autotuning routine of the MS has to be performed in conditions as close as possible to analytical conditions, i.e. under subcritical conditions. Unambiguous identification and structure elucidation of several additives in formulated car lubricants are also presented.

  20. Formation of diclofenac molecular ions as the effect of Cu(2+)-π interaction under electrospray ionization mass spectrometry conditions.

    PubMed

    Ostrowski, Wojciech; Linko, Katarzyna; Frański, Rafał

    2012-01-01

    Solutions containing diclofenac (M) and a copper salt [CuCl2, Cu(ClO4)2, Cu(NO3)2, CuSO4) were analysed by electrospray ionisation mass spectrometry (ESI-MS). Because of the cation-pi interactions in diclofenac-Cu(II) complexes, the diclofenac molecular ion M+* at m/z 295 was formed. It was found that the solvent composition (methanol versus water/methanol) and counter ion strongly affect the M+* ion formation. Formation pathways of ion M+* are discussed.

  1. Cosmic-ray ionisation of dense molecular clouds

    NASA Astrophysics Data System (ADS)

    Vaupre, Solenn

    2015-07-01

    Cosmic rays (CR) are of tremendous importance in the dynamical and chemical evolution of interstellar molecular clouds, where stars and planets form. CRs are likely accelerated in the shells of supernova remnants (SNR), thus molecular clouds nearby can be irradiated by intense fluxes of CRs. CR protons have two major effects on dense molecular clouds: 1) when they encounter the dense medium, high-energy protons (>280 MeV) create pions that decay into gamma-rays. This process makes SNR-molecular cloud associations intense GeV and/or TeV sources whose spectra mimic the CR spectrum. 2) at lower energies, CRs penetrate the cloud and ionise the gas, leading to the formation of molecular species characteristic of the presence of CRs, called tracers of the ionisation. Studying these tracers gives information on low-energy CRs that are unaccessible to any other observations. I studied the CR ionisation of molecular clouds next to three SNRs: W28, W51C and W44. These SNRs are known to be interacting with the nearby clouds, from the presence of shocked gas, OH masers and pion-decay induced gamma-ray emission. My work includes millimeter observations and chemical modeling of tracers of the ionisation in these dense molecular clouds. In these three regions, we determined an enhanced CR ionisation rate, supporting the hypothesis of an origin of the CRs in the SNR nearby. The evolution of the CR ionisation rate with the distance to the SNR brings valuable constraints on the propagation properties of low-energy CRs. The method used relies on observations of the molecular ions HCO+ and DCO+, which shows crucial limitations at high ionisation. Therefore, I investigated, both through modeling and observations, the chemical abundances of several other species to try and identity alternative tracers of the ionisation. In particular, in the W44 region, observations of N2H+ bring additional constraints on the physical conditions, volatile abundances in the cloud, and the ionisation

  2. Simultaneous measurement of proline and related compounds in oak leaves by high-performance ligand-exchange chromatography and electrospray ionization mass spectrometry for environmental stress studies.

    PubMed

    Oufir, Mouhssin; Schulz, Nadine; Sha Vallikhan, Patan Shaik; Wilhelm, Eva; Burg, Kornel; Hausman, Jean-Francois; Hoffmann, Lucien; Guignard, Cedric

    2009-02-13

    A mass spectrometer was coupled to high-performance ligand-exchange liquid chromatography (HPLEC) for simultaneous analysis of stress associated solutes such as proline, hydroxyproline, methylproline, glycine betaine and trigonelline extracted from leaves of drought stressed oaks and an internal standard namely N-acetylproline. Methanol/chloroform/water extracts were analyzed using an Aminex HPX-87C column and specifically quantified by the positive ion mode of an electrospray ionisation-mass spectrometry (ESI-MS) in single ion monitoring (SIM) mode. The recovery of N-acetyl proline added to oak leaf extracts ranged from 85.2 to 122.1% for an intra-day study. Standard calibration curves showed good linearity in the measured range from 0.3125 to 10micromolL(-1) with the lowest correlation coefficient of 0.99961 for trigonelline. The advantages of this alternative procedure, compared to previously published methods using fluorescence or amperometric detections, are the simultaneous and direct detection of osmoprotectants in a single chromatographic run, a minimal sample preparation, a good specificity and reduced limits of quantification, ranging from 0.1 to 0.6micromolL(-1). Fifty-six days of water deficit exposure resulted in increased foliar free proline levels (2.4-fold, P<0.001, 155micromolg(-1) FW) and glycine betaine contents (2.5-fold, P<0.05, 175micromolg(-1) FW) of drought stressed oak compared to control.

  3. Digital electrospray for controlled deposition.

    PubMed

    Deng, Weiwei; Waits, C Mike; Gomez, Alessandro

    2010-03-01

    Many novel functional structures are now fabricated by controlled deposition as a maskless, bottom-up fabrication technique. These applications require rapid and precise deposition of minute amounts of solutions/suspensions or their ultimate particle products in predefined patterns. The electrospray is a promising alternative to the commonly used inkjet printing because it can easily handle highly viscous liquid, avoid high shear rates, and has low risk of clogging. We demonstrate a proof-of-concept digital electrospray. This system consists of a 61-nozzle array microfabricated in silicon and a 61-element digital extractor fabricated using flexible polyimide substrates. "Digital" refers to the state of each electrospray source that can be tuned either on or off independently and responsively. We showed a resolution of 675 mum and a response frequency up to 100 Hz. With similar design and industry standard fabrication procedures, it is feasible to scale up the system to O(1000) sources with spatial resolution better than 250 mum and a O(kHz) response frequency. The latter is controlled by the viscous damping time.

  4. Effect of pressure on electrospray characteristics

    SciTech Connect

    Marginean, Ioan; Page, Jason S.; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.

    2009-11-02

    An experimental study of sub-ambient pressure electrosprays is reported. The pressure domain that affords stable electrospray operation appears to be limited by the vapor pressure of the liquid. The voltage driving the electrospray is shown to have a logarithmic dependence on the pressure. This scaling amends the relationship currently in use to calculate the electric field at the tip of the meniscus of an electrified liquid

  5. STRUCTURAL DETERMINATION AND QUANTITATIVE ANALYSIS OF BACTERIAL PHOSPHOLIPIDS USING LIQUID CHROMATOGRAPHY/ELECTROSPRAY IONIZATION/MASS SPECTROMETRY

    EPA Science Inventory

    This report presents a comprehensive spectral analysis of common bacterial phospholipids using electrospray/mass spectrometry (ESI/MS) under both negative and positive ionization conditions. Phospholipids under positive ionization yield sodium-adduct molecular ions which are mos...

  6. STRUCTURAL DETERMINATION AND QUANTITATIVE ANALYSIS OF BACTERIAL PHOSPHOLIPIDS USING LIQUID CHROMATOGRAPHY/ELECTROSPRAY IONIZATION/MASS SPECTROMETRY

    EPA Science Inventory

    This report presents a comprehensive spectral analysis of common bacterial phospholipids using electrospray/mass spectrometry (ESI/MS) under both negative and positive ionization conditions. Phospholipids under positive ionization yield sodium-adduct molecular ions which are mos...

  7. Ionisation and the Formation of Low-Mass Protostars

    NASA Astrophysics Data System (ADS)

    Wurster, James; Bate, M. R.; Price, D. J.

    2017-06-01

    Molecular clouds are known to have strong magnetic fields and low ionisation rates. Numerical simulations performed with these more realistic conditions yield results closer to those observed, and furthermore, suggest additional observational signatures not yet explored. I will discuss my simulations of the formation of a single protostar starting from one solar mass of gas; the models include a self-consistent treatment of all three non-ideal MHD processes. My focus will be on how the ionisation parameters and non-ideal MHD processes affect the formation of the protostar and its environment.

  8. [Bipolar ionisation of indoor air through ion generators mountable into inflow ventilation and conditioning].

    PubMed

    Dudarev, A A; Spichkin, G L; Denisikhina, D M; Burtsev, S I

    2010-01-01

    Experimental studies and digital modelling of artificial indoor air ionisation through bipolar ionisers mountable into inflow ventilation and conditioning proved possible creation of continuous even bipolar ion background in indoor air, similar to the natural one.

  9. Binary-Encounter-Bethe ionisation cross sections for simulation of DNA damage by the direct effect of ionising radiation.

    PubMed

    Plante, I; Cucinotta, F A

    2015-09-01

    DNA damage is of crucial importance in the understanding of the effects of ionising radiation. To refine existing DNA damage models, an approach using the Binary-Encounter-Bethe (BEB) cross sections was developed. The differential cross sections for ionisation of the molecular orbitals of the DNA bases, sugars and phosphates are calculated using the electron binding energy, the mean kinetic energy and the occupancy number of each orbital as parameters. The resulting cross section has an analytic form which is quite convenient to use for Monte-Carlo codes that randomly sample the energy loss occurring during an ionisation event. We also describe an algorithm to simulate the interactions of electrons with DNA in the radiation transport code RITRACKS using the integrated BEB cross section for the bases, sugar and phosphates.

  10. Ambient gas influence on electrospray potential as revealed by potential mapping within the electrospray capillary.

    PubMed

    Pozniak, Boguslaw P; Cole, Richard B

    2007-05-01

    The effect of ambient gas on potentials inside the electrospray (ES) capillary was investigated. Potential measurements and differential electrospray emitter potential (DEEP) maps were obtained with the help of a small, movable, disklike platinum wire electrode inserted into the ES capillary. Typical solvents used for electrospray mass spectrometry such as methanol and mixtures of methanol-water and chloroform/methanol have been tested. It was found that oxygen is readily adsorbed from the surrounding ambient gas into the spraying liquid. Following adsorption, it resides in, or near to, the Taylor cone, thereby affecting the electrochemical potential near the ES capillary exit, as well as the character of the inherent electrochemical reactions occurring during the ES process. The potentials measured in an air environment with reactive oxygen present are contrasted against those obtained in an inert nitrogen environment. The kinetics of oxygen admission have been found to be quite fast, i.e., occurring in a matter of seconds, but it takes far longer to purge the system of oxygen by changing the ambient atmosphere to nitrogen. The oxygen effect is present in negative and positive ion modes of ES, but the total ES current is not affected by the change of ambient gas. The magnitude of the oxygen effect owing to ambient air was compared to the effect caused by initially dissolving oxygen in the solution prior to the start of ES; it was found that the presence of oxygen in the ambient gas has a far greater consequence. These results indicate that the presence of reactive gases, such as molecular oxygen, in the region of the ES emitter may have unintended secondary effects on the ES process prior to mass spectrometric analysis.

  11. Positioning.

    ERIC Educational Resources Information Center

    Conone, Ruth M.

    The key to positioning is the creation of a clear benefit image in the consumer's mind. One positioning strategy is creating in the prospect's mind a position that takes into consideration the company's or agency's strengths and weaknesses as well as those of its competitors. Another strategy is to gain entry into a position ladder owned by…

  12. Nonintrusive measurement of ionisation in vegetation fire plasma

    NASA Astrophysics Data System (ADS)

    Mphale, K. M.; Heron, M.

    2008-02-01

    Vegetation fires are slightly ionised gaseous medium. Omnipresent alkali metal species in plant's organic structure are the main source of thermally produced electrons in the fires. In the flames, electron-neutral particle collisions dominate other modes of particle interaction. The collision regime absorbs some of the incident energy when the fire is illuminated with electromagnetic waves. The rate of electromagnetic wave absorption in the vegetation fires has implications on the safety of fire-fighters. During wildfire suppression, radio communication blackout at vhf/uhf has been experienced. This may be partly due to thermal ionisation in the fire. In the experiment, the extent of ionisation in vegetation fires is measured using a 2-port vector network analyser. X-band microwaves are caused to propagate combustion zones of eucalyptus bark and guinea grass fires with maximum temperatures of 1114 and 1054 K respectively. Alkali content in the vegetation fuel was different. Measurements show maximum ionisation in flames produced from guinea grass, which had almost twice much potassium as that of eucalyptus bark, to be 2.63×1016 m-3 while that produced in eucalyptus bark flame was 1.46×1016 m-3.

  13. High performance liquid chromatography-diode array and electrospray-mass spectrometry analysis of vardenafil, sildenafil, tadalafil, testosterone and local anesthetics in cosmetic creams sold on the Internet web sites.

    PubMed

    De Orsi, Daniela; Pellegrini, Manuela; Marchei, Emilia; Nebuloni, Paolo; Gallinella, Bruno; Scaravelli, Giulia; Martufi, Alessio; Gagliardi, Luigi; Pichini, Simona

    2009-10-15

    A simple high-performance liquid chromatography (HPLC) method with ultraviolet diode array (UV-DAD) and electrospray ionisation mass spectrometry (ESI-MS) detection has been developed for the determination of vardenafil, sildenafil, tadalafil, testosterone, procaine, lidocaine, prilocaine, and benzocaine in cosmetic creams sold as promising remedies for male erectile dysfunction and female genitals stimulation. The presence of these substances in commercial cosmetic samples is prohibited. Aliquots (1 g) of the cosmetic creams under investigation were diluted 1:100 in methanol, subjected to ultrasonic treatment, added with benzoic acid as internal standard, and analyzed by HPLC-DAD and HPLC-ESI-MS after a further 1:1000 dilution. The compounds were separated by reversed phase chromatography with water (0.02% trifluoroacetic acid) and acetonitrile gradient elution and detected by UV-DAD at 228, 255 and 290 nm and by ESI-MS positive ionisation mode. Benzoic acid was used as internal standard. Linearity was studied with UV-DAD detection from 2.5-7.8 to 250 microg/g range, depending on the different compounds and with ESI-MS in the 3.3-8.9 to 250 ng/g range. Good determination coefficients (r(2) > or = 0.99) were found in both UV-DAD and ESI-MS. Limits of quantifications ranged between 2.5 and 7.8 microg/g for HPLC-UV-DAD assay and between 3.3 and 8.9 ng/g for HPLC-ESI-MS assay depending on different analyzed substances. At three concentrations spanning the linear dynamic ranges of both UV-DAD and ESI-MS assay, mean recoveries were always higher than 90% for the different analytes and intra-assay and inter-assay precision always better than 15% and 12%. This method was successfully applied to the analysis of substances under investigations present in cosmetic creams, freely sold on the Internet web-sites.

  14. Resonance laser-induced ionisation of sodium vapour taking radiative transfer into account

    SciTech Connect

    Kosarev, N I; Shaparev, N Ya

    2006-04-30

    The problem of ionisation of atomic sodium in the field of resonance laser radiation is numerically solved taking radiative transfer into account. Seed electrons are produced due to the mechanism of associative ionisation, then they gain energy in superelastic processes (collisions of the second kind) and initiate the avalanche ionisation of the medium by electron impact. We studied the effect of secondary radiation on the laser pulse propagation upon competition between the ionising and quenching electron collisions with excited atoms, on the kinetics of ionisation-induced vapour bleaching, and the plasma channel expansion in the form of a halo. (interaction of laser radiation with matter)

  15. Nurses', physicians' and radiographers' perceptions of the safety of a nurse prescribing of ionising radiation initiative: A cross-sectional survey.

    PubMed

    Hyde, Abbey; Coughlan, Barbara; Naughton, Corina; Hegarty, Josephine; Savage, Eileen; Grehan, Jennifer; Kavanagh, Eoin; Moughty, Adrian; Drennan, Jonathan

    2016-06-01

    A new initiative was introduced in Ireland following legislative changes that allowed nurses with special training to prescribe ionising radiation (X-ray) for the first time. A small number of studies on nurse prescribing of ionising radiation in other contexts have found it to be broadly as safe as ionising radiation prescribing by physicians. Sociological literature on perceptions of safety indicates that these tend to be shaped by the ideological position of the professional rather than based on objective evidence. To describe, compare and analyse perceptions of the safety of a nurse prescribing of ionising radiation initiative across three occupational groups: nursing, radiography and medicine. A cross-sectional survey design. Participants were drawn from a range of clinical settings in Ireland. Respondents were 167 health professionals comprised of 49 nurses, 91 radiographers, and 27 physicians out of a total of 300 who were invited to participate. Non-probability sampling was employed and the survey was targeted specifically at health professionals with a specific interest in, or involvement with, the development of the nurse prescribing of ionising radiation initiative in Ireland. Comparisons of perspectives on the safety of nurse prescribing of ionising radiation across the three occupational groups captured by questionnaire were analysed using the Kruskal-Wallis H test. Pairwise post hoc tests were conducted using the Mann-Whitney U test. While the majority of respondents from all three groups perceived nurse prescribing of ionising radiation to be safe, the extent to which this view was held varied. A higher proportion of nurses was found to display confidence in the safety of nurse prescribing of ionising radiation compared to physicians and radiographers with differences between nurses' perceptions and those of the other two groups being statistically significant. That an occupational patterning emerged suggests that perceptions about safety and risk of

  16. Sampling probe for microarray read out using electrospray mass spectrometry

    DOEpatents

    Van Berkel, Gary J.

    2004-10-12

    An automated electrospray based sampling system and method for analysis obtains samples from surface array spots having analytes. The system includes at least one probe, the probe including an inlet for flowing at least one eluting solvent to respective ones of a plurality of spots and an outlet for directing the analyte away from the spots. An automatic positioning system is provided for translating the probe relative to the spots to permit sampling of any spot. An electrospray ion source having an input fluidicly connected to the probe receives the analyte and generates ions from the analyte. The ion source provides the generated ions to a structure for analysis to identify the analyte, preferably being a mass spectrometer. The probe can be a surface contact probe, where the probe forms an enclosing seal along the periphery of the array spot surface.

  17. Ionised outflows in z ~ 2.4 quasar host galaxies

    NASA Astrophysics Data System (ADS)

    Carniani, S.; Marconi, A.; Maiolino, R.; Balmaverde, B.; Brusa, M.; Cano-Díaz, M.; Cicone, C.; Comastri, A.; Cresci, G.; Fiore, F.; Feruglio, C.; La Franca, F.; Mainieri, V.; Mannucci, F.; Nagao, T.; Netzer, H.; Piconcelli, E.; Risaliti, G.; Schneider, R.; Shemmer, O.

    2015-08-01

    Aims: Outflows driven by active galactic nuclei (AGN) are invoked by galaxy evolutionary models to quench star formation and to explain the origin of the relations observed locally between super-massive black holes and their host galaxies. We here aim to detect extended ionised outflows in luminous quasars, where we expect the highest activity both in star formation and in black-hole accretion. Currently, there are only a few studies based on spatially resolved observations of outflows at high redshift, z > 2. Methods: We analysed a sample of six luminous (L > 1047 erg/s) quasars at z ~ 2.4, observed in H-band using the near-IR integral field spectrometer SINFONI at the VLT. We performed a kinematic analysis of the [Oiii] emission line at λ = 5007 Å. Results: We detect fast, spatially extended outflows in five out of six targets. [Oiii]λ5007 has a complex gas kinematic, with blue-shifted velocities of a few hundreds of km s-1 and line widths up to 1500 km s-1. Using the spectroastrometric method, we infer a size of the ionised outflows of up to ~2 kpc. The properties of the ionised outflows, mass outflow rate, momentum rate, and kinetic power, are correlated with the AGN luminosity. The increase in outflow rate with increasing AGN luminosity is consistent with the idea that a luminous AGN pushes away the surrounding gas through fast outflows that are driven by radiation pressure, which depends on the emitted luminosity. Conclusions: We derive mass outflow rates of about 6-700 M⊙ yr-1 for our sample, which are lower than those observed in molecular outflows. The physical properties of ionised outflows show dependences on AGN luminosity that are similar to those of molecular outflows, but indicate that the mass of ionised gas is lower than that of molecular outflows. Alternatively, this discrepancy between ionised and molecular outflows could be explained with different acceleration mechanisms. Based on Observations collected at the European Organisation for

  18. Determination of sodium tanshinone IIA sulfonate in plasma by liquid chromatography-electrospray ionisation-tandem mass spectrometry.

    PubMed

    Hao, Haiping; Wang, Guangji; Cui, Nan; Li, Jing; Ding, Zuoqi

    2007-11-01

    Sodium tanshinone IIA sulfonate (STS) is a water-soluble derivative of tanshinone IIa, an important lipophilic component contained in Salvia miltiorrhizae. A simple, sensitive and robust quantification method for STS based on LC-ESI-MS/MS was developed and validated, and has been successfully applied to the pharmacokinetic study. Liquid-liquid extraction was used for extracting STS from biological samples, with a satisfactory recovery exceeding 75% at all test concentrations. Isocratic mobile phase consisted of 75% acetonitrile and 25% water containing 0.005% ammonia acetate (pH 3). Good retention and baseline separation for STS and the selected internal standard, diclofenac sodium, were obtained on a Shim-pack VP-ODS analytical column under this condition. The method was linear in the concentration range of 1-500 ng/mL. The intra- and inter-day precisions (RSD%) were within 9.0%. The deviation of the assay accuracies was within +/-10.0%. STS was proved to be stable during all sample storing, preparation and analytic procedures. With a lower limit of quantitation at 1 ng/mL, this method has been proved to be sensitive enough for the pharmacokinetic study of STS. The plasma profile of STS followed a single intravenous dosing was well fitted to a three compartmental model.

  19. An electrospray ionisation-mass spectrometry screening of triacylglycerols in developing cultivated and wild peanut kernels (Arachis hypogaea L.).

    PubMed

    Cherif, Aicha O; Leveque, Nathalie; Ben Messaouda, Mhamed; Kallel, Habib; Moussa, Fathi

    2013-06-01

    The accumulation of triacylglycerols during the development of three varieties of peanuts was monitored in two Tunisian cultivated peanut (Trabelsia (AraT) and Chounfakhi (AraC)) and one wild Tunisian peanut (Arbi (AraA)). The presence of TAGs composed of rare fatty acid residues such as hexacosanoic acid (C(23:0)) and heneicosanoic acid (C(21:0)) among the triacylglycerols C(23:0) LL, C(23:0) OO and C(21:0) LL was noted. The major molecular species of triacylglycerol detected in the three peanut varieties were dioleoyl linoleoyl (OOL), 1,2,3-trioleyl (OOO), 1,2-dioleyl-3-palmitoyl (POO), 1,2-dilinoleoyl-3-oleyl (OLL) and 1-oleoyl-2-linoleoyl-3-linolenoyl (OLLn). The TAG composition and content were significantly different among the three peanut varieties. The three major TAGs were OOL (20.6%), OOO (15.6%) and OLLn (13.2%) in AraA; OOL (21.4%), OOO (20.1%) and POO (17.5%) in AraC and finally OLL (20.7%), OOO (19.8%) and OLL (17.7%) in AraT. Copyright © 2012 Elsevier Ltd. All rights reserved.

  20. Analysis of diterpenoid compounds from the latex of two Euphorbiaceae by liquid chromatography‒electrospray ionisation mass spectrometry.

    PubMed

    Sobottka, A M; Görick, C; Melzig, M F

    2016-09-01

    The latex of Euphorbia papillosa A.St.-Hil. and Sapium glandulosum (L.) Morong was phytochemically investigated by liquid chromatography/mass spectrometry. The results reveal the presence of tigliane-type diterpenoid compounds, particularly 12-deoxyphorbol esters, in both species. In addition, ingenane-type diterpene esters were found in the latex of E. papillosa. The latex of S. glandulosum showed only tigliane-type diterpenes, confirming the literature data on this genus. According to mass data, we are proposing the presence of 10 compounds derived from 12-deoxyphorbol monoesters and diesters, from one 12-deoxyphorbaldehyde, from two ingenol derivatives and from one nitrogen-containing phorbol ester in the latex of the analysed species. Considering that 12-deoxy tigliane diterpenes are described as antitumour and antiviral agents, these results indicate a pharmacological potential for these two Euphorbiaceae species.

  1. Electrospray Ionization on Solid Substrates

    PubMed Central

    So, Pui-Kin; Hu, Bin; Yao, Zhong-Ping

    2014-01-01

    Development of electrospray ionization on solid substrates (solid-substrate ESI) avoids the clogging problem encountered in conventional capillary-based ESI, allows more convenient sampling and permits new applications. So far, solid-substrate ESI with various materials, e.g., metals, paper, wood, fibers and biological tissue, has been developed, and applications ranging from analysis of pure compounds to complex mixtures as well as in vivo study were demonstrated. Particularly, the capability of solid-substrate ESI in direct analysis of complex samples, e.g., biological fluids and foods, has significantly facilitated mass spectrometric analysis in real-life applications and led to increasingly important roles of these techniques nowadays. In this review, various solid-substrate ESI techniques and their applications are summarized and the prospects in this field are discussed. PMID:26819900

  2. Thin-channel electrospray emitter

    DOEpatents

    Van Berkel, Gary J.

    2004-08-31

    An electrospray device includes a high voltage electrode chamber. The high voltage electrode chamber includes an inlet for receiving a fluid to be ionized and for directing the fluid into the chamber and at least one electrode having an exposed surface within the chamber. A flow channel directs fluid over a surface of the electrode and out of the chamber. The length of the flow channel over the electrode is greater than the height of the flow channel over the electrode, thereby producing enhanced mass transport to the working electrode resulting in improved electrolysis efficiency. An outlet is provided for transmitting the fluid out from the electrode chamber. A method of creating charged droplets includes flowing a fluid over an electrode where the length over the electrode is greater than the height of the fluid flowing over the electrode.

  3. Ionisation of a quantum dot by electric fields

    SciTech Connect

    Eminov, P A; Gordeeva, S V

    2012-08-31

    We have derived analytical formulas for differential and total ionisation probabilities of a two-dimensional quantum dot by a constant electric field. In the adiabatic approximation, we have calculated the probability of this process in the field of a plane electromagnetic wave and in a superposition of constant and alternating electric fields. The imaginary-time method is used to obtain the momentum distribution of the ionisation probability of a bound system by an intense field generated by a superposition of parallel constant and alternating electric fields. The total probability of the process per unit time is calculated with exponential accuracy. The dependence of the results obtained on the characteristic parameters of the problem is investigated. (laser applications and other topics in quantum electronics)

  4. THE INFLUENCE OF SALTS UPON THE IONISATION OF EGG ALBUMIN

    PubMed Central

    Sørensen, S. P. L.; Linderstrøm-Lang, K.; Lund, Ellen

    1927-01-01

    Introduction. A description is given of the principle followed in the experimental determination of the ionisation of egg albumin, its capacity to combine with acids and bases. Egg albumin is regarded as an ampholyte, and in accordance with J. N. Brønsted's definition of acids and bases, ampholytes are considered as substances capable of both taking up and giving off hydrogen ions. The theoretical treatment of the capacity of ampholytes to combine with acids (and bases) has been carried out on this basis. Section A. Several experimental series are noted, comprising the determination of the activity coefficient of the hydrogen ion (fH) in ammonium chloride solutions of different concentration. Section B. The general method of experimental determination of the ionisation (capacity to combine with adds and bases) of egg albumin in ammonium chloride and potassium chloride solutions is briefly described, and the results of the experiments are compared. Section C. 1). In a brief theoretical survey we have suggested that distinction should be made between isoelectric and isoionic reaction of an ampholyte, the former defined as the hydrogen ion activity (value of paH) at which the mean valency of the ampholyte is 0, the latter as the hydrogen ion activity at which the quantity of acid or base combined with the ampholyte is 0; or, as we prefer to express it, the hydrogen ion activity at which the specific hydrogen ionisation of the ampholyte is 0. If the ampholyte does not combine with other ions than the hydrogen ion, then isoelectric and isoionic reaction coincide. Isoionic reaction is determined by acid-combining experiments. The principle of this determination is briefly described. A theoretical investigation of the alteration with salt concentration of both isoelectric (isoionic) reaction and the shape and direction of the ionisation curves is made, with regard to ampholytes capable only of combining with hydrogen ions, on the basis of the Debye-Hückel formulæ and

  5. Airborne laser-spark for ambient desorption/ionisation.

    PubMed

    Bierstedt, Andreas; Riedel, Jens

    2016-01-01

    A novel direct sampling ionisation scheme for ambient mass spectrometry is presented. Desorption and ionisation are achieved by a quasi-continuous laser induced plasma in air. Since there are no solid or liquid electrodes involved the ion source does not suffer from chemical interferences or fatigue originating from erosive burning or from electrode consumption. The overall plasma maintains electro-neutrality, minimising charge effects and accompanying long term drift of the charged particles trajectories. In the airborne plasma approach the ambient air not only serves as the plasma medium but at the same time also slows down the nascent ions via collisional cooling. Ionisation of the analyte molecules does not occur in the plasma itself but is induced by interaction with nascent ionic fragments, electrons and/or far ultraviolet photons in the plasma vicinity. At each individual air-spark an audible shockwave is formed, providing new reactive species, which expands concentrically and, thus, prevents direct contact of the analyte with the hot region inside the plasma itself. As a consequence the interaction volume between plasma and analyte does not exceed the threshold temperature for thermal dissociation or fragmentation. Experimentally this indirect ionisation scheme is demonstrated to be widely unspecific to the chemical nature of the analyte and to hardly result in any fragmentation of the studied molecules. A vast ensemble of different test analytes including polar and non-polar hydrocarbons, sugars, low mass active ingredients of pharmaceuticals as well as natural biomolecules in food samples directly out of their complex matrices could be shown to yield easily accessible yet meaningful spectra. Since the plasma medium is humid air, the chemical reaction mechanism of the ionisation is likely to be similar to other ambient ionisation techniques. Wir stellen hier eine neue Ionisationsmethode für die Umgebungsionisation (ambient ionisation) vor. Sowohl die

  6. High ionisation absorption in low mass X-ray binaries

    NASA Astrophysics Data System (ADS)

    Ponti, G.; Bianchi, S.; Muñoz-Darias, T.; De, K.; Fender, R.; Merloni, A.

    2016-05-01

    The advent of the new generation of X-ray telescopes yielded a significant step forward in our understanding of ionised absorption generated in the accretion discs of X-ray binaries. It has become evident that these relatively weak and narrow absorption features, sporadically present in the X-ray spectra of some systems, are actually the signature of equatorial outflows, which might carry away more matter than that being accreted. Therefore, they play a major role in the accretion phenomenon. These outflows (or ionised atmospheres) are ubiquitous during the softer states but absent during the power-law dominated, hard states, suggesting a strong link with the state of the inner accretion disc, presence of the radio-jet and the properties of the central source. Here, we discuss the current understanding of this field.

  7. IEC STANDARDS FOR INDIVIDUAL MONITORING OF IONISING RADIATION

    SciTech Connect

    Voytchev, Miroslav; Ambrosi, P.; Behrens, R.; Chiaro Jr, Peter John

    2011-01-01

    This paper presents IEC/SC 45B Radiation protection instrumentation and its standards for individual monitoring of ionising radiation: IEC 61526 Ed. 3 for active personal dosemeters and IEC 62387-1 for passive integrating dosimetry systems. The transposition of these standards as CENELEC (European) standards is also discussed together with the collaboration between IEC/SC 45B and ISO/TC 85/SC 2.

  8. Fully kinetic simulations of magnetic reconnection in partially ionised gases

    NASA Astrophysics Data System (ADS)

    Innocenti, M. E.; Jiang, W.; Lapenta, G.; Markidis, S.

    2016-12-01

    Magnetic reconnection has been explored for decades as a way to convert magnetic energy into kinetic energy and heat and to accelerate particles in environments as different as the solar surface, planetary magnetospheres, the solar wind, accretion disks, laboratory plasmas. When studying reconnection via simulations, it is usually assumed that the plasma is fully ionised, as it is indeed the case in many of the above-mentioned cases. There are, however, exceptions, the most notable being the lower solar atmosphere. Small ionisation fractions are registered also in the warm neutral interstellar medium, in dense interstellar clouds, in protostellar and protoplanetary accreditation disks, in tokamak edge plasmas and in ad-hoc laboratory experiments [1]. We study here how magnetic reconnection is modified by the presence of a neutral background, i.e. when the majority of the gas is not ionised. The ionised plasma is simulated with the fully kinetic Particle-In-Cell (PIC) code iPic3D [2]. Collisions with the neutral background are introduced via a Monte Carlo plug-in. The standard Monte Carlo procedure [3] is employed to account for elastic, excitation and ionization electron-neutral collisions, as well as for elastic scattering and charge exchange ion-neutral collisions. Collisions with the background introduce resistivity in an otherwise collisionless plasma and modifications of the particle distribution functions: particles (and ions at a faster rate) tend to thermalise to the background. To pinpoint the consequences of this, we compare reconnection simulations with and without background. References [1] E E Lawrence et al. Physical review letters, 110(1):015001, 2013. [2] S Markidis et al. Mathematics and Computers in Simulation, 80(7):1509-1519, 2010. [3] K Nanbu. IEEE Transactions on plasma science, 28(3):971-990, 2000.

  9. IEC standards for individual monitoring of ionising radiation.

    PubMed

    Voytchev, M; Ambrosi, P; Behrens, R; Chiaro, P

    2011-03-01

    This paper presents IEC/SC 45B 'Radiation protection instrumentation' and its standards for individual monitoring of ionising radiation: IEC 61526 Ed. 3 for active personal dosemeters and IEC 62387-1 for passive integrating dosimetry systems. The transposition of these standards as CENELEC (European) standards is also discussed together with the collaboration between IEC/SC 45B and ISO/TC 85/SC 2.

  10. Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector.

    PubMed

    Dixon, R Brent; Bereman, Michael S; Muddiman, David C; Hawkridge, Adam M

    2007-10-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented.

  11. Erich Regener and the ionisation maximum of the atmosphere

    NASA Astrophysics Data System (ADS)

    Carlson, P.; Watson, A. A.

    2014-12-01

    In the 1930s the German physicist Erich Regener (1881-1955) did important work on the measurement of the rate of production of ionisation deep under water and in the atmosphere. Along with one of his students, Georg Pfotzer, he discovered the altitude at which the production of ionisation in the atmosphere reaches a maximum, often, but misleadingly, called the Pfotzer maximum. Regener was one of the first to estimate the energy density of cosmic rays, an estimate that was used by Baade and Zwicky to bolster their postulate that supernovae might be their source. Yet Regener's name is less recognised by present-day cosmic ray physicists than it should be, largely because in 1937 he was forced to take early retirement by the National Socialists as his wife had Jewish ancestors. In this paper we briefly review his work on cosmic rays and recommend an alternative naming of the ionisation maximum. The influence that Regener had on the field through his son, his son-in-law, his grandsons and his students, and through his links with Rutherford's group in Cambridge, is discussed in an appendix. Regener was nominated for the Nobel Prize in Physics by Schrödinger in 1938. He died in 1955 at the age of 73.

  12. 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.

  13. 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.

  14. Determination of patulin in apple and derived products by UHPLC-MS/MS. Study of matrix effects with atmospheric pressure ionisation sources.

    PubMed

    Beltrán, Eduardo; Ibáñez, María; Sancho, Juan Vicente; Hernández, Félix

    2014-01-01

    Sensitive and reliable analytical methodology has been developed for the measurement of patulin in regulated foodstuffs by using ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) with triple quadrupole analyser. Solid samples were extracted with ethyl acetate, while liquid samples were directly injected into the chromatographic system after dilution and filtration without any clean-up step. Chromatographic separation was achieved in less than 4min. Electrospray (ESI) and atmospheric pressure chemical ionisation (APCI) sources were evaluated, in order to assess matrix effects. The use of ESI source caused strong signal suppression in samples; however, matrix effect was negligible using APCI, allowing quantification with calibration standards prepared in solvent. The method was validated in four different apple matrices (juice, fruit, puree and compote) at two concentrations at the low μgkg(-1) level. Average recoveries (n=5) ranged from 71% to 108%, with RSDs lower than 14%. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Electron interactions with positively and negatively multiply charged biomolecular clusters

    NASA Astrophysics Data System (ADS)

    Feketeová, Linda

    2012-07-01

    Interactions of positively and negatively multiply charged biomolecular clusters with low-energy electrons, from ~ 0 up to 50 eV of electron energy, were investigated in a high resolution Fourier-Transform Ion Cyclotron Resonance mass spectrometer equipped with an electrospray ionisation source. Electron-induced dissociation reactions of these clusters depend on the energy of the electrons, the size and the charge state of the cluster. The positively charged clusters [Mn+2H]2+ of zwitterionic betaines, M = (CH3)2XCH2CO2 (X = NCH3 and S), do capture an electron in the low electron energy region (< 10 eV). At higher electron energies neutral evaporation from the cluster becomes competitive with Coulomb explosion. In addition, a series of singly charged fragments arise from bond cleavage reactions, including decarboxylation and CH3 group transfer, due to the access of electronic excited states of the precursor ions. These fragmentation reactions depend on the type of betaine (X = NCH3 or S). For the negative dianionic clusters of tryptophan [Trp9-2H]2-, the important channel at low electron energies is loss of a neutral. Coulomb explosion competes from 19.8 eV and dominates at high electron energies. A small amount of [Trp2-H-NH3]- is observed at 21.8 eV.

  16. Alkylation of DNA by melphalan: investigation of capillary liquid chromatography-electrospray ionization tandem mass spectrometry in the study of the adducts at the nucleoside level.

    PubMed

    Van den Driessche, Bart; Lemière, Filip; Van Dongen, Walter; Esmans, Eddy L

    2003-02-25

    Nitrogen mustards are among the oldest cancer chemotherapeutic agents and remain the drugs of choice for treatment of many human cancers. A serious complication of treatment with nitrogen mustards is the increased risk of a secondary leukaemia in long-term survivors because not all alkylating agent interactions with DNA result in cell death. In an earlier study 2'-deoxy-5'-mononucleotide/melphalan adducts have been analysed by us by LC-ES MSMS. In this work we want to present the first results of the analysis of the corresponding 2'-deoxynucleoside/melphalan adducts from DNA hydrolysates by column switching/capillary LC-ES tandem mass spectrometry. Nucleosides, compared to nucleotides, give better chromatographic results and show a good sensitivity under electrospray (+) [ES(+)] ionisation. Several adducts were identified under ES(+) conditions. Mono-alkylated nucleoside adducts alkylated at the base moiety were identified for dGuo, dCyd and dAdo. Structures were identified by recording the low-energy CAD product ion scans. Also a mono-alkylated nucleotide pdA with alkylation position at the phosphate moiety could be detected. This proves that in the case of phosphate alkylation the enzymatic dephosphorylation reaction was inhibited. A Jurkat cell suspension was treated with melphalan (1 mM) and incubated at 37 degrees C (5% CO(2)). After 6 and 48 h, the DNA was isolated and enzymatically hydrolysed. The corresponding nucleoside pool was evaluated with the developed LC-MS method. In the 48-h experiment, one adduct could be identified as a N-7 alkylated dGuo. In the 6-h experiment, no adducts could be found. Additional experiments were done wherein Jurkat-DNA, isolated from a non-treated cell culture, was treated with melphalan. These results were analogous with the data found in melphalan-treated calf thymus DNA. Additionally, we tried to determine the exact alkylation position by interpreting high-resolution fragmentation spectra.

  17. Analysis of solvent dyes in refined petroleum products by electrospray ionization mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.

    2010-01-01

    Solvent dyes are used to color refined petroleum products to enable differentiation between gasoline, diesel, and jet fuels. Analysis for these dyes in the hydrocarbon product is difficult due to their very low concentrations in such a complex matrix. Flow injection analysis/electrospray ionization/mass spectrometry in both negative and positive mode was used to optimize ionization of ten typical solvent dyes. Samples of hydrocarbon product were analyzed under similar conditions. Positive electrospray ionization produced very complex spectra, which were not suitably specific for targeting only the dyes. Negative electrospray ionization produced simple spectra because aliphatic and aromatic moieties were not ionized. This enabled screening for a target dye in samples of hydrocarbon product from a spill.

  18. Threshold law for positron-atom impact ionisation

    NASA Technical Reports Server (NTRS)

    Temkin, A.

    1982-01-01

    The threshold law for ionisation of atoms by positron impact is adduced in analogy with our approach to the electron-atom ionization. It is concluded the Coulomb-dipole region of the potential gives the essential part of the interaction in both cases and leads to the same kind of result: a modulated linear law. An additional process which enters positron ionization is positronium formation in the continuum, but that will not dominate the threshold yield. The result is in sharp contrast to the positron threshold law as recently derived by Klar on the basis of a Wannier-type analysis.

  19. The influence of stopping power on the ionisation quench factor.

    PubMed

    García, G; Grau, Malonda A

    2002-01-01

    Stopping power values for high energies have been computed applying the first Born approximation and the Bethe formula. However, this approximation tends to overestimate these cross sections at low energies, reaching discrepancies on the order of 50% at energies below 1 keV for most of the molecular targets of interest. In this paper we propose a method to obtain accurate low energy stopping powers of electrons by combining total cross section measurements with a theoretical treatment of the elastic process. We determine the optimum value of the kB parameter of ionisation quenching for the stopping power obtained in this paper.

  20. Laboratory astrophysics experiments relating to ionising and weakly radiative shocks

    NASA Astrophysics Data System (ADS)

    Cross, Joseph; Foster, John; Graham, Peter; Busschaert, Clotilde; Charpentier, Nicolas; Danson, Colin; Doyle, Hugo; Drake, R. Paul; Falize, Emeric; Fyrth, Jim; Gumbrell, Edward; Koenig, Michel; Kuranz, Carolyn; Loupias, Berenice; Michaut, Claire; Patankar, Sid; Skidmore, Jonathan; Spindloe, Christopher; Tubman, Ellie; Woolsey, Nigel; Yurchak, Roman; Gregori, Gianluca

    2014-10-01

    The aim of the POLAR project is to simulate, in the laboratory, the accretion shock region of a magnetic cataclysmic variable binary star system. Scaling laws have shown that laser experiments can be related to astrophysical phenomena by matching relevant dimensionless parameters. As well as forming a reverse shock, relevant to the POLAR project, the experimental system is also likely formed of a weakly radiating shock and an ionisation front. Results from our experiment at the Orion Laser are presented here, alongside comparisons to simulation and the astrophysical case (of relevance to triggered star formation).

  1. Feedback regulated escape of ionising radiation from high redshift galaxies

    NASA Astrophysics Data System (ADS)

    Trebitsch, M.; Blaizot, J.

    2016-12-01

    Small galaxies are thought to provide the bulk of the radiation necessary to reionise the Universe by z ˜ 6. Their ionising efficiency is usually quantified by their escape fraction f_{esc}, but it is extremely hard to constrain from observations. With the goal of studying the physical processes that determine the values of the escape fraction, we have run a series of high resolution, cosmological, radiative hydrodynamics simulations centred on three galaxies. We find that the variability of the escape fraction follows that of the star formation rate, and that local feedback is necessary for radiation to escape.

  2. Intercomparison of ionisation chamber measurements from (125)I seeds.

    PubMed

    Davies, J B; Enari, K F; Baldock, C

    2007-05-01

    The reference air kerma rates of a set of individual (125)I seeds were calculated from current measurements of a calibrated re-entrant ionisation chamber. Single seeds were distributed to seven Australian brachytherapy centres for the same measurement with the user's instrumentation. Results are expressed as the ratio of the reference air kerma rate measured by the Australian Nuclear Science & Technology Organisation (ANSTO) to the reference air kerma rate measured at the centre. The intercomparison ratios of all participants were within +/-5% of unity.

  3. Production and properties of electrosprayed sericin nanopowder

    NASA Astrophysics Data System (ADS)

    Hazeri, Najmeh; Tavanai, Hossein; Moradi, Ali Reza

    2012-06-01

    Sericin is a proteinous substrate that envelops fibroin (silk) fiber, and its recovery provides significant economical and social benefits. Sericin is an antibacterial agent that resists oxidation and absorbs moisture and UV light. In powder form, sericin has a wide range of applications in food, cosmetics and drug delivery. Asides from other techniques of producing powder, such as precipitation and spray drying, electrospraying can yield solid nanoparticles, particularly in the submicron range. Here, we report the production of sericin nanopowder by electrospraying. Sericin sponge was recovered from Bombyx mori cocoons through a high-temperature, high-pressure process, followed by centrifugation and freeze drying of the sericin solution. The electrospraying solution was prepared by dissolving the sericin sponge in dimethyl sulfoxide. We demonstrate that electrospraying is capable of producing sericin nanopowder with an average particle size of 25 nm, which is by far smaller than the particles produced by other techniques. The electrosprayed sericin nanopowder consists of small crystallites and exhibits a high moisture absorbance.

  4. Production and properties of electrosprayed sericin nanopowder

    PubMed Central

    Hazeri, Najmeh; Tavanai, Hossein; Moradi, Ali Reza

    2012-01-01

    Sericin is a proteinous substrate that envelops fibroin (silk) fiber, and its recovery provides significant economical and social benefits. Sericin is an antibacterial agent that resists oxidation and absorbs moisture and UV light. In powder form, sericin has a wide range of applications in food, cosmetics and drug delivery. Asides from other techniques of producing powder, such as precipitation and spray drying, electrospraying can yield solid nanoparticles, particularly in the submicron range. Here, we report the production of sericin nanopowder by electrospraying. Sericin sponge was recovered from Bombyx mori cocoons through a high-temperature, high-pressure process, followed by centrifugation and freeze drying of the sericin solution. The electrospraying solution was prepared by dissolving the sericin sponge in dimethyl sulfoxide. We demonstrate that electrospraying is capable of producing sericin nanopowder with an average particle size of 25 nm, which is by far smaller than the particles produced by other techniques. The electrosprayed sericin nanopowder consists of small crystallites and exhibits a high moisture absorbance. PMID:27877498

  5. Novel electrosprayed nanospherules for enhanced aqueous solubility and oral bioavailability of poorly water-soluble fenofibrate

    PubMed Central

    Yousaf, Abid Mehmood; Mustapha, Omer; Kim, Dong Wuk; Kim, Dong Shik; Kim, Kyeong Soo; Jin, Sung Giu; Yong, Chul Soon; Youn, Yu Seok; Oh, Yu-Kyoung; Kim, Jong Oh; Choi, Han-Gon

    2016-01-01

    Purpose The purpose of the present research was to develop a novel electrosprayed nanospherule providing the most optimized aqueous solubility and oral bioavailability for poorly water-soluble fenofibrate. Methods Numerous fenofibrate-loaded electrosprayed nanospherules were prepared with polyvinylpyrrolidone (PVP) and Labrafil® M 2125 as carriers using the electrospray technique, and the effect of the carriers on drug solubility and solvation was assessed. The solid state characterization of an optimized formulation was conducted by scanning electron microscopy, powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopic analyses. Oral bioavailability in rats was also evaluated for the formulation of an optimized nanospherule in comparison with free drug and a conventional fenofibrate-loaded solid dispersion. Results All of the electrosprayed nanospherule formulations had remarkably enhanced aqueous solubility and dissolution compared with free drug. Moreover, Labrafil M 2125, a surfactant, had a positive influence on the solubility and dissolution of the drug in the electrosprayed nanospherule. Increases were observed as the PVP/drug ratio increased to 4:1, but higher ratios gave no significant increases. In particular, an electrosprayed nanospherule composed of fenofibrate, PVP, and Labrafil M 2125 at the weight ratio of 1:4:0.5 resulted in a particle size of <200 nm with the drug present in the amorphous state. It demonstrated the highest solubility (32.51±2.41 μg/mL), an excellent dissolution (~85% in 10 minutes), and an oral bioavailability ~2.5-fold better than that of the free drug. It showed similar oral bioavailability compared to the conventional solid dispersion. Conclusion Electrosprayed nanospherules, which provide improved solubility and bioavailability, are promising drug delivery tools for oral administration of poorly water-soluble fenofibrate. PMID:26834471

  6. Novel electrosprayed nanospherules for enhanced aqueous solubility and oral bioavailability of poorly water-soluble fenofibrate.

    PubMed

    Yousaf, Abid Mehmood; Mustapha, Omer; Kim, Dong Wuk; Kim, Dong Shik; Kim, Kyeong Soo; Jin, Sung Giu; Yong, Chul Soon; Youn, Yu Seok; Oh, Yu-Kyoung; Kim, Jong Oh; Choi, Han-Gon

    2016-01-01

    The purpose of the present research was to develop a novel electrosprayed nanospherule providing the most optimized aqueous solubility and oral bioavailability for poorly water-soluble fenofibrate. Numerous fenofibrate-loaded electrosprayed nanospherules were prepared with polyvinylpyrrolidone (PVP) and Labrafil(®) M 2125 as carriers using the electrospray technique, and the effect of the carriers on drug solubility and solvation was assessed. The solid state characterization of an optimized formulation was conducted by scanning electron microscopy, powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopic analyses. Oral bioavailability in rats was also evaluated for the formulation of an optimized nanospherule in comparison with free drug and a conventional fenofibrate-loaded solid dispersion. All of the electrosprayed nanospherule formulations had remarkably enhanced aqueous solubility and dissolution compared with free drug. Moreover, Labrafil M 2125, a surfactant, had a positive influence on the solubility and dissolution of the drug in the electrosprayed nanospherule. Increases were observed as the PVP/drug ratio increased to 4:1, but higher ratios gave no significant increases. In particular, an electrosprayed nanospherule composed of fenofibrate, PVP, and Labrafil M 2125 at the weight ratio of 1:4:0.5 resulted in a particle size of <200 nm with the drug present in the amorphous state. It demonstrated the highest solubility (32.51±2.41 μg/mL), an excellent dissolution (~85% in 10 minutes), and an oral bioavailability ~2.5-fold better than that of the free drug. It showed similar oral bioavailability compared to the conventional solid dispersion. Electrosprayed nanospherules, which provide improved solubility and bioavailability, are promising drug delivery tools for oral administration of poorly water-soluble fenofibrate.

  7. Simultaneous determination of riboflavin, pyridoxine, nicotinamide, caffeine and taurine in energy drinks by planar chromatography-multiple detection with confirmation by electrospray ionization mass spectrometry.

    PubMed

    Aranda, Mario; Morlock, Gertrud

    2006-10-27

    A new high-throughput method was developed to detect simultaneously riboflavin (Vitamin B(2)), pyridoxine (Vitamin B(6)), nicotinamide (Vitamin B(3)), caffeine and taurine in energy drinks by multiple detection. Ten samples of energy drinks and six samples of beverages containing caffeine were prepared by degassing in an ultrasonic bath for 20 min. After chromatography, multi-wavelength scanning was performed by: (1) UV-absorbance measurement at 261 nm for nicotinamide and 275 nm for caffeine, (2) fluorescence measurement at 366/>400 and 313/>340 nm for riboflavin and pyridoxine, respectively, and (3) Vis-absorbance measurement at 525 nm for taurine, after post-chromatographic derivatization with ninhydrin reagent. Calibrations were linear or polynomial with determination coefficients r(2)>0.999. Overall recoveries of the five compounds were between 81 and 106% at three different concentration levels. Repeatabilities (RSD, %) of all substances in matrix were determined to be between 0.8 and 1.5%. Intermediate precisions (RSD, %) ranged between 3.6 and 7.4% for riboflavin, 2.8 and 6.3% for nicotinamide, 2.5 and 4.4% for caffeine, 2.1 and 2.9% for taurine and 0.5 and 4.0% for pyridoxine at different concentration levels. Mass confirmation was performed by a single quadrupole MS in positive electrospray ionisation (ESI) scan mode for all substances except taurine (negative mode). This method offers a good alternative for routine analysis due to its simplicity and at the same time reliability.

  8. Electrospray droplet impact secondary ion mass spectrometry using a vacuum electrospray source.

    PubMed

    Takaishi, R; Sakai, Y; Hiraoka, K; Wada, H; Morita, S; Nakashima, T; Nonami, H

    2015-08-15

    In electrospray droplet impact (EDI) developed in our laboratory, an atmospheric pressure electrospray source has been used. To increase the ion beam intensity and reduce the evacuation load, a vacuum electrospray cluster ion source using a silica capillary was developed. A silica capillary with a tip inner diameter of 8 µm was used for vacuum electrospray using aqueous 10% methanol. To stabilize the flow rate of the liquid for nano-electrospray, a home-made constant pressure liquid pump was also developed. By using the silica tip nano-electrospray emitter and a constant pressure pump, stable electrospray with flow rate of 22 nL/min was realized without using any heating system such as laser irradiation. Comparative study of mass spectra obtained by atmospheric pressure EDI (A-EDI) and vacuum EDI (V-EDI) was made for various samples such as thermometer molecule, peptide, polystyrene, Alq(3), NPD, C(60), indium, and SiO(2). V-EDI showed slightly milder ionization than A-EDI. Because V-EDI gave higher target current (5-10 nA) than A-EDI (a few nA at most), V-EDI secondary ion mass spectrometry (SIMS) would be a useful technique for the surface and interface analysis. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Capillary electrophoresis electrospray ionization mass spectrometry interface

    DOEpatents

    Smith, Richard D.; Severs, Joanne C.

    1999-01-01

    The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an anolyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

  10. Multidisciplinary approach to assess the sensitivity of dwarf tomato plants to low-LET ionising radiation

    NASA Astrophysics Data System (ADS)

    De Micco, Veronica; De Pascale, Stefania; Aronne, Giovanna; Paradiso, Roberta; Vitaglione, Paola; Turano, Mimmo; Arena, Carmen

    Ionising radiation, acting alone or in interaction with microgravity and other environmental constraints, may affect plant at molecular, morpho-structural and physiological level. The intensity of the plant’s response depends on the properties of radiation and on the features of the plant itself. Indeed, different species are characterised by different susceptibility to radiation which may change during the life course. The aim of this research was to study the radiosensitivity to low-LET ionising radiation of plants of dwarf tomato (Solanum lycopersicum L. ‘Microtom’) at two phenological phases (vegetative and reproductive), within the purpose of analysing plants for consideration as candidates for Bioregenerative Life Support Systems (BLSS) in Space. To pursue this objective, plants of the cultivar Microtom were irradiated with different doses of X-rays either at the stage of the second true leaf (VP - vegetative phase) or when at least one flower was blossomed (RP - reproductive phase). Plant’s response to ionising radiation was assessed through a multidisciplinary approach combining genetic analyses, ecophysiological measurements, morpho-anatomical characterisation of leaves and fruits, nutritional analyses of fruits. Growth, molecular and morpho-functional traits were measured during plant development up to fruiting in both VP and RP plant groups, and compared with non-irradiated control plants. Plant growth was monitored weekly recording parameters such as plant height, number of leaves, leaf area, flowering and fruiting rate. Potential DNA alterations were explored through Random Amplified Polymorphic DNA (RAPD) technique. The efficiency of the photosynthetic apparatus was evaluated by determining photosynthetic pigment composition, photochemistry and leaf gas exchanges. Leaf and fruit structure were analysed through light and epi-fluorescence microscopy. Leaf anatomical traits related to photosynthetic efficiency, and to structural radioprotection

  11. Partial ionisation cross-sections of 2-propanol and ethanal

    NASA Astrophysics Data System (ADS)

    Vacher, J. R.; Jorand, F.; Blin-Simiand, N.; Pasquiers, S.

    2006-04-01

    Electron impact ionisation of 2-propanol and ethanal is studied using mass spectrometry. Cross-sections of the formation of molecular ions and ionic fragments are measured between 14 and 86 eV. Free energy changes are evaluated using ab initio calculations. For 2-propanol, two ions, identified as CH 3CHOH + (45 amu) and CH3CHCH3+ (43 amu), contribute more than 75% to the total cross-section over the whole range of electron energies and are produced by simple bond cleavage in the molecular ion. Both processes occur spontaneously, leaving the molecular ion as a minority species. For ethanal, two ions, identified as HCO + (29 amu) and CH 3CO + (43 amu), and the molecular ion (44 amu) contribute more than 80% to the total cross-section. The ions of 29 and 43 amu result from a simple bond cleavage in the molecular ion. These sprocesses are not spontaneous and the contribution of the molecular ion becomes predominant at 15 eV and is therefore significant over the whole range of ionisation energies.

  12. Kr-81m calibration factor for the npl ionisation chamber.

    PubMed

    Johansson, Lena; Stroak, Andrew

    2006-01-01

    A general method has been developed for the measurement of the activity concentration of 81mKr gas. Due to its short half-life, 13.1s, this gas has to be eluted from a 81Rb/81mKr generator. The 81Rb parent has a half-life of about 4.6 h. The calibration was done in two steps: firstly, a gamma-ray spectrometer was calibrated using 51Cr and 139Ce sources, nuclides with gamma-ray energies bracketing that of 81mKr (190.5 keV). The measurement geometry was equivalent to that of the 81mKr measurement; the sources were inserted into two collimated PTFE tubes in front of the gamma-ray detector. Secondly, a calibration factor for the NPL radionuclide calibrator was determined with a specially designed ionisation chamber insert. The 81mKr gas passed in front of the gamma-ray detector in PTFE tubing before and after entering the ionisation chamber. The calibration factor for 81mKr in the radionuclide calibrator with this geometry was independent of the gas flow rate within determined limits. The analytical calculations of the activity determination, uncertainties and measurement criteria are discussed.

  13. A low background ionisation chamber for alpha-spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilsenach, Heinrich; Zuber, Kai; Krüger, Felix; Hartmann, Andreas; Sobiella, Manfred

    2017-09-01

    The goal of designing a low background ionisation chamber is to measure long lived α-decay half-lives which might interfere with rare event searches. Such decays play a part in many fields in nuclear physics and are difficult to measure. A lot of Geiger-Nutall studies also depend on them. Among others the research is specifically aimed at the precision measurements of α emitters mainly within the Lanthanide region. The excellent energy resolution would also allow to search for excited states in α-decays. To achieve this goal a gridded ionisation chamber was constructed using the Frisch-Grid design. A background rate of only 10.9(6) counts per day has been achieved in the energy region of 1 MeV to 9 MeV and improvements are possible. This low background rate and size of the chamber allows precision measurements of long living alpha decays with half-lives in the region of 1 × 1015 years.

  14. Surface tension effects on submerged electrosprays

    PubMed Central

    Marín, Álvaro G.; Loscertales, Ignacio G.; Barrero, Antonio

    2012-01-01

    Electrosprays are a powerful technique to generate charged micro/nanodroplets. In the last century, the technique has been extensively studied, developed, and recognized with a shared Nobel price in Chemistry in 2002 for its wide spread application in mass spectrometry. However, nowadays techniques based on microfluidic devices are competing to be the next generation in atomization techniques. Therefore, an interesting development would be to integrate the electrospray technique into a microfluidic liquid-liquid device. Several works in the literature have attempted to build a microfluidic electrospray with disputable results. The main problem for its integration is the lack of knowledge of the working parameters of the liquid-liquid electrospray. The “submerged electrosprays” share similar properties as their counterparts in air. However, in the microfluidic generation of micro/nanodroplets, the liquid-liquid interfaces are normally stabilized with surface active agents, which might have critical effects on the electrospray behavior. In this work, we review the main properties of the submerged electrosprays in liquid baths with no surfactant, and we methodically study the behavior of the system for increasing surfactant concentrations. The different regimes found are then analyzed and compared with both classical and more recent experimental, theoretical and numerical studies. A very rich phenomenology is found when the surface tension is allowed to vary in the system. More concretely, the lower states of electrification achieved with the reduced surface tension regimes might be of interest in biological or biomedical applications in which excessive electrification can be hazardous for the encapsulated entities. PMID:24155865

  15. 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.

  16. On-line micellar electrokinetic chromatography-electrospray ionization mass spectrometry using anodically migrating micelles

    SciTech Connect

    Yang, L.; Harrata, A.K.; Lee, C.S. |

    1997-05-15

    On-line micellar electrokinetic chromatography (MEKC)-electrospray ionization mass spectrometry (ESIMS) is demonstrated for the analysis of chlorotriazine herbicides and barbiturates. In this study, the micellar velocity is directly manipulated by the adjustment of electroosmosis rather than the electrophoretic velocity of the micelle. The electroosmotic flow is adjusted against the electrophoretic velocity of the micelle by changing the solution pH in MEKC. The elimination of MEKC surfactant introduction into ESIMS is achieved with an anodically migrating micelle, moving away from the electrospray interface. The effects of moving surfactant boundary in the MEKC capillary on separation efficiency and resolution of triazine herbicides and barbiturates are investigated. The mass detection of herbicides and barbiturates sequentially eluted from the MEKC capillary is acquired using the positive and negative electrospray modes, respectively. 30 refs., 8 figs., 3 tabs.

  17. Transferring calibration coefficients from ionisation chambers used for diagnostic radiology to transmission chambers.

    PubMed

    Yoshizumi, Maíra T; Caldas, Linda V E

    2012-07-01

    In this work, the response of a double volume transmission ionisation chamber, developed at the Instituto de Pesquisas Energéticas e Nucleares, was compared to that of a commercial transmission chamber. Both ionisation chambers were tested in different X-ray beam qualities using secondary standard ionisation chambers as reference dosimeters. These standard ionisation chambers were a parallel-plate and a cylindrical ionisation chambers, used for diagnostic radiology and mammography beam qualities, respectively. The response of both transmission chambers was compared to that of the secondary standard chambers to obtain coefficients of equivalence. These coefficients allow the transmission chambers to be used as reference equipment. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Trace analysis of tiamulin in honey by liquid chromatography-diode array-electrospray ionization mass spectrometry detection.

    PubMed

    Nozal, M J; Bernal, J L; Martín, M T; Jiménez, J J; Bernal, J; Higes, M

    2006-05-26

    A liquid chromatography with diode array or electrospray ionisation mass spectrometry detection (LC-DAD-ESI-MS) method for the determination of tiamulin residues in honey is presented. The procedure employs a solid-phase extraction (SPE) on polymeric cartridges for the isolation of tiamulin from honey samples diluted in aqueous solution of tartaric acid. Chromatographic separation of the tiamulin is performed, in isocratic mode, on a C18 column using methanol and ammonium carbonate 0.1% in water, in proportion (30:70, v/v). Average analyte recoveries were from 88 to 106% in replica sets of fortified honey samples. The LC-ESI-MS method detection limits differ from 0.5 microg kg(-1) for clear honeys to 1.2 microg kg(-1) for dark honeys. The developed method has been applied to the analysis of tiamulin residues in multifloral honey samples collected from veterinary treated beehives.

  19. CAPILLARY ELECTROPHORESIS-ELECTROSPRAY MASS SPECTRA OF THE HERBICIDES PARAQUAT AND DIQUAT

    EPA Science Inventory

    The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% m...

  20. CAPILLARY ELECTROPHORESIS-ELECTROSPRAY MASS SPECTRA OF THE HERBICIDES PARAQUAT AND DIQUAT

    EPA Science Inventory

    The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% m...

  1. A Study of the Complexation of Mercury(II) with Dicysteinyl Tetrapeptides by Electrospray Ionization Mass Spectrometry.

    PubMed

    Mazlo, Johanna; Ngu-Schwemlein, Maria

    2016-01-08

    In this study we evaluated a method for the characterization of complexes, formed in different relative ratios of mercury(II) to dicysteinyl tetrapeptide, by electrospray ionization orbitrap mass spectrometry. This strategy is based on previous successful characterization of mercury-dicysteinyl complexes involving tripeptides by utilizing mass spectrometry among other techniques. Mercury(II) chloride and a dicysteinyl tetrapeptide were incubated in a degassed buffered medium at varying stoichiometric ratios. The complexes formed were subsequently analyzed on an electrospray mass spectrometer consisting of a hybrid linear ion- and orbi- trap mass analyzer. The electrospray ionization mass spectrometry (ESI-MS) spectra were acquired in the positive mode and the observed peaks were then analyzed for distinct mercury isotopic distribution patterns and associated monoisotopic peak. This work demonstrates that an accurate stoichiometry of mercury and peptide in the complexes formed under specified electrospray ionization conditions can be determined by using high resolution ESI MS based on distinct mercury isotopic distribution patterns.

  2. Resonance ionisation mass spectrometry of krypton and its applications in planetary science

    NASA Astrophysics Data System (ADS)

    Strashnov, I.; Gilmour, J. D.

    2014-06-01

    A new resonance ionisation time-of-flight mass spectrometer for determining krypton isotope ratios in extraterrestrial samples is presented. Laser heating is used to extract gas from mg-size samples. A cryogenic sample concentrator is employed. Atoms continuously condense on a 75 K stainless steel substrate at the back plate of a Wiley-McLaren laser ion source from where they are desorbed by a pulsed 1064 nm laser and resonantly ionized in the plume. A three-colour (116.5 nm, 558.1 nm and 1064 nm) excitation scheme is used. Tuneable coherent Vacuum Ultraviolet (vuv) radiation near 116.5 nm is generated by four-wave sum frequency mixing of 252.5 nm and 1507 nm pulsed dye laser beams in a binary mixture of negatively and positively dispersive gases (Xe and Ar). Isotope effects have been observed that reduce the reproducibility of isotope ratio measurements between odd-mass, non-zero nuclear spin isotopes and even-mass, zero nuclear spin isotopes. This can be minimised and stabilised by controlling the laser fluences, experimental geometry, and the population of the magnetic sub-levels of the excited atomic states used in the ionisation process. Once stability is achieved, sample-standard bracketing (during which the known isotope ratios of a standard are determined before and after the measurements of the sample under the same conditions) allows precision and reproducibility of 1 % for the major isotope ratios to be achieved in samples krypton atoms. Detection limits of atoms/isotope have been demonstrated, ratios of Kr in meteorites have been made with 5-10 % precision. Applications of the instrument in various areas of planetary science are also discussed.

  3. Simultaneous determination of banned acid orange dyes and basic orange dyes in foodstuffs by liquid chromatography-tandem electrospray ionization mass spectrometry via negative/positive ion switching mode.

    PubMed

    Fang, Guozhen; Wu, Yu; Dong, Xiaomeng; Liu, Cuicui; He, Shaoyuan; Wang, Shuo

    2013-04-24

    Simultaneous detection of two classes of dyes possessing different chemical properties is difficult. In this study, through negative/positive ion switching mode, simultaneous determination of four typical acid orange dyes and three typical basic orange dyes was achieved by a single high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, and the analytical efficiency of multiresidues identification was greatly improved. To enhance detection sensitivity, the sample pretreatment conditions and HPLC-MS/MS determining conditions were carefully optimized. Under optimal conditions, good linearity was obtained over the range of 5-500 μg L(-1) with a correlation coefficient (R(2)) >0.9998. Limits of detection (LODs) and limits of quantification (LOQs) of the seven dyes were 0.5-3.0 and 2.0-6.0 μg kg(-1), respectively. The recoveries of the seven dyes in soybean products and marinated eggs were 74-126% with relative standard deviations (RSDs) of 2.22-25.4%, suggesting the developed method is promising for the accurate quantification of the seven dyes at trace levels in foods.

  4. Analysis of metal-EDTA complexes by electrospray mass spectrometry

    SciTech Connect

    Baron, D.; Hering, J.G.

    1998-07-01

    Solutions of the strong complexing agent ethylenediaminetetraacetic acid (EDTA) and Cu, Pb, Cd, Al, and Fe(III) were examined by electrospray mass spectrometry (ES/MS). Uncomplexed EDTA and metal-EDTA complexes survive the electrospray process intact and can be detected simultaneously by mass spectrometry. Best sensitivity was achieved in the positive ion mode in which EDTA and EDTA-metal complexes (present in solution as anions) were detected as protonated species with a single positive charge. Except for the protonation, the aqueous metal-EDTA complexes are preserved and neither fragmentation of complexes nor formation of clusters with more than one metal or ligand were observed in the mass spectra. Detection limits are between approximately 1 to 2 {micro}M for uncomplexed EDTA and for the Cu-EDTA and Pb-EDTA complexes, with a linear range up to 10{sup {minus}4} M. Calibrations based on solutions with equimolar concentrations of EDTA and Cu or Pb can be used to quantify EDTA-metal complexes in solutions with excess EDTA or metal, and in solutions with more than one metal present. Isotopic signatures of metals in the metal-ligand complexes are preserved, allowing the identification of the metal in a metal-ligand complex. Isotopic signatures of metals can therefore aid in the identification of metal-ligand complexes in unknown samples.

  5. Using ambient ozone for assignment of double bond position in unsaturated lipids.

    PubMed

    Ellis, Shane R; Hughes, Jessica R; Mitchell, Todd W; in het Panhuis, Marc; Blanksby, Stephen J

    2012-03-07

    Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.

  6. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, Richard D.; Udseth, Harold R.; Barinaga, Charles J.

    1995-01-01

    An improvement to the system and method for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity.

  7. Hazards of ionising radiation: 100 years of observations on man.

    PubMed Central

    Doll, R.

    1995-01-01

    In November 1895, when Conrad Röntgen serendipitously discovered X-rays, epidemiology was effectively limited to the study of infectious disease. What little epidemiological work was done in other fields was done as part of clinical medicine or under the heading of geographical pathology. The risks from exposure to X-rays and subsequently from other types of ionising radiation were consequently discovered by qualitative association or animal experiment. They did not begin to be quantified in humans until half a century later, when epidemiology emerged as a scientific discipline capable of quantifying risks of non-infectious disease and the scientific world was alerted to the need for assessing the effects of the radiation to which large populations might be exposed by the use of nuclear energy in peace and war. PMID:8519643

  8. Review of retrospective dosimetry techniques for external ionising radiation exposures.

    PubMed

    Ainsbury, E A; Bakhanova, E; Barquinero, J F; Brai, M; Chumak, V; Correcher, V; Darroudi, F; Fattibene, P; Gruel, G; Guclu, I; Horn, S; Jaworska, A; Kulka, U; Lindholm, C; Lloyd, D; Longo, A; Marrale, M; Monteiro Gil, O; Oestreicher, U; Pajic, J; Rakic, B; Romm, H; Trompier, F; Veronese, I; Voisin, P; Vral, A; Whitehouse, C A; Wieser, A; Woda, C; Wojcik, A; Rothkamm, K

    2011-11-01

    The current focus on networking and mutual assistance in the management of radiation accidents or incidents has demonstrated the importance of a joined-up approach in physical and biological dosimetry. To this end, the European Radiation Dosimetry Working Group 10 on 'Retrospective Dosimetry' has been set up by individuals from a wide range of disciplines across Europe. Here, established and emerging dosimetry methods are reviewed, which can be used immediately and retrospectively following external ionising radiation exposure. Endpoints and assays include dicentrics, translocations, premature chromosome condensation, micronuclei, somatic mutations, gene expression, electron paramagnetic resonance, thermoluminescence, optically stimulated luminescence, neutron activation, haematology, protein biomarkers and analytical dose reconstruction. Individual characteristics of these techniques, their limitations and potential for further development are reviewed, and their usefulness in specific exposure scenarios is discussed. Whilst no single technique fulfils the criteria of an ideal dosemeter, an integrated approach using multiple techniques tailored to the exposure scenario can cover most requirements.

  9. Protection of the environment from ionising radiation: ethical issues.

    PubMed

    Oughton, Deborah

    2003-01-01

    The paper identifies some of the main ethical issues concerning the protection of the environment from radiation and suggests ways in which ethics can aid in developing a system of protection. After a presentation of background on ethical theory and environmental ethics, three main issues related to environmental protection are discussed: First, the question of valuing the environment and implications for the definition of harm and monetary valuation of environmental goods; second, difficulties with scientific uncertainty and applications of the precautionary principle; and third, issues concerned with the distribution of risk and its relevance for participation in decision-making. In summary, the paper argues that there are strong ethical grounds to provide for the protection of the environment and that, all other things being equal, there is no reason to treat ionising radiation differently to other environmental stressors. Copyright 2002 Elsevier Science Ltd.

  10. Migration levels of PVC plasticisers: Effect of ionising radiation treatment.

    PubMed

    Zygoura, Panagiota D; Paleologos, Evangelos K; Kontominas, Michael G

    2011-09-01

    Migration levels of commercial plasticisers [di-(2-ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC)] from polyvinyl chloride (PVC) film into the EU specified aqueous food simulants (distilled water, 3% w/v acetic acid and 10% v/v ethanol) were monitored as a function of time. Migration testing was carried out at 40°C for 10days (EEC, 1993). Determination of the analytes was performed by applying the analytical methodology based on surfactant (Triton X-114) mediated extraction prior to gas chromatographic-flame ionisation detection (GC-FID) recently proposed by our group. The study focuses on the determination of the effect of gamma radiation on plasticiser migration into the selected simulants. PVC cling film used was subjected to ionising treatment with a [(60)Co] source at doses equal to 5, 15 and 25kGy. DEHA and ATBC migration into the EU aqueous simulating solvents was limited, yielding final concentrations in the respective ranges 10-100μg/l and 171-422μg/l; hence, ATBC demonstrated a stronger interaction with all three simulants compared to DEHA. Migration data, with respect to ATBC, showed that the most aggressive simulant seemed to be the 10% ethanol, while in the case of DEHA the 3% aqueous acetic acid exhibited the highest extraction efficiency; distilled water demonstrated the lowest migration in both cases. With regard to PVC treatment with gamma rays, high radiation doses up to 25kGy produced a statistically significant (p<0.05) effect on the migration of both plasticisers.

  11. Electron impact ionisation cross sections of iron hydrogen clusters

    NASA Astrophysics Data System (ADS)

    Huber, Stefan E.; Sukuba, Ivan; Urban, Jan; Limtrakul, Jumras; Probst, Michael

    2016-09-01

    We computed electron impact ionisation cross sections (EICSs) of iron hydrogen clusters, FeH n with n = 1,2, ...,10, from the ionisation threshold to 10 keV using the Deutsch-Märk (DM) and the binary-encounter-Bethe (BEB) formalisms. The maxima of the cross sections for the iron hydrogen clusters range from 6.13 × 10-16 cm2 at 60 eV to 8.76 × 10-16 cm2 at 76 eV for BEB-AE (BEB method based on quantum-chemical data from all-electron basis sets) calculations, from 4.15 × 10-16 cm2 at 77 eV to 7.61 × 10-16 cm2 at 80 eV for BEB-ECP (BEB method based on quantum-chemical data from effective-core potentials for inner-core electrons) calculations and from 2.49 × 10-16 cm2 at 43.5 eV to 7.04 × 10-16 cm2 at 51 eV for the DM method. Cross sections calculated via the BEB method are substantially higher than the ones obtained via the DM method, up to a factor of about two for FeH and FeH2. The formation of Fe-H bonds depopulates the iron 4 s orbital, causing significantly lower cross sections for the small iron hydrides compared to atomic iron. Both the DM and BEB cross sections can be fitted perfectly against a simple expression used in modelling and simulation codes in the framework of nuclear fusion research. The energetics of the iron hydrogen clusters change substantially when exact exchange is present in the density functional, while the cluster geometries do not depend on this choice.

  12. Ionisation Equilibrium for the Non-Maxwellian Electron n-Distributions in Solar Flares: Updated Calculations

    NASA Astrophysics Data System (ADS)

    Dzifčáková, Elena; Dudík, Jaroslav

    2015-12-01

    We use the latest available atomic data to calculate the ionisation and recombination rates for the non-Maxwellian n-distributions, which were shown previously to provide a good fit to the enhanced intensities of dielectronic satellite lines during solar flares. The ionisation and recombination coefficients are subsequently used to derive the ionisation equilibrium. To do so, we consider odd values of n ranging from 1 to 19, i.e., from Maxwellian to strongly non-Maxwellian cases. These calculations involve all elements with proton number up to 30, i.e., H to Zn. The n-distributions modify both the ionisation and the recombination rates. The ionisation rates decrease more steeply at lower pseudo-temperatures, while the radiative recombination rate is reduced due to a lower number of low-energy electrons. The peaks of the dielectronic recombination rates become narrower. These changes are reflected in the ionisation equilibrium. Ion abundance peaks become narrower and can also be shifted, mostly towards higher temperatures. The He-like ions are an important exception, as they are formed in a larger temperature range than that for the Maxwellian distribution. The ions Si xiii - xiv used previously for the diagnostics of the n-distributions are affected only weakly, confirming the determination of n. The ionisation equilibria are available as the electronic supplementary material in a format compatible with the CHIANTI database.

  13. INTERACTION OF LASER RADIATION WITH MATTER: Resonance laser-induced ionisation of sodium vapour taking radiative transfer into account

    NASA Astrophysics Data System (ADS)

    Kosarev, N. I.; Shaparev, N. Ya

    2006-04-01

    The problem of ionisation of atomic sodium in the field of resonance laser radiation is numerically solved taking radiative transfer into account. Seed electrons are produced due to the mechanism of associative ionisation, then they gain energy in superelastic processes (collisions of the second kind) and initiate the avalanche ionisation of the medium by electron impact. We studied the effect of secondary radiation on the laser pulse propagation upon competition between the ionising and quenching electron collisions with excited atoms, on the kinetics of ionisation-induced vapour bleaching, and the plasma channel expansion in the form of a halo.

  14. Ionising sources in the coma of 67P probed by Rosetta

    NASA Astrophysics Data System (ADS)

    Heritier, Kevin; Galand, Marina; Henri, Pierre; Eriksson, Anders; Odelstad, Elias; Altwegg, Kathrin; Beth, Arnaud; Broiles, Thomas; Burch, Jim; Carr, Christopher; Cupido, Emanuele; Glassmeier, Karl-Heinz; Nilsson, Hans; Richter, Ingo; Rubin, Martin; Vallieres, Xavier; Vigren, Erik

    2017-04-01

    An ionospheric model has been developed in order to quantify the ion number density in the coma of 67P/Churyumov-Gerasimenko. The model is driven by Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA)/Cometary Pressure Sensor (COPS) neutral density and assumes isentropic expansion for the neutral density profile. The two ionisation sources considered are photo-ionisation by solar extreme ultraviolet (EUV) radiation and electron-impact ionisation. The EUV radiation is estimated from fluxes measured by the Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED)/ Solar EUV Experiment (SEE), taking into account the phase shift and the heliocentric distance ratio; between Earth and comet 67P. The electron-impact ionisation production rates are derived from Rosetta Plasma Consortium (RPC)-Ion and Electron Sensor (IES) integrated electron fluxes and corrected for the S/C potential from RPC/LAngmuir Probe (LAP) measurements. Our results are compared with in situ measurements of the plasma density from RPC-Mutual Impedance Probe (MIP) and RPC-LAP. There is a good agreement between the modelled and RPC observed electron densities. The ionospheric model enables to distinguish the relative contributions of the different sources to the total cometary plasma. At high heliocentric distances, electron-impact ionisation becomes the dominant ionisation source and is enhanced over the winter hemisphere. As the solar activity has decreased since the beginning of the mission in 2014, the relative importance of photo-ionisation has decreased as well. However, at low heliocentric distances, photo-ionisation seems to be the most dominant ionising source, in particular through the perihelion period in summer 2015.

  15. Bio-electrospraying the nematode Caenorhabditis elegans: studying whole-genome transcriptional responses and key life cycle parameters

    PubMed Central

    Mongkoldhumrongkul, Napachanok; Swain, Suresh C.; Jayasinghe, Suwan N.; Stürzenbaum, Stephen

    2010-01-01

    Bio-electrospray, the direct jet-based cell handling approach, is able to handle a wide range of cells (spanning immortalized, primary to stem cells). Studies at the genomic, genetic and the physiological levels have shown that, post-treatment, cellular integrity is unperturbed and a high percentage (more than 70%, compared with control) of cells remain viable. Although, these results are impressive, it may be argued that cell-based systems are oversimplistic. Therefore, it is important to evaluate the bio-electrospray technology using sensitive and dynamically developing multi-cellular organisms that share, at least some, similarities with multi-cell microenviorments encountered with tissues and organs. This study addressed this issue by using a well-characterized model organism, the non-parasitic nematode Caenorhabditis elegans. Nematode cultures were subjected to bio-electrospraying and compared with positive (heat shock) and negative controls (appropriate laboratory culture controls). Overall, bio-electrospraying did not modulate the reproductive output or induce significant changes in in vivo stress-responsive biomarkers (heat shock proteins). Likewise, whole-genome transcriptomics could not identify any biological processes, cellular components or molecular functions (gene ontology terms) that were significantly enriched in response to bio-electrospraying. This demonstrates that bio-electrosprays can be safely applied directly to nematodes and underlines its potential future use in the creation of multi-cellular environments within clinical applications. PMID:19776148

  16. Photo-ionisation mass spectrometry as detection method for gas chromatography. Optical selectivity and multidimensional comprehensive separations.

    PubMed

    Zimmermann, Ralf; Welthagen, Werner; Gröger, Thomas

    2008-03-14

    Mass spectrometry (MS) with soft ionisation techniques (i.e. ionisation without fragmentation of the analyte molecules) for gaseous samples exhibits interesting analytical properties for direct analysis applications (i.e. direct inlet mass spectrometric on-line monitoring) as well as mass spectrometric detection method for gas chromatography (GC-MS). Commonly either chemical ionisation (CI) or field ionisation (FI) is applied as soft ionisation technology for GC-MS. An interesting alternative to the CI and FI technologies methods are photo-ionisation (PI) methods. PI overcomes some of the limitations of CI and FI and furthermore add some unique analytical properties. The resonance enhanced multi-photon ionisation (REMPI) method uses intense UV-laser pulses (wavelength range approximately 350-193 nm) for highly selective, sensitive and soft ionisation of predominately aromatic compounds. The single photon ionisation (SPI) method utilises VUV light (from lamps or laser sources, wavelengths range approximately 150-110 nm) can be used for a universal soft ionisation of organic molecules. In this article the historical development as well as the current status and concepts of gas chromatography hyphenated to photo-ionisation mass spectrometry are reviewed.

  17. Predictive value of derived calcium figures based on the measurement of ionised calcium.

    PubMed

    Gardner, M D; Dryburgh, F J; Fyffe, J A; Jenkins, A S

    1981-03-01

    The algorithms used in this hospital to assess calcium status are calculated ionised serum calcium and the serum calcium concentration adjusted for albumin. In order to establish their clinical usefulness, they were compared with the ionised calcium concentration measured on the Nova 2 instrument in patients with various calcium and protein abnormalities. Good correlation was found between the measured and calculated values. The predictive values for the calculated results and for total serum calcium concentrations are presented. In this series, the derived values were useful in predicting the serum ionised calcium concentration of the patients studied.

  18. Ionisation effect on the electron localisation in the subcycle waveform shaping scheme

    NASA Astrophysics Data System (ADS)

    Wang, Zhuo; Feng, Zhengpeng; Long, Hua

    2015-03-01

    We have theoretically studied the ionisation effect on the asymmetric dissociation of H+2 exposed to the synthesised multicycle infrared pulses of different wavelengths by solving the time-dependent Schr?dinger equation without using the Born-Oppenheimer approximation. It has been demonstrated that the ionisation does slightly influence the electron localisation for the relatively low pulse intensity (less than 1014 W/cm2). However, our further results show that the ionisation effect becomes much more significant when increasing the pulse intensity, leading to a distinctly different mechanism responsible for the enhancement of the electron localisation.

  19. Rapid screening method for determination of Ecstasy and amphetamines in urine samples using gas chromatography-chemical ionisation mass spectrometry.

    PubMed

    Pellegrini, M; Rosati, F; Pacifici, R; Zuccaro, R; Romolo, F S; Lopez, A

    2002-04-05

    The need for analytical screening tests more reliable and valid to detect amphetamine and related "designer drugs" in biological samples is becoming critical, due to the increasing diffusion of these drugs on the European illegal market. The most common screening procedures based on immunoassays suffer a number of limitations, including low sensitivity, lack of specificity and limited number of detectable substances. This paper describes a screening method based on gas-chromatography-mass-spectrometry (GC/MS) using positive chemical ionisation (PCI) detection. Methanol was used as reactant gas in the ionisation chamber. Molecular ions of different compounds were monitored, allowing a sensitivity of 5-10 ng/ml with high selectivity. The sensitivity of the method gives positive results in samples taken 48-72 h after intake of one dose of 50-100 mg. The method is simple and rapid. Sample preparation was limited to one liquid-liquid extraction, without any hydrolysis and derivatisation. Hydrolysis is critical to identify metabolites excreted as conjugates. Blank urine samples spiked with known amounts of amphetamine (AM), methylamphetamine (MA), methylenedioxyamphetamine (MDA), methylenedioxymethylamphetamine (MDMA), methylenedioxyethylamphetamine (MDEA) and methylenedioxyphenyl-N-methyl-2-butanamine (MBDB) were analysed. The method was successfully tested on real samples of urine from people, whose use of amphetamine was suspected, and results were compared with results obtained with immunoassays.

  20. Electrospray ionization of volatiles in breath

    NASA Astrophysics Data System (ADS)

    Martínez-Lozano, P.; de La Mora, J. Fernández

    2007-08-01

    Recent work by Zenobi and colleagues [H. Chen, A. Wortmann, W. Zhang, R. Zenobi, Angew. Chem. Int. Ed. 46 (2007) 580] reports that human breath charged by contact with an electrospray (ES) cloud yields many mass peaks of species such as urea, glucose, and other ions, some with molecular weights above 1000 Da. All these species are presumed to be involatile, and to originate from breath aerosols by so-called extractive electrospray ionization EESI [H. Chen, A. Venter, R.G. Cooks, Chem. Commun. (2006) 2042]. However, prior work by Fenn and colleagues [C.M. Whitehouse, F. Levin, C.K. Meng, J.B. Fenn, Proceedings of the 34th ASMS Conference on Mass Spectrometry and Allied Topics, Denver, 1986 p. 507; S. Fuerstenau, P. Kiselev, J.B. Fenn, Proceedings of the 47th ASMS Conference on Mass Spectrometry, 1999, Dallas, TX, 1999] and by Hill and colleagues [C. Wu, W.F. Siems, H.H. Hill Jr., Anal. Chem. 72 (2000) 396] have reported the ability of electrospray drops to ionize a variety of low vapor pressure substances directly from the gas phase, without an apparent need for the vapor to be brought into the charging ES in aerosol form. The Ph.D. Thesis of Martínez-Lozano [P. Martínez-Lozano Sinués, Ph.D. Thesis, Department of Thermal and Fluid Engineering, University Carlos III of Madrid; April 5, 2006 (in Spanish); http://hdl.handle.net/10016/655] had also previously argued that the numerous human breath species observed via a similar ES ionization approach were in fact ionized directly from the vapor. Here, we observe that passage of the breath stream through a submicron filter does not eliminate the majority of the breath vapors seen in the absence of the filter. We conclude that direct vapor charging is the leading mechanism in breath ionization by electrospray drops, though aerosol ionization may also play a role.

  1. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, R.D.; Udseth, H.R.; Barinaga, C.J.

    1995-06-13

    An improvement to the system and method is disclosed for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity. 10 figs.

  2. Modeling Electrospray Deposition of Nanoparticle Inks

    NASA Astrophysics Data System (ADS)

    Li, Ao; Fideles da Silva, Jefferson; Yong, Xin

    2015-11-01

    Electrospray of nanoparticle inks is of great importance to the manufacturing of functional materials. In this study, we develop a new three-dimensional multiphysics method to model the electrospray of colloidal suspension to a flat substrate. The Lagrangian Particle Tracking (LPT) transport equation is coupled to mass and heat transfer using convective droplet vaporization model, which allow us to track each particle-laden ink droplets and dry nanoparticles in the electrospray plume and probe the deposit structures. Herein, we consider dilute inks that are experimentally relevant, assuming monodisperse nanoparticles. We characterize the overall statistics of the plume and the dynamics of individual ink droplet or dry nanoparticle. It is shown that the segregation effect affects not only primary and satellite droplets but also dry nanoparticles. We observe nanoparticles deposit structure changing process, in particular time evolution of the density profile along radial direction. Our results show that the region of high nanoparticle density transitioning from only the edge to both the edge and center, which agrees with previous experimental studies.

  3. Self-assembled nanostructures via electrospraying

    NASA Astrophysics Data System (ADS)

    Jayasinghe, S. N.

    2006-07-01

    A concentrated nanoparticulate-based ethylene glycol suspension was prepared and electrosprayed at optimum and stable cone-jet mode conditions. Using laser spectroscopy, the droplets were measured and found to range within ∼0.23-3.8 μm. In parallel to spectroscopy-assisted sizing, a volume equivalence route for estimating droplet sizes was carried out by measuring contact angles and diameters of the deposits. The electrosprayed nanosuspension relics were examined using optical and transmission electron microscopy. These deposits were further characterized using energy-dispersive X-rays and selected area electron diffraction. Simultaneously deposits were formed by a controlled route through needle deposition without the presence of an electric field. The structures formed in this non-electric field driven route are compared with those formed with electric fields. Thus, elucidating electrosprays as a competing nanofabrication route for forming self-assemblies with a wide range of nanomaterials in the nanoscale for top-down based bottom-up assembly of structures.

  4. Ionisation Mechanisms in AN Optically Pumped Mercury Vapour.

    NASA Astrophysics Data System (ADS)

    Counsell, G. F.

    Available from UMI in association with The British Library. Requires signed TDF. A plasma formed in a mercury vapour by optical pumping at visible and U.V. wavelengths from a high current mercury discharge, has been investigated with a view to gaining an understanding of the ionisation processes giving rise to the plasma. These were believed to generate both atomic and molecular ions. The results of this work have applications in the fields of fluorescent lighting and the mercury-nitrogen laser. The plasma was studied with a variety of diagnostic tools. Electron number densities and temperatures were determined using Langmuir probes operating in the orbital motion limited regime. Populations of the 6^3 P triplet states, believed to be the only significantly populated excited states in the plasma, were determined using absorption spectroscopy. Lastly, a quadrupole mass spectrometer, coupled to the plasma with an electrostatic ion transport system, was used to investigate the flux of atomic and molecular ions to a body at floating potential in the plasma. The Langmuir probe and absorption spectroscopy results were included into a model describing ion motions in the plasma, based around the ion fluid equations and including source terms for the generation of atomic and molecular ions, both by electron impact and by binary collisions of atoms in the 6^3P triplet states. Where possible, ionisation rats in the model were calculated using published cross-sections. However, for the heavy body collisional processes in particular, many of these are unknown. Consequently, an attempt was made to determine these cross-sections by generating results from the model that could be compared to experimental measurements of the atomic and molecular ion fluxes to the mass spectrometer. A number of computational experiments were carried out, varying the cross-sections until a good fit to the experimental measurements was achieved. Using this technique it was possible to estimate cross

  5. Fabrication of micro-patterns via near-field electrospray

    NASA Astrophysics Data System (ADS)

    Li, Wenwang; Zheng, Gaofeng; Xu, Lei; Wang, Xiang

    2016-11-01

    A near-field electrospray process is developed to deposited micro-patterns. Compared with conventional electrospray, near field electrospray uses a steel probe instead of capillary nozzle, and its nozzle-to-substrate distance is shortened to several millimeters to realize micro-scale deposition area. The liquid is supplied by discretely dipping the probe into solution in advance so that electrospray process maintains until the consumption of liquid adhered at the probe tip. The influence of solution conductivity and applied voltage on deposition are investigated, as increasing solution conductivity and high applied voltage may promote the electrospray process and enlarge the line width. In addition, micro-patterns with various materials are directly electrosprayed.

  6. Formation of metal-ion adducts and evidence for surface-catalyzed ionization in electrospray analysis of pharmaceuticals and pesticides

    USGS Publications Warehouse

    Thurman, E.M.; Ferrer, I.

    2002-01-01

    The formation of metal ion adducts in liquid chromatography/mass spectrometry positive-ion electrospray analysis of pharmaceuticals and pesticides was investigated. The evidence of surface-catalyzed ionization in the electrospray analysis was also studied. Both positive and negative ion mass spectrometry were used for the analysis of the products. It was found that the sodium adducts formed in the analysis included single, double, and triple sodium adducts. Adduction was found to occur by attachment of the metal ion to carboxyl, carbonyl and aromatic pi electrons of the molecule.

  7. Ion recombination correction factor in scanned light-ion beams for absolute dose measurement using plane-parallel ionisation chambers

    NASA Astrophysics Data System (ADS)

    Rossomme, S.; Horn, J.; Brons, S.; Jäkel, O.; Mairani, A.; Ciocca, M.; Floquet, V.; Romano, F.; Rodriguez Garcia, D.; Vynckier, S.; Palmans, H.

    2017-07-01

    Based on international reference dosimetry protocols for light-ion beams, a correction factor (k s) has to be applied to the response of a plane-parallel ionisation chamber, to account for recombination of negative and positive charges in its air cavity before these charges can be collected on the electrodes. In this work, k s for IBA PPC40 Roos-type chambers is investigated in four scanned light-ion beams (proton, helium, carbon and oxygen). To take into account the high dose-rates used with scanned beams and LET-values, experimental results are compared to a model combining two theories. One theory, developed by Jaffé, describes the variation of k s with the ionization density within the ion track (initial recombination) and the other theory, developed by Boag, describes the variation of k s with the dose rate (volume recombination). Excellent agreement is found between experimental and theoretical k s-values. All results confirm that k s cannot be neglected. The solution to minimise k s is to use the ionisation chamber at high voltage. However, one must be aware that charge multiplication may complicate the interpretation of the measurement. For the chamber tested, it was found that a voltage of 300 V can be used without further complication. As the initial recombination has a logarithmic variation as a function of 1/V, the two-voltage method is not applicable to these scanned beams.

  8. Medical effects and risks of exposure to ionising radiation.

    PubMed

    Mettler, Fred A

    2012-03-01

    Effects and risk from exposure to ionising radiation depend upon the absorbed dose, dose rate, quality of radiation, specifics of the tissue irradiated and other factors such as the age of the individual. Effects may be apparent almost immediately or may take decades to be manifest. Cancer is the most important stochastic effect at absorbed doses of less than 1 Gy. The risk of cancer induction varies widely across different tissues; however, the risk of fatal radiation-induced cancer for a general population following chronic exposure is about 5% Sv(-1). Quantification of cancer risk at doses of less than 0.1 Gy remains problematic. Hereditary risks from irradiation that might result in effects to offspring of humans appear to be much lower and any such potential risks can only be estimated from animal models. At high doses (over 1 Gy) cell killing and modification causes deterministic effects such as skin burns, and bone marrow depression, in which case immunosuppression becomes a critical issue. Acute whole body penetrating gamma irradiation at doses in excess of 2 Gy results in varying degrees of acute radiation sickness and doses over 10 Gy are usually lethal as a result of combined organ injury.

  9. Dosimetry of ionising radiation in modern radiation oncology

    NASA Astrophysics Data System (ADS)

    Kron, Tomas; Lehmann, Joerg; Greer, Peter B.

    2016-07-01

    Dosimetry of ionising radiation is a well-established and mature branch of physical sciences with many applications in medicine and biology. In particular radiotherapy relies on dosimetry for optimisation of cancer treatment and avoidance of severe toxicity for patients. Several novel developments in radiotherapy have introduced new challenges for dosimetry with small and dynamically changing radiation fields being central to many of these applications such as stereotactic ablative body radiotherapy and intensity modulated radiation therapy. There is also an increasing awareness of low doses given to structures not in the target region and the associated risk of secondary cancer induction. Here accurate dosimetry is important not only for treatment optimisation but also for the generation of data that can inform radiation protection approaches in the future. The article introduces some of the challenges and highlights the interdependence of dosimetric calculations and measurements. Dosimetric concepts are explored in the context of six application fields: reference dosimetry, small fields, low dose out of field, in vivo dosimetry, brachytherapy and auditing of radiotherapy practice. Recent developments of dosimeters that can be used for these purposes are discussed using spatial resolution and number of dimensions for measurement as sorting criteria. While dosimetry is ever evolving to address the needs of advancing applications of radiation in medicine two fundamental issues remain: the accuracy of the measurement from a scientific perspective and the importance to link the measurement to a clinically relevant question. This review aims to provide an update on both of these.

  10. ER stress induced by ionising radiation in IEC-6 cells.

    PubMed

    Zhang, Bo; Wang, Yan; Pang, Xueli; Su, Yongping; Ai, Guoping; Wang, Tao

    2010-06-01

    Ionising radiation (IR) can evoke a series of biochemical events inside the cell. However, whether IR can directly induce endoplasmic reticulum (ER) stress is not clear. In our previous study, we found that there might be a causative link between IR and ER stress. In this study, we further characterised the type of ER stress induced by IR. Rat intestinal epithelial cells IEC-6 were irradiated at a dose of 10 Gy, and total RNA and proteins were harvested at indicated time points. The mRNA and protein expression of immunoglobulin heavy chain binding protein (BiP) and glucose regulated protein 94 (GRP94) was detected along with proteins associated with ER stress signal pathways. Our results indicated that IR induced up-regulation of ER stress marker including BiP and GRP94 at protein and mRNA levels in IEC-6 cells. Increased phosphorylation of eukaryotic translation initiation factor 2 (eIF2alpha) and induced mRNA splicing of X-box binding protein 1 (XBP1) suggested that PERK (interferon-induced double-stranded RNA-activated protein kinase (PRKR) -like endoplasmic reticulum kinase) and IRE1 (inositol requirement 1) signal transduction pathways were involved in this kind of ER stress. However, the active form of activating transcription factor 6 (ATF6) did not change significantly in irradiated cells, which suggested that the ATF6 pathway was not involved. Thus, we concluded that IR could induce moderate ER stress directly in IEC-6 cells.

  11. Planar flow-by electrode capacitive electrospray ion source

    DOEpatents

    Van Berkel, Gary J.

    2004-01-13

    An electrospray ion source includes a chamber including a channel region therein, the channel including at least one inlet for directing a solution into the channel and at least a first and a second outlet for transmitting the solution or derivatives therefrom out from channel. Structure for separating ions in the solution is provided from separating the solution into at least a first and a second flow stream portion. The first flow stream portion is enriched in negative ions and the second flow stream portion is enriched in positive ions. The first flow stream portion is adapted to exit the chamber through the first outlet while the second flow stream portion is adapted to exit the chamber through the second outlet. A method of charge separation can include the step of simultaneously providing at least two gas phase ion stream portions having opposite polarity.

  12. Perspective on Electrospray Ionization and Its Relation to Electrochemistry

    NASA Astrophysics Data System (ADS)

    Pozniak, Boguslaw P.; Cole, Richard B.

    2015-03-01

    The phenomenon of electrospraying of liquids is presented from the perspective of the electrochemistry involved. Basics of current and liquid flow in the capillary and spray tip are discussed, followed by specifics of charging and discharging of the sprayed liquid surface. Fundamental theories and numerical modeling relating electrospray current to solution and spray parameters are described and then compared with our own experimentally obtained data. The method of mapping potentials and currents inside the electrospray capillary by using an inserted electrically-isolated small wire probe electrode is discussed in detail with illustrations from new and published data. Based on these experimentally obtained results, a new mathematical model is derived. The introduced "nonlinear resistor electrospray capillary model" divides the electrospray capillary into small sections, adds their contributions, and then, by transition to infinitely small section thickness, produces analytical formulas that relate current and potential maps to other properties of the electrospraying liquid: primarily conductivity and current density. The presentation of the model is undertaken from an elementary standpoint, and it offers the possibility to obtain quantitative information regarding operating parameters from typical analytical systems subjected to electrospray. The model stresses simplicity and ease of use; examples applying experimental data are shown and some predictions of the model are also presented. The developed nonlinear resistor electrospray capillary model is intended to provide a new quantitative basis for improving the understanding of electrochemical transformations occurring in the electrospray emitter. A supplemental material section gives full derivation of the model and discusses other consequences.

  13. Vacuum electrospray of volatile liquids assisted by infrared laser irradiation.

    PubMed

    Ninomiya, Satoshi; Chen, Lee Chuin; Suzuki, Hiroaki; Sakai, Yuji; Hiraoka, Kenzo

    2012-04-15

    Current large cluster sources such as C(60) or argon utilize gas-phase sources which are of low-brightness and cannot be focused efficiently to better than 1 micron diameter spot size. The development of a high-brightness large cluster ion source is of critical importance to achieve high resolution in secondary ion mass spectrometry (SIMS) imaging of organics. We propose a new high-brightness large cluster ion source, and a technique for producing a stable electrospray of volatile liquids under vacuum. It is known that vacuum electrospray of volatile liquids such as water is extremely difficult because of freezing of the liquids introduced in vacuum by evaporative cooling. To avoid freezing, the tip of the electrospray emitter was irradiated by a continuous wave infrared laser. Without continuous laser irradiation the vacuum electrospray of a water/methanol solution was unstable with respect to the shapes of the Taylor cone and current, whereas continuous laser irradiation produced a stable electrospray of water. The typical modes of electrospray were clearly observed with an optical microscope even under vacuum conditions. A stable vacuum electrospray could be achieved by improving the vacuum pressure to suppress electric discharge and by using the laser to maintain the liquid state. This is the first description of the production of a stable vacuum electrospray of volatile liquids such as water. This vacuum electrospray technique can be expected to produce a novel high-brightness large cluster ion beam source. Copyright © 2012 John Wiley & Sons, Ltd.

  14. Mass spectrometric detection of trace anions: The evolution of paired-ion electrospray ionization (PIESI).

    PubMed

    Breitbach, Zachary S; Berthod, Alain; Huang, Ke; Armstrong, Daniel W

    2016-01-01

    The negative-ion mode of electrospray ionization mass spectrometry (ESI-MS) is intrinsically less sensitive than the positive-ion mode. The detection and quantitation of anions can be performed in positive-ion mode by forming specific ion-pairs during the electrospray process. The paired-ion electrospray ionization (PIESI) method uses specially synthesized multifunctional cations to form positively charged adducts with the anions to be analyzed. The adducts are detected in the positive-ion mode and at higher m/z ratios to produce excellent signal-to-noise ratios and limits of detection that often are orders of magnitude better than those obtained with native anions in the negative-ion mode. This review briefly summarizes the different analytical approaches to detect and separate anions. It focuses on the recently introduced PIESI method to present the most effective dicationic, tricationic, and tetracationic reagents for the detection of singly and multiply charged anions and some zwitterions. The mechanism by which specific structural molecular architectures can have profound effects on signal intensities is also addressed.

  15. Transport and Deposition of Electrosprayed Nanoparticles

    NASA Astrophysics Data System (ADS)

    Brown, Nicholas; Chiarot, Paul

    2015-11-01

    In an electrospray, high electric potentials are utilized to generate a fine aerosol of a conductive solvent. For this study, the solvent consisted of nanoparticles dispersed in alcohol. The nanoparticle suspensions act as printable nanoparticle inks. In this process, a glass capillary tube is held as a high electric potential relative to a grounded reference plate located below the tip. Droplets are ejected from the tube and are directed towards the ground plate. If the solvent is sufficiently volatile, it will rapidly evaporate while the droplets are in flight (due to the high surface area to volume ratio) leaving behind dry, highly charged nanoparticles. The droplets/nanoparticles are deposited onto a target substrate that is place onto the grounded plate. The transport of any individual droplet/nanoparticle from the emitter tip to the target substrate is a stochastic process. This transport can be modeled using a Monte Carlo simulation. The probability of an individual particle being deposited at a given location on the target substrate is directly related to the electric potential at that location. In other words, the probability function that determines the deposition is directly related to the electric potential at the substrate. The total potential is comprised of the applied electric potential required to generate the electrospray, the induced charge on the surface of the target dielectric, and the charge on the individual particles themselves. We report on the structure of droplet/nanoparticle deposits printed using electrospray. The evolution of the deposit is investigated over time using experimental studies and Monte Carlo simulations. The deposit structure passes through four distinct regimes that are characterized by repeatable bulk features.

  16. Excitation and Ionisation dynamics in high-frequency plasmas

    NASA Astrophysics Data System (ADS)

    O'Connell, D.

    2008-07-01

    Non-thermal low temperature plasmas are widely used for technological applications. Increased demands on plasma technology have resulted in the development of various discharge concepts based on different power coupling mechanisms. Despite this, power dissipation mechanisms in these discharges are not yet fully understood. Of particular interest are low pressure radio-frequency (rf) discharges. The limited understanding of these discharges is predominantly due to the complexity of the underlying mechanisms and difficult diagnostic access to important parameters. Optical measurements are a powerful diagnostic tool offering high spatial and temporal resolution. Optical emission spectroscopy (OES) provides non-intrusive access, to the physics of the plasma, with comparatively simple experimental requirements. Improved advances in technology and modern diagnostics now allow deeper insight into fundamental mechanisms. In low pressure rf discharges insight into the electron dynamics within the rf cycle can yield vital information. This requires high temporal resolution on a nano-second time scale. The optical emission from rf discharges exhibits temporal variations within the rf cycle. These variations are particularly strong, in for example capacitively coupled plasmas (CCPs), but also easily observable in inductively coupled plasmas (ICPs), and can be exploited for insight into power dissipation. Interesting kinetic and non-linear coupling effects are revealed in capacitive systems. The electron dynamics exhibits a complex spatio-temporal structure. Excitation and ionisation, and, therefore, plasma sustainment is dominated through directed energetic electrons created through the dynamics of the plasma boundary sheath. In the relatively simple case of an asymmetric capacitively coupled rf plasma the complexity of the power dissipation is exposed and various mode transitions can be clearly observed and investigated. At higher pressure secondary electrons dominate the

  17. The electrospray: Fundamentals and combustion applications

    NASA Technical Reports Server (NTRS)

    Gomez, Alessandro

    1993-01-01

    Liquid fuel dispersion in practical systems is typically achieved by spraying the fuel into a polydisperse distribution of droplets evaporating and burning in a turbulent gaseous environment. In view of the nearly unsurmountable difficulties of this two-phase flow, it would be useful to use an experimental arrangement that allow a systematic study of spray evolution and burning in configurations of gradually increasing levels of complexity, starting from laminar sprays to fully turbulent ones. An Electrostatic Spray (ES) of charged droplets lends itself to this type of combustion experiments under well-defined conditions and can be used to synthesize gradually more complex spray environments. In its simplest configuration, a liquid is fed into a small metal tube maintained at several kilovolts relative to a ground electrode few centimeters away. Under the action of the electric field, the liquid meniscus at the outlet of the capillary takes a conical shape, with a thin jet emerging from the cone tip. This jet breaks up farther downstream into a fine spray of charged droplets. Several advantages distinguish the electrospray from alternative atomization techniques: the self-dispersion property of the spray due to coulombic repulsion; the absence of droplet coalescence; the potential control of the trajectories of charged droplets by suitable disposition of electrostatic fields; and the decoupling of atomization, which is strictly electrostatic, from gas flow processes. Furthermore, as recently shown in our laboratory, the electrospray can produce quasi-monodisperse droplets over a very broad size range (1-100 microns). The ultimate objective of this research project is to study the formation and burning of electrosprays of liquid fuels first in laminar regimes and then in turbulent ones. Combustion will eventually be investigated in conditions of three-dimensional droplet-droplet interaction, for which experimental studies have been limited to either qualitative

  18. Simultaneous radar and video meteors—II: Photometry and ionisation

    NASA Astrophysics Data System (ADS)

    Weryk, Robert J.; Brown, Peter G.

    2013-06-01

    Simultaneous radar and video measurements of meteors were made using the Canadian Meteor Orbit Radar (CMOR) and several Gen-III image-intensified CCD cameras primarily to relate radar meteor electron line density, q, to video meteor photon radiant power, I. We find that log10q=log10I+(12.56±0.49) leading to M=(38.7±1.2)-2.5log10q, where M is the meteor magnitude in the Gen-III video bandpass (470-850 nm) corresponding to q at the radar specular point. The ratio of the ionisation coefficient to luminous efficiency, β/τI, was estimated from our observations of q/I to functionally depend on speed and radiant power. For our average meteor photon radiant power of I=64W, we find log10β/τI=(3.00±0.62)log10v-(4.27±1.37). By adopting β computed according to Jones (1997), which we approximate as log10β=5.84-0.09v0.5-9.56/log10v (roughly proportional to v4 between 20 and 40 km/s), a corresponding estimate of τI for our intensified spectral bandpass was made using our measurements of q/I. We find a peak bolometric value of τI=5.9% at 41 km/s. The main uncertainties associated with our analysis are the unknown spectra of individual meteors which affect our estimate of absolute radiant power, and uncertain values of the initial trail radius which makes estimates of q problematic. Our results suggest that the video meteor mass scale is an order of magnitude smaller than previously thought at these higher speeds, and implies that the total meteoroid mass influx between 10-5 and 10-8kg is lower than previous studies would suggest.

  19. A novel method for bacterial inactivation using electrosprayed water nanostructures

    NASA Astrophysics Data System (ADS)

    Pyrgiotakis, Georgios; McDevitt, James; Yamauchi, Toshiyuki; Demokritou, Philip

    2012-08-01

    This is a study focusing on the potential to deactivate biological agents (bacteria and endospores) using engineered water nanostructures (EWNS). The EWNS were generated using an electrospray device that collects water by condensing atmospheric water vapor on a Peltier-cooled electrode. A high voltage is applied between the collection electrode and a grounded electrode resulting in aerosolization of the condensed water and a constant generation of EWNS. Gram-negative Serratia marcescens, gram-positive Staphylococcus aureus, and Bacillus atrophaeus endospores were placed on stainless steel coupons and exposed to generated EWNS at multiple time intervals. Upon exposures, the bacteria were recovered and placed on nutrient agar to grow, and the colony forming units were counted. Ozone levels as well as air temperature and relative humidity were monitored during the experiments. Qualitative confirmation of bacterial destruction was also obtained by transmission electron microscopy. In addition, important EWNS aerosol properties such as particle number concentration as a function of size as well as the average surface charge of the generated EWNS were measured using real-time instrumentation. It was shown that the novel electrospray method can generate over time a constant flux of EWNS. EWNS have a peak number concentration of 8,000 particles per cubic centimeter with a modal peak size around 20 nm. The average surface charge of the generated EWNS was found to be 10 ± 2 electrons per particle. In addition, it was shown that the EWNS have the potential to deactivate both bacteria types from surfaces. At the same administrate dose, however, the endospores were not inactivated. This novel method and the unique properties of the generated EWNS could potentially be used to develop an effective, environmentally friendly, and inexpensive method for bacteria inactivation.

  20. Development of a new ionisation chamber, for HP(10) measurement, using Monte-Carlo simulation and experimental methods.

    PubMed

    Silva, H; Cardoso, J; Oliveira, C

    2011-03-01

    An ionisation chamber that directly measures the quantity personal dose equivalent, H(p)(10), is used as a secondary standard in some metrology laboratories. An ionisation chamber of this type was first developed by Ankerhold. Using the Monte-Carlo simulation, the dose in the sensitive volume as a function of the IC dimensions and the effects of the several components of the ionising chamber have been investigated. Based on these results, a new ionising chamber, lighter than the previous ones, is constructed and experimentally tested.

  1. Laser diagnostics of an evaporating electrospray

    NASA Astrophysics Data System (ADS)

    Yi, Tongxun

    2014-01-01

    An electrospray atomizer generates monodisperse, dilute sprays when working in the cone-jet mode. Evolution of an electrospray with droplet diameter below 10 μm is studied with phase Doppler particle analyzer (PDPA) and the exciplex-PLIF technique. The evaporation rate constant is determined from droplet velocity and diameter measured with a PDPA and is found to sharply increase with the velocity slip and the coflow temperature. Fluorescence around 400 nm, usually referred to as TMPD fluorescence, is calibrated with a heated, laminar, coflow vapor jet diluted with nitrogen. The TMPD fluorescence yield nonlinearly increases with temperature up to 538 K and then declines. Single-shot images show that fluorescence around 400 nm is mainly generated from TMPD vapor and that from droplets can be neglected as a first analysis; however, fluorescence around 490 nm, usually referred to as exciplex fluorescence, is generated from both droplets and fuel vapor immediately around droplets. Exciplex fluorescence is correlated with PDPA measurements and TMPD fluorescence. Effects of temperature, fuel composition, overlap of fluorescent spectra, and chemical equilibrium for exciplex formation are discussed. Technical challenges for quantitative exciplex-PLIF measurements are highlighted.

  2. 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

  3. Some thoughts on electrospray ionization mechanisms.

    PubMed

    Crotti, Sara; Seraglia, Roberta; Traldi, Pietro

    2011-01-01

    Electrospray ionization (ESI) mechanisms are highly complex, due to a series of physical and chemical phenomena taking place on a complex system, as a solution is. In fact, even if the solution of an analyte in a protic medium can be considered at first sight to be a two-component system, the presence of solvent dissociation equilibria and the possible interactions solvent-solvent dissociation products, solvent dissociation products-analyte make this system highly complex, also for the presence of possible ionic compounds (for example, Na(+), K(+)) which strongly affect the above equilibria. A high number of research articles have been published, mainly devoted to charged droplet production and to gas-phase ion generation. They all show the high complexity of the processes affecting electrospray measurements related to either the chemical equilibria present in the condensed phase and to electrolysis processes at the emitter tip or to the processes occurring in the sprayed droplets. As a result, the chemical composition inside the small droplets from which the analyte ions are generated can be significantly different from those in sprayed solution. In this review, after a short survey of the proposed ESI mechanisms, some experiments are described. They were performed to examine if ion mobility in solution, before the formation of the sprayed charged droplets, can affect the ESI results. The data, obtained by studying both inorganic and organic analytes, indicate that the ESI spectra are dependent on the analyte dimension and charge state which, as a consequence, affect their ion mobility in solution.

  4. Salt Tolerance of Desorption Electrospray Ionization (DESI)

    SciTech Connect

    Jackson, Ayanna U.; Talaty, Nari; Cooks, R G; Van Berkel, Gary J

    2007-01-01

    Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.

  5. Coaxial electrospray of microparticles and nanoparticles for biomedical applications

    PubMed Central

    Zhang, Leilei; Huang, Jiwei; Si, Ting; Xu, Ronald X

    2013-01-01

    Coaxial electrospray is an electrohydrodynamic process that produces multilayer microparticles and nanoparticles by introducing coaxial electrified jets. In comparison with other microencapsulation/nanoencapsulation processes, coaxial electrospray has several potential advantages such as high encapsulation efficiency, effective protection of bioactivity and uniform size distribution. However, process control in coaxial electrospray is challenged by the multiphysical nature of the process and the complex interplay of multiple design, process and material parameters. This paper reviews the previous works and the recent advances in design, modeling and control of a coaxial electrospray process. The review intends to provide general guidance for coaxial electrospray and stimulate further research and development interests in this promising microencapsulation/nanoencapsulation process. PMID:23249155

  6. Coaxial electrospray of microparticles and nanoparticles for biomedical applications.

    PubMed

    Zhang, Leilei; Huang, Jiwei; Si, Ting; Xu, Ronald X

    2012-11-01

    Coaxial electrospray is an electrohydrodynamic process that produces multilayer microparticles and nanoparticles by introducing coaxial electrified jets. In comparison with other microencapsulation/nanoencapsulation processes, coaxial electrospray has several potential advantages such as high encapsulation efficiency, effective protection of bioactivity and uniform size distribution. However, process control in coaxial electrospray is challenged by the multiphysical nature of the process and the complex interplay of multiple design, process and material parameters. This paper reviews the previous works and the recent advances in design, modeling and control of a coaxial electrospray process. The review intends to provide general guidance for coaxial electrospray and stimulate further research and development interests in this promising microencapsulation/nanoencapsulation process.

  7. Surface ionisation of molecular H2 and atomic H Rydberg states at doped silicon surfaces

    NASA Astrophysics Data System (ADS)

    Sashikesh, G.; So, E.; Ford, M. S.; Softley, T. P.

    2014-09-01

    The detection of ions or electrons from the surface ionisation of molecular H2 and atomic H Rydberg states incident at doped Si surfaces is investigated experimentally to analyse the effect of the dopant charge distribution on the surface-ionisation processes. In both experimental studies, the molecular H2 and atomic H Rydberg states are generated via two-colour vacuum ultraviolet--ultraviolet (VUV-UV) resonant excitation. For H2, various Stark states of the N+ = 2, n = 17 manifold are populated in the presence of an electric field. The variation of the observed surface-ionisation signal with surface dopant concentration and type, shows similar characteristics for all the Stark states. A comparison is made between these ion-detected surface-ionisation profiles and those obtained via electron detection. Different trends as a function of dopant concentration and type are observed for the two cases, explained by the greater effect of surface charges on the post-ionisation ion trajectory compared to the electron trajectory. For the atomic-H Rydberg states with principal quantum number ? populated in the absence of a Stark field, the observed behaviour is similar to the interaction of molecular H2 Rydberg states at the same surfaces, and these measurements confirm that the observed effects are attributable to the nature of the target surface rather than the specific atomic or molecular Rydberg species.

  8. Total ionisation cross sections for chlorofluoromethanes and CClx radicals by electron impact

    NASA Astrophysics Data System (ADS)

    Gupta, Dhanoj; Antony, Bobby

    2014-07-01

    We report here the total ionisation cross section for chlorofluoromethanes, namely CCl3F (Freon 11), CCl2F2 (Freon 12), CClF3 (Freon 13), CHCl2F (Freon 21), CHClF2 (Freon 22), CH2ClF (Freon 31), CCl4 and CClx (x = 1-3), radicals by electron impact from ionisation threshold to 2 keV. The total inelastic cross section is obtained employing a complex optical potential formalism and solving the Schrödinger equation through partial wave analysis. Using the complex scattering potential-ionisation contribution method, the total ionisation cross section is derived from the inelastic cross section for these targets. The results obtained are then compared with the existing experimental and theoretical data, wherever available. The present result shows reasonable agreement with previous data. For the CClx radicals, the ionisation cross section is predicted for the first time. The data reported here have immense interest to atmospheric and technological plasma modelling.

  9. Ionising irradiation alters the dynamics of human long interspersed nuclear elements 1 (LINE1) retrotransposon.

    PubMed

    Tanaka, Atsushi; Nakatani, Youko; Hamada, Nobuyuki; Jinno-Oue, Atsushi; Shimizu, Nobuaki; Wada, Seiichi; Funayama, Tomoo; Mori, Takahisa; Islam, Salequl; Hoque, Sheikh Ariful; Shinagawa, Masahiko; Ohtsuki, Takahiro; Kobayashi, Yasuhiko; Hoshino, Hiroo

    2012-09-01

    It is important to identify the mechanism by which ionising irradiation induces various genomic alterations in the progeny of surviving cells. Ionising irradiation activates mobile elements like retrotransposons, although the mechanism of its phenomena consisting of transcriptions and insertions of the products into new sites of the genome remains unclear. In this study, we analysed the effects of sparsely ionising X-rays and densely ionising carbon-ion beams on the activities of a family of active retrotransposons, long interspersed nuclear elements 1 (L1). We used the L1/reporter knock-in human glioma cell line, NP-2/L1RP-enhanced GFP (EGFP), that harbours full-length L1 tagged with EGFP retrotransposition detection cassette (L1RP-EGFP) in the chromosomal DNA. X-rays and carbon-ion beams similarly increased frequencies the transcription from L1RP-EGFP and its retrotransposition. Short-sized de novo L1RP-EGFP insertions with 5'-truncation were induced by X-rays, while full-length or long-sized insertions (>5 kb, containing ORF1 and ORF2) were found only in cell clones irradiated by the carbon-ion beams. These data suggest that X-rays and carbon-ion beams induce different length of de novo L1 insertions, respectively. Our findings thus highlight the necessity to investigate the mechanisms of mutations caused by transposable elements by ionising irradiation.

  10. Preliminary investigation of the application of on-line membrane extraction of trifluoroacetic acid as an aid to improvement of negative ion electrospray mass spectrometry data.

    PubMed

    New, A P; Wolff, J C; Crabtree, S; Freitas do Santos, L; Okafo, G; Lee, J; Divan, K

    2001-04-13

    We have recently investigated the biodegradation of a number of acidic aromatic compounds that give excellent chromatography using trifluoroacetic acid (TFA) based HPLC methods. Unfortunately HPLC methods using TFA are not usually compatible with detection by negative ion mass spectrometry as TFA suppresses ionisation of the analyte during the electrospray process. We present a preliminary investigation of the use of an anion-exchange micro-membrane suppressor to remove TFA on-line post column with the aim of improvement of mass spectral data using an aromatic acid as an example, Thus LC-MS using a TFA based HPLC method with negative ion mass spectral detection is shown to be possible with good sensitivity.

  11. A new cluster-ion-beam source for secondary ion mass spectrometry (SIMS) using the electrospray of a pure ionic liquid under high vacuum

    NASA Astrophysics Data System (ADS)

    Fujiwara, Yukio; Saito, Naoaki; Nonaka, Hidehiko; Nakanaga, Taisuke; Ichimura, Shingo

    2010-06-01

    Electrospray characteristics were studied using a pure room-temperature molten salt (i.e., an ionic liquid) at pressures around 10 -5 Pa as well as at atmospheric pressure. The ionic liquid N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide was tested, which has negligible vapor pressure and high conductivity. During electrospray, the ionic liquid was introduced at a constant flow rate into a stainless-steel capillary (i.d. 30 μm). It was demonstrated that stable electrosprayed currents exceeding ±1 μΑ were continuously produced in both positive and negative modes. The electrosprayed currents in a high vacuum were twice those at atmospheric pressure. It was found that gas pressure rose slightly with increasing electrosprayed currents. Residual gas analysis revealed that gas component at negative mode was different from that at positive mode. Experimental results indicate that vacuum electrospray of pure ionic liquids is applicable to a massive-cluster beam source for SIMS.

  12. Impact ionisation mass spectrometry of polypyrrole-coated pyrrhotite microparticles

    NASA Astrophysics Data System (ADS)

    Hillier, Jon K.; Sternovsky, Zoltan; Armes, Steven P.; Fielding, Lee A.; Postberg, Frank; Bugiel, Sebastian; Drake, Keith; Srama, Ralf; Kearsley, Anton T.; Trieloff, Mario

    2014-07-01

    Cation and anion impact ionization mass spectra of polypyrrole-coated pyrrhotite cosmic dust analogue particles are analysed over a range of cosmically relevant impact speeds. Spectra with mass resolutions of 150-300 were generated by hypervelocity impacts of charged particles, accelerated to up to 37 km s-1 in a Van de Graaff electrostatic accelerator, onto a silver target plate in the Large Area Mass Analyzer (LAMA) spectrometer. Ions clearly indicative of the polypyrrole overlayer are identified at masses of 93, 105, 117, 128 and 141 u. Organic species, predominantly derived from the thin (20 nm) polypyrrole layer on the surface of the particles, dominate the anion spectra even at high (>20 km s-1) impact velocities and contribute significantly to the cation spectra at velocities lower than this. Atomic species from the pyrrhotite core (Fe and S) are visible in all spectra at impact velocities above 6 km s-1 for 56Fe+, 9 km s-1 for 32S+ and 16 km s-1 for 32S- ions. Species from the pyrrhotite core are also frequently visible in cation spectra at impact speeds at which surface ionisation is believed to dominate (<10 km s-1), although the large number of organic peaks complicates the identification of characteristic molecular species. A thin oxidised surface layer on the pyrrhotite particles is indicated by weak spectral features assigned to iron oxides and iron oxy-hydroxides, although the definitive identification of sulfates and hydrated sulfates from the oxidation process was not possible. Silver was confirmed as an excellent choice for the target plate of an impact ionization mass spectrometer, as it provided a unique isotope signature for many target-projectile cluster peaks at masses above 107-109 u. The affinity of Ag towards a dominant organic fragment ion (CN-) derived from fragmentation of the polypyrrole component led to molecular cluster formation. This resulted in an enhanced sensitivity to a particular particle component, which may be of great use

  13. Simulation studies on a prototype ionisation chamber for measurement of personal dose equivalent, Hp(10).

    PubMed

    Cardoso, J; Carvalho, A F; Oliveira, C

    2007-01-01

    A prototype ionisation chamber for direct measurement of the personal dose equivalent, Hp(10), similar to the one developed by the Physikalisch-Technische Bundesantalt (PTB), was designed and constructed by the Metrological Laboratory of Ionizing Radiation (LMRI) of Nuclear and Technological Institute (ITN). Tests already performed have shown that the behaviour of this chamber is very similar to the PTB chamber, mainly the energy dependence for the X-ray radiation qualities of the ISO 4037-1 narrow series N-30, N-40, N-60, N-80, N-100 and N-120 and also for gamma radiation of 137Cs and 60Co. However, the results obtained also show a dependence on the energy and angles of incident radiation and a low magnitude of the electrical response of the ionisation chamber. In order to optimise the performance of the chamber, the LMRI initiated numerical simulation of this ionisation chamber by Monte Carlo method using the MCNPX code.

  14. Compound coverage enhancement of electrospray ionization mass spectrometry through the addition of a homemade needle.

    PubMed

    Xiao, Shun; Qian, Shuai; Wang, Yi; Zhang, Yufeng; Cheng, Yiyu

    2013-03-21

    The response of many previously low-detectable or undetectable compounds in electrospray ionization mass spectrometry (ESI-MS) has been enhanced by the addition of a simple, homemade needle into the traditional ESI interface. The needle located between the ESI emitter and the ion sweep cone (inlet of the detector) would ionize those neutral gaseous compounds, formed during electrospray, by a corona discharge process. The mobile phases, ESI parameters and positions of the needle were investigated and optimized. Several groups of compounds and herbal extracts were tested using the homemade set-up. Both the results of the flow injection and the hyphenated MS analyses showed significant enhancement effects of our homemade needle. The advantages of the proposed method include low cost, simplicity and practicality.

  15. Determination of macrolide antibiotics in chicken tissues by liquid chromatography-electrospray mass spectrometry

    NASA Astrophysics Data System (ADS)

    Salikin, Jamilah; Abdullah, Aminah

    2013-11-01

    A methodusingliquid chromatography-electrospray mass spectrometry (LC-(ESI)MS) for the simultaneous determination of three macrolides (tylosin, spiramycin and tilmicosin) in poultry muscle has been developed. The drugs were extracted with EDTA McIlvaine buffer, filter through celite 545 and the extracts were cleaned up by SPE Oasis HLB cartridge. Separation was carried out in end-capped silica-based C18 column and mobile phases containing trifluoroacetic acid-acetonitrile with a binary gradient system at a flow rate 0.5 ml/min. Detection was performed by single mass spectrometry with electrospray ionization in the positive mode. Several parameters affecting the mass spectra were studied. Chicken samples from the market were analyzed to check the residue of macrolide antibiotics.

  16. Structural characterization of secoiridoid glycosides by high-performance liquid chromatography/electrospray ionization mass spectrometry.

    PubMed

    Wang, Shufang; Xu, Yimin; Chen, Pinghong; Zhang, Yufeng

    2014-07-30

    The fragmentation behavior of seven secoiridoid glycosides (SIGs) isolated from Gentiana triflora Pall., a traditional Chinese medicine, was investigated by electrospray ionization ion trap mass spectrometry (ESI-IT-MS). Multistage electrospray ionization mass spectrometry (ESI-MS(n)) experiments both in positive- and negative-ion mode were used to elucidate the main fragmentation pathways of these compounds. In full scan mass spectra, different deprotonated or protonated molecules were observed for compounds with different basic structure. Ring cleavages of the aglycon moiety were observed in MS(2) spectra and the characteristic ions provided valuable information on the basic structural skeletons. Their fragmentation pathways and fragment ion structures were proposed. The established fragmentation patterns have been successfully used to identify eleven SIGs in the extract of Gentiana triflora Pall. Copyright © 2014 John Wiley & Sons, Ltd.

  17. System and method for liquid extraction electrospray-assisted sample transfer to solution for chemical analysis

    DOEpatents

    Kertesz, Vilmos; Van Berkel, Gary J.

    2016-07-12

    A system for sampling a surface includes a surface sampling probe comprising a solvent liquid supply conduit and a distal end, and a sample collector for suspending a sample collection liquid adjacent to the distal end of the probe. A first electrode provides a first voltage to solvent liquid at the distal end of the probe. The first voltage produces a field sufficient to generate electrospray plume at the distal end of the probe. A second electrode provides a second voltage and is positioned to produce a plume-directing field sufficient to direct the electrospray droplets and ions to the suspended sample collection liquid. The second voltage is less than the first voltage in absolute value. A voltage supply system supplies the voltages to the first electrode and the second electrode. The first electrode can apply the first voltage directly to the solvent liquid. A method for sampling for a surface is also disclosed.

  18. Multiresidue analysis of seven anticoagulant rodenticides by high-performance liquid chromatography/electrospray/mass spectrometry.

    PubMed

    Marek, LeEtta J; Koskinen, William C

    2007-02-07

    Mice and rat populations are commonly controlled by two classes of rodenticide anticoagulants, coumarins and indandiones. However, poisoning of nontarget animals also often occurs. For cases such as these, a rapid, multiresidue method, which provides positive confirmation for both classes of anticoagulant rodenticides, is needed by diagnostic laboratories. A method was developed for the determination of seven anticoagulant rodenticides, coumafuryl, pindone, warfarin, diphacinone, chlorophacinone, bromadiolone, and brodifacoum, in diverse matrices, animal feed, cooked beef, and fruit-flavored beverages using high-performance liquid chromatography/electrospray/mass spectrometry. Detection was by MS/MS with electrospray ionization in negative mode. Confirmation was by retention time, m/z of molecular ion, and two parent-daughter transitions. Recoveries from selected the matrices ranged from 61 to 117%. Limits of quantitation were as low as 1.5-4.5 ng g-1. The developed method was rapid and provided the simultaneous confirmation and quantification of the seven anticoagulant rodenticides.

  19. Electrospray mass spectral fragmentation study of N,N'-disubstituted imidazolium ionic liquids.

    PubMed

    Lesimple, Alain; Mamer, Orval; Miao, Weishi; Chan, Tak Hang

    2006-01-01

    The tandem positive electrospray mass spectrometry (ESMS(n)) fragmentation of ionic liquids incorporating the 1-methyl-imidazolium ring substituted on N(II) with an alkyl chain functionalized with an alcohol, carboxylic acid, or an iodobenzyl or iodobenzoyl ester is presented for the first time. The influence of chain length and function is studied. Esterified structures led to intense CID fragments lacking the imidazolium ring allowing full characterization of the ester moiety. Fragment ion compositions for this interesting and newly important class of compounds are established through accurate mass data and deuterium labeling. The presence of the cationic ring system produces intense even electron molecular cations in electrospray that undergo multiple stages of CID to yield fragments which often are radical cations. Unusual losses of methyl and hydrogen radicals are frequently noted.

  20. The ionisation energy of cyclopentadienone: a photoelectron-photoion coincidence study

    NASA Astrophysics Data System (ADS)

    Ormond, Thomas K.; Hemberger, Patrick; Troy, Tyler P.; Ahmed, Musahid; Stanton, John F.; Ellison, G. Barney

    2015-08-01

    Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck-Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is ? 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

  1. Neutral and ionised gas around the post-red supergiant IRC +10 420 at AU size scales

    NASA Astrophysics Data System (ADS)

    Oudmaijer, R. D.; de Wit, W. J.

    2013-03-01

    Context. IRC +10 420 is one of the few known massive stars in rapid transition from the red supergiant phase to the Wolf-Rayet or luminous blue variable phase. Aims: The star has an ionised wind and using the Brγ line we assess the mass-loss on spatial scales of ~1 AU. Methods: We present new VLT Interferometer AMBER data which are combined with all other AMBER data present in the literature. The final dataset covers a position angle range of ~180° and baselines up to 110 m. The spectrally dispersed visibilities, differential phases and line flux are conjointly analysed and modelled. We also present the first AMBER/FINITO observations which cover a larger wavelength range and allow us to observe the Na i doublet at 2.2 μm. The data are complemented by X-Shooter data, which provide a higher spectral resolution view. Results: The Brγ emission line and the Na i doublet are both spatially resolved. After correcting the AMBER data for the fact that the lines are not spectrally resolved, we find that Brγ traces a ring with a diameter of 4.18 mas, in agreement with higher spectral resolution data. We consider a geometric model in which the Brγ emission emerges from the top and bottom rings of an hour-glass shaped structure, viewed almost pole-on. It provides satisfactory fits to most visibilities and differential phases. The fact that we detect line emission from a neutral metal like Na i within the ionised region, a very unusual occurrence, suggests the presence of a dense pseudo-photosphere. Conclusions: The ionised wind can be reproduced with a polar wind, which could well have the shape of an hour-glass. Closer in, the resolved Na i emission is found to occur on scales barely larger than the continuum. This fact and that many yellow hypergiants exhibit this comparatively rare emission hints at the presence of a "Yellow" or even "White Wall" in the Hertzsprung-Russell diagram, preventing them from visibly evolving to the blue. Based on observations at ESO, and in

  2. Dynamics of ionisation and entanglement in the 'atom + quantum electromagnetic field' system

    SciTech Connect

    Sharapova, P R; Tikhonova, O V

    2012-03-31

    The dynamics of a model Rydberg atom in a strong nonclassical electromagnetic field is investigated. The field-induced transitions to the continuum involving different numbers of photons (with intermediate states in the discrete spectrum) are taken into account and the specific features of ionisation in 'squeezed' field states are considered in comparison with the case of classical light. A significant decrease in the ionisation rate is found, which is caused by the interference stabilisation of the atomic system. The entanglement of the atomic and field subsystems, the temporal dynamics of the correlations found, and the possibility of measuring them are analysed.

  3. Molybdic acid ionisation under hydrothermal conditions to 300 °C

    NASA Astrophysics Data System (ADS)

    Minubayeva, Z.; Seward, T. M.

    2010-08-01

    This UV spectrophotometric study was aimed at providing precise, experimentally derived thermodynamic data for the ionisation of molybdic acid (H 2MoO 4) from 30 to 300 °C and at equilibrium saturated vapour pressures. The determination of the equilibrium constants and associated thermodynamic parameters were facilitated by spectrophotometric measurements using a specially designed high temperature optical Ti-Pd flow-through cell with silica glass windows. The following van't Hoff isochore equations describe the temperature dependence of the first and second ionisation constants of molybdic acid up to 300 °C:

  4. A micro-gap, air-filled ionisation chamber as a detector for criticality accident dosimetry.

    PubMed

    Murawski, Ł; Zielczyński, M; Golnik, N; Gryziński, M A

    2014-10-01

    A micro-gap air-filled ionisation chamber was designed for criticality dosimetry. The special feature of the chamber is its very small gap between electrodes of only 0.3 mm. This prevents ion recombination at high dose rates and minimises the influence of gas on secondary particles spectrum. The electrodes are made of polypropylene because of higher content of hydrogen in this material, when compared with soft tissue. The difference between neutron and gamma sensitivity in such chamber becomes practically negligible. The chamber's envelope contains two specially connected capacitors, one for polarising the electrodes and the other for collecting the ionisation charge.

  5. Nanoparticle preparation of Mefenamic acid by electrospray drying

    SciTech Connect

    Zolkepali, Nurul Karimah Bakar, Noor Fitrah Abu Anuar, Nornizar; Naim, M. Nazli; Bakar, Mohd Rushdi Abu

    2014-02-24

    Nanoparticles preparation of Mefenamic acid (MA) by using an electrospray drying method was conducted in this study. Electrospray drying is a process that uses electrostatic force to disperse a conductive liquid stream into fine charged droplets through the coulomb fission of charges in the liquid and finally dry into fine particles. Electrospray drying modes operation usually in Taylor cone jet, and it was formed by controlling applied voltage and liquid flow rate. A conductive liquid (2.77–8.55μScm{sup −1}) which is MA solution was prepared by using acetone with concentration 0.041 and 0.055 M before pumping at a flow rate of 3–6ml/h. By applying the applied voltage at 1.3–1.5 kV, Taylor cone jet mode was formed prior to the electrospray. During electrospray drying process, solvent evaporation from the droplet was occurring that leads to coulomb disruption and may generate to nanoparticles. The dried nanoparticles were collected on a grounded substrate that was placed at varying distance from the electrospray. MA particle with size range of 100–400 nm were produced by electrospray drying process. Characterization of particles by using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) show that particles formed into polymorph I.

  6. Electrospray and tandem mass spectrometry in biochemistry.

    PubMed Central

    Griffiths, W J; Jonsson, A P; Liu, S; Rai, D K; Wang, Y

    2001-01-01

    Over the last 20 years, biological MS has changed out of all recognition. This is primarily due to the development in the 1980s of 'soft ionization' methods that permit the ionization and vaporization of large, polar, and thermally labile biomolecules. These developments in ionization mode have driven the design and manufacture of smaller and cheaper mass analysers, making the mass spectrometer a routine instrument in the biochemistry laboratory today. In the present review the revolutionary 'soft ionization' methods will be discussed with particular reference to electrospray. The mass analysis of ions will be described, and the concept of tandem MS introduced. Where appropriate, examples of the application of MS in biochemistry will be provided. Although the present review will concentrate on the MS of peptides/proteins and lipids, all classes of biomolecules can be analysed, and much excellent work has been done in the fields of carbohydrate and nucleic acid biochemistry. PMID:11311115

  7. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, R.D.; Udseth, H.R.; Olivares, J.A.

    1994-10-18

    A system and method for analyzing molecular constituents of a composition sample include: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g.,{+-}2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit. 21 figs.

  8. Electrospray and tandem mass spectrometry in biochemistry.

    PubMed

    Griffiths, W J; Jonsson, A P; Liu, S; Rai, D K; Wang, Y

    2001-05-01

    Over the last 20 years, biological MS has changed out of all recognition. This is primarily due to the development in the 1980s of 'soft ionization' methods that permit the ionization and vaporization of large, polar, and thermally labile biomolecules. These developments in ionization mode have driven the design and manufacture of smaller and cheaper mass analysers, making the mass spectrometer a routine instrument in the biochemistry laboratory today. In the present review the revolutionary 'soft ionization' methods will be discussed with particular reference to electrospray. The mass analysis of ions will be described, and the concept of tandem MS introduced. Where appropriate, examples of the application of MS in biochemistry will be provided. Although the present review will concentrate on the MS of peptides/proteins and lipids, all classes of biomolecules can be analysed, and much excellent work has been done in the fields of carbohydrate and nucleic acid biochemistry.

  9. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, R.P.; Udseth, H.R.; Olivares, J.A.

    1989-12-05

    A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., [+-]2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit. 21 figs.

  10. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, Richard D.; Udseth, Harold R.; Olivares, Jose A.

    1994-10-18

    A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit.

  11. Combined electrophoresis-electrospray interface and method

    DOEpatents

    Smith, Richard P.; Udseth, Harold R.; Olivares, Jose A.

    1989-01-01

    A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit.

  12. Submerged electrosprays: a versatile approach for microencapsulation.

    PubMed

    Jayasinghe, S N

    2007-08-01

    The unearthing of fundamental science and technology associated with microencapsulation is an ongoing exciting scientific endeavour focused on by several scientists. Encapsulated structures (containing either a gas, molecules or materials) previously have been shown as having widespread applications across the physical and life sciences. In particular, such methodologies used for forming encapsulations in medical-related studies have shown great promise from diagnostics and imaging, to gene therapy and drug delivery which are only a few amongst several other applications. At present there are numerous 'jet-based' manifestations available for microencapsulation, these primarily root from either capillary or channel-based techniques. The driving mechanisms employed in these approaches exploit aerodynamic/pressure gradients to piezoelectricity. In this paper submerged electrosprays a multipurpose electric field driven jet-based technique is explored for forming near mono-dispersed encapsulations sized in the micrometer range. Our studies elucidate the ability to form microencapsulations containing either a gas or a micro/nanoparticulate-based material suspension as capsules sized in the ranges approximately 65-80 microm, approximately 8-25 microm to approximately 3-14 microm, respectively. We believe this technique can significantly contribute to the microencapsulation field of research based on both the size of the generated encapsulations to the containment of immiscible high viscosity particulate-based suspensions. Furthermore our investigations show the ability to control the production of these encapsulations in terms of both their size and rate of generation with ease; hence demonstrating this electrospray-assisted microencapsulation route as having a wide range of applications. It should be noted that in its present form this technique could be explored for generating emulsions with a variety of materials especially with living organisms for applications in the

  13. Recombination in liquid filled ionisation chambers with multiple charge carrier species: Theoretical and numerical results

    NASA Astrophysics Data System (ADS)

    Aguiar, P.; González-Castaño, D. M.; Gómez, F.; Pardo-Montero, J.

    2014-10-01

    Liquid-filled ionisation chambers (LICs) are used in radiotherapy for dosimetry and quality assurance. Volume recombination can be quite important in LICs for moderate dose rates, causing non-linearities in the dose rate response of these detectors, and needs to be corrected for. This effect is usually described with Greening and Boag models for continuous and pulsed radiation respectively. Such models assume that the charge is carried by two different species, positive and negative ions, each of those species with a given mobility. However, LICs operating in non-ultrapure mode can contain different types of electronegative impurities with different mobilities, thus increasing the number of different charge carriers. If this is the case, Greening and Boag models can be no longer valid and need to be reformulated. In this work we present a theoretical and numerical study of volume recombination in parallel-plate LICs with multiple charge carrier species, extending Boag and Greening models. Results from a recent publication that reported three different mobilities in an isooctane-filled LIC have been used to study the effect of extra carrier species on recombination. We have found that in pulsed beams the inclusion of extra mobilities does not affect volume recombination much, a behaviour that was expected because Boag formula for charge collection efficiency does not depend on the mobilities of the charge carriers if the Debye relationship between mobilities and recombination constant holds. This is not the case in continuous radiation, where the presence of extra charge carrier species significantly affects the amount of volume recombination.

  14. Age at exposure to ionising radiation and cancer mortality among Hanford workers: follow up through 1994

    PubMed Central

    Wing, S; Richardson, D

    2005-01-01

    Background: Studies of workers at the plutonium production factory in Hanford, WA have led to conflicting conclusions about the role of age at exposure as a modifier of associations between ionising radiation and cancer. Aims: To evaluate the influence of age at exposure on radiation risk estimates in an updated follow up of Hanford workers. Methods: A cohort of 26 389 workers hired between 1944 and 1978 was followed through 1994 to ascertain vital status and causes of death. External radiation dose estimates were derived from personal dosimeters. Poisson regression was used to estimate associations between mortality and cumulative external radiation dose at all ages, and in specific age ranges. Results: A total of 8153 deaths were identified, 2265 of which included cancer as an underlying or contributory cause. Estimates of the excess relative risk per Sievert (ERR/Sv) for cumulative radiation doses at all ages combined were negative for all cause and leukaemia and positive for all cancer and lung cancer. Cumulative doses accrued at ages below 35, 35–44, and 45–54 showed little association with mortality. For cumulative dose accrued at ages 55 and above (10 year lag), the estimated ERR/Sv for all cancers was 3.24 (90% CI: 0.80 to 6.17), primarily due to an association with lung cancer (ERR/Sv: 9.05, 90% CI: 2.96 to 17.92). Conclusions: Associations between radiation and cancer mortality in this cohort are primarily a function of doses at older ages and deaths from lung cancer. The association of older age radiation exposures and cancer mortality is similar to observations from several other occupational studies. PMID:15961623

  15. Electrospray mass spectrometric evidence for the occurrence of two major variants in native pig pepsin A.

    PubMed Central

    Green, B N; Jones, A T; Roberts, N B

    1996-01-01

    Native pig pepsin was analysed by negative ion electrospray mass spectrometry in order to rationalize anomalies between the published sequences. Outstanding variations in otherwise identical sequences indicate that amino acid residue 242 is either Asp or Tyr, and in some determinations an additional Ile is inserted at position 230. Mass spectrometric evidence is consistent with the presence, in the native enzyme, of two variants in comparable abundance, with either Asp or Tyr at residue 242. There is no evidence for the additional Ile at position 230. PMID:8546690

  16. Electrosprayed nanoparticles for drug delivery and pharmaceutical applications

    PubMed Central

    Sridhar, Radhakrishnan; Ramakrishna, Seeram

    2013-01-01

    Nanotechnology based Pharma has emerged significantly and has influenced the Pharma industry up to a considerable extent. Nanoparticles technology holds a good share of the nanotech Pharma and is significant in comparison with the other domains. Electrospraying technology answers the potential needs of nanoparticle production such as scalability, reproducibility, effective encapsulation etc. Many drugs have been electrosprayed with and without polymer carriers. Drug release characteristics are improved with the incorporation of biodegradable polymer carriers which sustain the release of encapsulated drug. Electrospraying is acknowledged as an important technique for the preparation of nanoparticles with respect to pharmaceutical applications. Herein we attempted to consolidate the reports pertaining to electrospraying and their corresponding therapeutic application area. PMID:23512013

  17. Corona discharges with water electrospray for Escherichia coli biofilm eradication on a surface.

    PubMed

    Kovalova, Zuzana; Leroy, Magali; Kirkpatrick, Michael J; Odic, Emmanuel; Machala, Zdenko

    2016-12-01

    Low-temperature plasma (cold), a new method for the decontamination of surfaces, can be an advantageous alternative to the traditional chemical methods, autoclave or dry heat. Positive and negative corona discharges in air were tested for the eradication of 48-h Escherichia coli biofilms grown on glass slides. The biofilms were treated by cold corona discharge plasma for various exposure times. Water electrospray from the high voltage electrode was applied in some experiments. Thermostatic cultivation of the biofilm, and confocal laser scanning microscopy (CLSM) of the biofilm stained with fluorescent dyes were used for biocidal efficiency quantification. Up to 5 log10 reduction of bacterial concentration in the biofilm was measured by thermostatic cultivation after exposure to both corona discharges for 15min. This decontamination efficiency was significantly enhanced by simultaneous water electrospray through the plasma. CLSM showed that the live/dead ratio after treatment remained almost constant inside the biofilm; only cells on the top layers of the biofilm were affected. DAPI fluorescence showed that biofilm thickness was reduced by about 1/3 upon exposure to the corona discharges with electrospray for 15min. The biofilm biomass loss by about 2/3 was confirmed by crystal violet assay.

  18. Annealing of GaSb Single Crystals in Ionised Hydrogen Atmosphere

    DTIC Science & Technology

    2001-01-01

    and Applications 46 of Single Crystals, Antoni Rogaski, Krzysztof Adamiec, Pawel Madejczyk, Editors, Proceedings of SPIE Vol. 4412 (2001) © 2001...1-50 hours. Hydrogen ionised by means of a deuterium lamp flew through this annealing reactor. After cooling the quartz ampoule, the carrier

  19. The Effects of Ionising Radiation on MEMS Silicon Strain Gauges: Preliminary Background and Methodology

    DTIC Science & Technology

    2006-09-01

    tuneable radar, structural health monitoring (corrosion and strain sensing) and power production . 2. Ionising Radiation Susceptibility of...materials this displacement damage affects the electronic energy states, which can give rise to several processes, including increased thermal ...are smaller and lighter than the current generation of detectors. The lower costs associated with mass- production of MEMS could also allow greater

  20. Identification of carbohydrates by matrix-free material-enhanced laser desorption/ionisation mass spectrometry.

    PubMed

    Hashir, Muhammad Ahsan; Stecher, Guenther; Bakry, Rania; Kasemsook, Saowapak; Blassnig, Bernhard; Feuerstein, Isabel; Abel, Gudrun; Popp, Michael; Bobleter, Ortwin; Bonn, Guenther K

    2007-01-01

    Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is a sensitive mass spectrometric technique which utilises acidic materials as matrices for laser energy absorption, desorption and ionisation of analytes. These matrix materials produce background signals particularly in the low-mass range and make the detection and identification of small molecules difficult and nearly impossible. To overcome this problem this paper introduces matrix-free material-enhanced laser desorption/ionisation mass spectrometry (mf-MELDI-MS) for the screening and analysis of small molecules such as carbohydrates. For this purpose, 4,4'-azo-dianiline was immobilised on silica gel enabling the absorption of laser energy sufficient for successful desorption and ionisation of low molecular weight compounds. The particle and pore sizes, the solvent system for suspension and the sample preparation procedures have been optimised. The newly synthesised MELDI material delivered excellent spectra with regard to signal-to-noise ratio and detection sensitivity. Finally, wheat straw degradation products and Salix alba L. plant extracts were analysed proving the high performance and excellent behaviour of the introduced material.

  1. For discussion: obtaining consent for ionising radiation: has the time come?

    PubMed

    Mendelson, Richard M

    2010-10-01

    The aim of this paper is to promote debate on the issues surrounding the provision of information to, and the obtaining of valid consent from patients exposed to ionising radiation (IR) from diagnostic and interventional imaging procedures. This is especially pertinent in view of recent interest in the risks of IR expressed in the medical and lay press.

  2. Examining Pre-Service Teachers' Use of Atomic Models in Explaining Subsequent Ionisation Energy Values

    ERIC Educational Resources Information Center

    Wheeldon, Ruth

    2012-01-01

    Chemistry students' explanations of ionisation energy phenomena often involve a number of non-scientific or inappropriate ideas being used to form causality arguments. Research has attributed this to many science teachers using these ideas themselves (Tan and Taber, in "J Chem Educ" 86(5):623-629, 2009). This research extends this work by…

  3. Exploring Learners' Conceptual Resources: Singapore a Level Students' Explanations in the Topic of Ionisation Energy

    ERIC Educational Resources Information Center

    Taber, Keith S.; Tan, Kim Chwee Daniel

    2007-01-01

    This paper describes findings from a study to explore Singapore A-level (Grades 11 and 12, 16-19 yr old) students' understanding of ionisation energy, an abstract and complex topic that is featured in school chemistry courses. Previous research had reported that students in the United Kingdom commonly use alternative notions based on the perceived…

  4. The impact of high and low dose ionising radiation on the central nervous system.

    PubMed

    Betlazar, Calina; Middleton, Ryan J; Banati, Richard B; Liu, Guo-Jun

    2016-10-01

    Responses of the central nervous system (CNS) to stressors and injuries, such as ionising radiation, are modulated by the concomitant responses of the brains innate immune effector cells, microglia. Exposure to high doses of ionising radiation in brain tissue leads to the expression and release of biochemical mediators of 'neuroinflammation', such as pro-inflammatory cytokines and reactive oxygen species (ROS), leading to tissue destruction. Contrastingly, low dose ionising radiation may reduce vulnerability to subsequent exposure of ionising radiation, largely through the stimulation of adaptive responses, such as antioxidant defences. These disparate responses may be reflective of non-linear differential microglial activation at low and high doses, manifesting as an anti-inflammatory or pro-inflammatory functional state. Biomarkers of pathology in the brain, such as the mitochondrial Translocator Protein 18kDa (TSPO), have facilitated in vivo characterisation of microglial activation and 'neuroinflammation' in many pathological states of the CNS, though the exact function of TSPO in these responses remains elusive. Based on the known responsiveness of TSPO expression to a wide range of noxious stimuli, we discuss TSPO as a potential biomarker of radiation-induced effects.

  5. Examining Pre-Service Teachers' Use of Atomic Models in Explaining Subsequent Ionisation Energy Values

    ERIC Educational Resources Information Center

    Wheeldon, Ruth

    2012-01-01

    Chemistry students' explanations of ionisation energy phenomena often involve a number of non-scientific or inappropriate ideas being used to form causality arguments. Research has attributed this to many science teachers using these ideas themselves (Tan and Taber, in "J Chem Educ" 86(5):623-629, 2009). This research extends this work by…

  6. Liquid chromatography with electrospray ion trap mass spectrometry for the determination of five azaspiracids in shellfish.

    PubMed

    Lehane, M; Braña-Magdalena, A; Moroney, C; Furey, A; James, K J

    2002-03-15

    Azaspiracid poisoning (AZP) is a new human toxic syndrome that is caused by the consumption of shellfish that have been feeding on harmful marine microalgae. A liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of the three most prevalent toxins, azaspiracid (AZA1), 8-methylazaspiracid (AZA2) and 22-demethylazaspiracid (AZA3) as well as the isomeric hydroxylated analogues, AZA4 and AZA5. Separation of five azaspiracids was achieved on a C18 column (Luna-2, 150 x 2 mm, 5 microm) with isocratic elution using acetonitrile-water containing trifluoroacetic acid and ammonium acetate as eluent modifiers. Using an electrospray ionisation (ESI) source with an ion-trap mass spectrometer, the spectra showed the protonated molecules, [M+H]+, with most major product ions due to the sequential loss of two water molecules. A characteristic fragmentation pathway that was observed in each azaspiracid was due to the cleavage of the A-ring at C9-C10 for each toxin. It was possible to select unique ion combinations to distinguish between the isomeric azaspiracids, AZA4 and AZA5. Highly sensitive LC-MS3 analytical methods were compared and the detection limits were 5-40 pg on-column. Linear calibrations were obtained for AZA1 in shellfish in the range 0.05-1.00 microg/ml (r2 = 0.9974) and good reproducibility was observed with a relative standard deviation (%RSD) of 1.8 for 0.9 microg AZAI/ml (n=5). The %RSD values for the minor toxins, AZA4 and AZA5, using LC-MS3 (A-ring fragmentation) were 12.3 and 8.1 (0.02 microg/ml; n=7), respectively. The selectivity of toxin determination was enhanced using LC-MS-MS with high energy WideBand activation.

  7. Formation of unexpected ions from a first-generation polyamidoamine dendrimer by use of methanol: an artefact due to electrospray emitter corrosion?

    PubMed

    Maire, Florian; Lange, Catherine M

    2010-04-15

    We report the formation of unexpected ions during the analyses of a first-generation polyamidoamine dendrimer in negative ion mode using an ion trap equipped with an electrospray ionisation source. These surprising ions corresponded to an increase of 12 m/z units over those expected. The formation of the unexpected ions was dependent on the tuning of the solution flow rate and the capillary high voltage. In addition, measurements of unusual value of the current suggested that a reaction was occurring in the corona plasma. The influence of methanol in this phenomenon was demonstrated by using CD(3)OH in the sample preparation. We propose two structures to explain the observed adduct based on the results of MS(2) experiments and by referring to previous work dealing with 12 m/z units addition. We showed that a corona discharge caused by alterations taking place to the electrospray capillary emitter was the origin of these unexpected ions. Finally, we discuss the mechanism involved in the formation of the ions and we propose means to control such artefacts.

  8. Determination of alprostadil in rat plasma by ultra performance liquid chromatography-electrospray ionization-tandem mass spectrometry after intravenous administration.

    PubMed

    Lin, Xia; Zhang, Yu; Cui, Yue; Wang, Lin; Wang, Jing; Tang, Xing

    2009-05-01

    A rapid, highly selective ultra performance liquid chromatography-electrospray ionisation-tandem mass spectrometry method (UPLC-ESI-MS/MS) was developed and validated for the determination and pharmacokinetic investigation of alprostadil in rat plasma. After a simple sample preparation procedure involving a one-step liquid-liquid extraction, alprostadil and the internal standard, diphenhydramine, were chromatographed on an ACQUITY UPLC BEH C(18) column with gradient elution using a mobile phase consisting of acetonitrile and water (containing 0.1% formic acid) at a flow rate of 0.25 mL min(-1). The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring (MRM) mode via an electrospray ionization (ESI) source. The calibration curve was linear (r(2)=0.99) over the concentration range 0.4-250.0 ng mL(-1), with a lower limit of quantification of 0.4 ng mL(-1) for alprostadil. The inter- and intra-day precision (%R.S.D.) was less than 8.5% and 2.4%, respectively, and the accuracy (RE%) was between 9.3% and 1.0% (n=6). Alprostadil in rat plasma was stable when stored at room temperature for 0.5h and at -20 degrees C for two weeks. The method was very rapid, simple and reliable, and was employed for the first time for the pharmacokinetic studies of alprostadil in rats after a single intravenous administration of 50 microg kg(-1).

  9. Catalyst layers for proton exchange membrane fuel cells prepared by electrospray deposition on Nafion membrane

    NASA Astrophysics Data System (ADS)

    Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Martín, A. J.; Daza, L.

    The electrospray deposition method has been used for preparation of catalyst layers for proton exchange membrane fuel cells (PEMFC) on Nafion membrane. Deposition of Pt/C + ionomer suspensions on Nafion 212 gives rise to layers with a globular morphology, in contrast with the dendritic growth observed for the same layers when deposited on the gas diffusion layer, GDL (microporous carbon black layer on carbon cloth) or on metallic Al foils. Such a change is discussed in the light of the influence of the Nafion substrate on the electrospray deposition process. Nafion, which is a proton conductor and electronic insulator, gives rise to the discharge of particles through proton release and transport towards the counter electrode, compared with the direct electron transfer that takes place when depositing on an electronic conductor. There is also a change in the electric field distribution in the needle to counter-electrode gap due to the presence of Nafion, which may alter conditions for the electrospray effect. If discharging of particles is slow enough, for instances with a low membrane protonic conductivity, the Nafion substrate may be charged positively yielding a change in the electric field profile and, with it, in the properties of the film. Single cell characterization is carried out with Nafion 212 membranes catalyzed by electrospray on the cathode side. It is shown that the internal resistance of the cell decreases with on-membrane deposited cathodic catalyst layers, with respect to the same layers deposited on GDL, giving rise to a considerable improvement in cell performance. The lower internal resistance is due to higher proton conductivity at the catalyst layer-membrane interface resulting from on-membrane deposition. On the other hand, electroactive area and catalyst utilization appear little modified by on-membrane deposition, compared with on-GDL deposition.

  10. Generation of gas-phase zirconium fluoroanions by electrospray of an ionic liquid

    SciTech Connect

    Gary S. Groenewold; James E. Delmore; Michael T. Benson; Tetsuya Tsuda; Rika Hagiwara

    2014-06-01

    RATIONALE: When measuring extremely wide isotope ratios (= 1 x 109) accelerator mass spectrometry (AMS) is the instrument of choice, however it requires an anion for injection into the tandem accelerator. Since many elements do not have positive electronegativities they do not form stable negative atomic ions, and hence are not compatible for isotope ratio measurement using AMS. Thus new approaches for forming anions are sought; fluoroanions are particularly attractive because fluorine is monoisotopic, and thus will not have overlapping isobars with the isotope of interest. METHODS: An approach is described for making zirconium fluoroanions using the fluorinating ionic liquid (IL) 1-ethyl-3-methylimidazolium fluorohydrogenate, which was used to generate abundant [ZrF5-] using electrospray ionization. The IL was dissolved in acetonitrile, combined with a dilute solution of either Zr4+ or ZrO2+, and then electrosprayed. Mass analysis and collision induced dissociation were conducted using a time-of-flight mass spectrometer. Cluster structures were predicted using density functional theory calculations. RESULTS: The fluorohydrogenate IL solutions generated abundant [ZrF5-] starting from solutions of both Zr4+ and ZrO2+. The mass spectra also contained IL-bearing cluster ions, whose compositions indicated the presence of [ZrF6]2- in solution, a conclusion supported by the structural calculations. Rinsing out the zirconium-IL solution with acetonitrile decreased the IL clusters, but enhanced [ZrF5]-, which was sorbed by the polymeric electrospray supply capillary, and then released upon rinsing. This reduced the ion background in the mass spectrum. CONCLUSIONS: The fluorohydrogenate-IL solutions are a facile way to form zirconium fluoroanions in the gas phase using electrospray. The approach has potential as a source of fluoroanions for injection into an AMS, which would enable high-sensitivity measurement of minor zirconium isotopes, and benefits from the absence of

  11. Subcellular analysis by laser ablation electrospray ionization mass spectrometry

    DOEpatents

    Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

    2014-12-02

    In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

  12. Fabrication and Testing of Tapered Electro-spray Nozzles

    DTIC Science & Technology

    2012-09-01

    oxidized nozzle with broken top cap. 15 The ultrasonic breaking of the etch mask was found to be a low-yield methodology, with some caps breaking...Fabrication and Testing of Tapered Electro-spray Nozzles by Brendan M. Hanrahan and C. Mike Waits ARL-TR-6226 September 2012...September 2012 Fabrication and Testing of Tapered Electro-spray Nozzles Brendan M. Hanrahan and C. Mike Waits Sensors and Electron Devices

  13. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  14. Feasibility of formation of hot ions in electrospray.

    PubMed

    Takáts, Zoltán; Drahos, László; Schlosser, Gitta; Vékey, Károly

    2002-12-15

    Internal energy changes during the electrospray process have been studied. Our results suggest that, contrary to conventional wisdom, ions that are quite hot are formed in electrospray, even without acceleration in the cone-skimmer region. The main role of the curtain gas seems to be not to break up existing clusters but, rather, to cool down the nascent ions and to prevent cluster formation by shielding them from solvent vapors.

  15. Validated Method for Strigolactone Quantification by Ultra High-Performance Liquid Chromatography - Electrospray Ionisation Tandem Mass Spectrometry Using Novel Deuterium Labelled Standards.

    PubMed

    Boutet-Mercey, Stéphanie; Perreau, François; Roux, Amélie; Clavé, Guillaume; Pillot, Jean-Paul; Schmitz-Afonso, Isabelle; Touboul, David; Mouille, Grégory; Rameau, Catherine; Boyer, François-Didier

    2017-08-29

    Strigolactones (SLs) are important plant hormones. They are difficult to analyse because they occur in very small concentrations especially in comparison with other plant hormones and other substances can interfere with their detection. To develop a procedure for the extraction, purification and quantification of SLs from plant roots. Samples were prepared by extraction of plant root tissues with ethyl acetate. Then the extracts were further purified with silica column chromatography. The natural SLs in the final extracts were quantified using novel deuterium labelled SLs. The results of the methodology were compared with those of the procedure of Yoneyama and coworkers. This procedure required about 1-g root samples to detect and quantify simultaneously the SLs (orobanchyl acetate and fabacyl acetate) concentration with high reliability. A method was developed for determining endogenous fabacyl acetate and orobanchyl acetate in plant tissue based on novel deuterium labelled standards. A method of orobanchol quantification using a synthetic SL GR24 as internal standard was proposed. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  16. Evaluation of matrix solid-phase dispersion (MSPD) extraction for multi-fenicols determination in shrimp and fish by liquid chromatography-electrospray ionisation tandem mass spectrometry.

    PubMed

    Tao, Yanfei; Zhu, Fangwei; Chen, Dongmei; Wei, Huimin; Pan, Yuanhu; Wang, Xu; Liu, Zhenli; Huang, Lingli; Wang, Yulian; Yuan, Zonghui

    2014-05-01

    A quantitative LC-MS/MS method was developed for the determination of chloramphenicol (CAP), thiamphenicol (TAP), florfenicol (FF) and florfenicol amine (FFA) in shrimp and fish. This rapid simple and effective extraction method was based on matrix solid-phase dispersion (MSPD). The best results were obtained using C18 as dispersant sorbent. The correlation coefficient (r) with each matrix-matched calibration curve is higher than 0.999 at the range of 0.05-0.8μg/kg for CAP and FF, 0.1-1.6μg/kg for FFA and TAP. CCα and CCβ of the fenicols upon the method were ranged from 0.01 to 0.09μg/kg and 0.04 to 0.25μg/kg respectively. In the fortified levels recoveries of the four compounds ranged from 83.8% to 98.8% with RSDs lower than 13.7%. The proposed method has been applied successfully to the analysis of CAP, TAP, FF and FFA in shrimp and fish samples, which demonstrates that this method is fast, sensitive, reliable and environmental friendly.

  17. Quantitative analysis of phenolic compounds in Chinese hawthorn (Crataegus spp.) fruits by high performance liquid chromatography-electrospray ionisation mass spectrometry.

    PubMed

    Liu, Pengzhan; Kallio, Heikki; Lü, Deguo; Zhou, Chuansheng; Yang, Baoru

    2011-08-01

    Eleven major phenolic compounds (hyperoside, isoquercitrin, chlorogenic acid, ideain, epicatechin, two procyanidin (PA) dimers, three PA trimers and a PA dimer-hexoside) were quantified in the fruits of 22 cultivars/origins of three species of the Chinese hawthorn (Crataegus spp.) by HPLC-ESI-MS-SIR. Hyperoside (0.1-0.8mg/g dry mass [DM]), isoquercitrin (0.1-0.3mg/g DM), chlorogenic acid (0.2-1.6mg/g DM), epicatechin (0.9-11.7mg/g DM), PA B2 (0.7-12.4mg/g DM), PA dimer II (0.1-1.5mg/g DM), PA trimer I (0.1-2.7mg/g DM), PA trimer II (0.7-6.9mg/g DM), PA trimer III (0.01-1.2mg/g DM) and a PA dimer-hexoside (trace-1.1mg/g DM) were detected in all the samples. Ideain (0.0-0.7mg/g DM) was found in all the samples except Crataegus scabrifolia. Significant correlations between the contents of individual PA aglycons were observed (r>0.9, P<0.01). A strong correlation between flavonols was also shown (r=0.71, P<0.01). Fruits of Crataegus pinnatifida var. major had higher contents of PAs but lower contents of flavonols compared with Crataegus brettschneideri. The fruits of C. scabrifolia contained the highest level of PA dimer-hexoside, which was present in trace amounts in the fruits of C. pinnatifida.

  18. Determination of quinolones and fluoroquinolones in fish tissue and seafood by high-performance liquid chromatography with electrospray ionisation tandem mass spectrometric detection.

    PubMed

    Johnston, Lesley; Mackay, Lindsey; Croft, Meg

    2002-12-20

    A reversed-phase high-performance liquid chromatographic method with tandem mass-spectrometric detection was developed and validated for the simultaneous analysis of eight quinolones and fluoroquinolones (oxolinic acid, flumequine, piromidic acid, enrofloxacin, ciprofloxacin, danofloxacin, sarafloxacin and orbifloxacin) in trout tissue, prawns and abalone. The analytes were extracted from homogenised tissue using acetonitrile and the extracts subjected to an automated two-stage solid-phase extraction process involving polymeric reversed-phase and anion-exchange cartridges. Good recoveries were obtained for all analytes and the limit of quantification was 5 microg/kg (10 microg/kg for ciprofloxacin). The limit of detection was 1-3 microg/kg, depending on the analyte and matrix. Confirmation of the identity of a residue was achieved by further tandem mass-spectrometric analysis. A procedure for estimating the uncertainty associated with the measurement is presented.

  19. Identification of hydrolysable tannins in the reaction zone of Eucalyptus nitens wood by high performance liquid chromatography--electrospray ionisation mass spectrometry.

    PubMed

    Barry, K M; Davies, N W; Mohammed, C L

    2001-01-01

    The first detailed analysis of the phenolic constituents of the reaction zones (tissue of antimicrobial defence) from the sapwood of a Eucalyptus spp. is presented. Plantation-grown Eucalyptus nitens trees with stem decay resulting from pruning wounds were sampled and extracts were prepared from healthy sapwood and from reaction zone tissue. Analysis by HPLC with ESI-MS revealed that a diverse range of hydrolysable tannins are present in both healthy sapwood and in reaction zone extracts, including over 30 gallotannins, ellagitannins and phenols. Eight tannins were unequivocally identified, including the gallotannins tri-O-galloyl-beta-D-glucose, tetra-O-galloyl-beta-D-glucose and penta-O-galloyl-beta-D-glucose, and the ellagitannins pedunculagin, tellimagrandin I, casuarinin, casuarictin and tellimagrandin II. The phenols gallic acid, ellagic acid and catechin were also identified. The ellagitannins (particularly pedunculagin) are considerably more abundant in the reaction zone than in the healthy sapwood and may contribute to the effectiveness of the reaction zone as an antimicrobial barrier.

  20. Validation of a method for the analysis of quinolones residues in bovine muscle by liquid chromatography with electrospray ionisation tandem mass spectrometry detection.

    PubMed

    Rubies, A; Vaquerizo, R; Centrich, F; Compañó, R; Granados, M; Prat, M D

    2007-04-15

    A liquid chromatography-tandem mass spectrometry method for the determination and confirmation of nine quinolones was optimised and validated according to Commission Decision 2002/657/EC. Analytes were extracted from veal muscle with water and extracts purified with 96-well plates Oasis HLB cartridges. Separation was carried out in a silica-based C(18) column (50mmx2.1mm) with mobile phases consisting of water/acetonitrile mixtures containing acetic acid. Linear calibration curves in the ranges 4-400 and 50-800ngg(-1), with correlation coefficients at least 0.995, were obtained for all the analytes. At concentration levels above 10ngg(-1), quantification errors were lower than 10% and repeatability and within-laboratory reproducibility standard deviations below 6% and 10%, respectively. Decision limits and detection capabilities are reported.

  1. Detecting equilibrium cytochrome c folding intermediates by electrospray ionisation mass spectrometry: Two partially folded forms populate the molten-globule state

    PubMed Central

    Grandori, Rita

    2002-01-01

    Nanoelectrospray ionization mass spectrometry (nano-ESI-MS) is applied to the characterization of ferric cytochromec (cytc) conformational states under different solvent conditions. The methanol-induced molten-globule state in the pH range 2.6–3.0 is found to be populated by two distinct, partially folded conformers IA and IB. The more compact intermediate IB resembles that induced by glycerol in acid-unfolded cytc. The less compact one, IA, also can be induced by destabilization of the native structure by trifluoroethanol. IA and IB can be detected, in the absence of additives, around the midpoint of the acid-induced unfolding transition, providing direct evidence for involvement of equilibrium folding intermediates in cytc conformational transitions at low pH. This study shows that mass spectrometry can contribute to the characterization of molten-globule states of proteins by detection of distinct, although poorly populated, conformations involved in a dynamic equilibrium. PMID:11847268

  2. Simultaneous determination of phenolic compounds in Cynthiana grape (Vitis aestivalis) by high performance liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Ramirez-Lopez, L M; McGlynn, W; Goad, C L; Mireles Dewitt, C A

    2014-04-15

    Phenolic acids, flavanols, flavonols and stilbenes (PAFFS) were isolated from whole grapes, juice, or pomace and purified using enzymatic hydrolysis. Only anthocyanin mono-glucosides and a few of the oligomers from Cynthiana grape (Vitis aestivalis) were analysed. Flavonoid-anthocyanin mono-glucosides (FA) were isolated using methanol/0.1% hydrochloric acid extraction. In addition, crude extractions of phenolic compounds from Cynthiana grape using 50% methanol, 70% methanol, 50% acetone, 0.01% pectinase, or petroleum ether were also evaluated. Reverse phase high performance liquid chromatography (RP-HPLC) with photodiode array (PDA) detector was used to identify phenolic compounds. A method was developed for simultaneous separation, identification and quantification of both PAFFS and FA. Quantification was performed by the internal standard method using a five points regression graph of the UV-visible absorption data collected at the wavelength of maximum absorbance for each analyte. From whole grape samples nine phenolic compounds were tentatively identified and quantified. The individual phenolic compounds content varied from 3 to 875 mg kg⁻¹ dry weight. For juice, twelve phenolic compounds were identified and quantified. The content varied from 0.07 to 910 mg kg⁻¹ dry weight. For pomace, a total of fifteen phenolic compounds were tentatively identified and quantified. The content varied from 2 mg kg⁻¹ to 198 mg kg⁻¹ dry matter. Results from HPLC analysis of the samples showed that gallic acid and (+)-catechin hydrate were the major phenolic compounds in both whole grapes and pomace. Cyanidin and petunidin 3-O-glucoside were the major anthocyanin glucosides in the juice. Published by Elsevier Ltd.

  3. Tackling matrix effects during development of a liquid chromatographic-electrospray ionisation tandem mass spectrometric analysis of nine basic pharmaceuticals in aqueous environmental samples.

    PubMed

    Van de Steene, Jet C; Mortier, Kjell A; Lambert, Willy E

    2006-08-04

    When developing an LC-MS/MS-method matrix effects are a major issue. The effect of co-eluting compounds arising from the matrix can result in signal enhancement or suppression. During method development much attention should be paid to diminish matrix effects as much as possible. The present work evaluates matrix effects from aqueous environmental samples in the simultaneous analysis of a group of nine specific pharmaceuticals with LC-ESI/MS/MS: flubendazole, propiconazole, pipamperone, cinnarizine, ketoconazole, miconazole, rabeprazole, itraconazole and domperidone. Solutions to diminish signal suppression were examined: optimisation of the sample preparation, decrease of the flow rate, and the use of appropriate internal standards. Several SPE-stationary phases were tested in view of retention of the analytes: Oasis HLB, C8, Phenyl, Strata X-polymer RP sorbent and Strata X-polymeric SCX/RP sorbent. Oasis HLB showed the best retention for all analytes. The Oasis HLB SPE-method was optimised, but analyses showed high matrix suppression. Therefore, a second SPE-method, on a phenyl stationary phase (the second best option), was also optimised. A comparison of the matrix effect was made between the two procedures: the phenyl-method was less subject to matrix effects, however, the average matrix effect (ME%) of 46% indicated that matrix effects where still present. Several optimisation options for the phenyl-method were evaluated: addition of a ferric nitrate solution before extraction, application of an alkaline wash step, and use of a second SPE-cartridge, either a NH2-column or a florisil column. A more efficient sample clean-up was achieved by applying the extract after extraction on the phenyl column and after dilution with chloroform, onto a NH2-column (average ME%: 53%). In addition, applying a post-column split (1:5), further reduced matrix effects (average ME%: 65%). Labelled internal standards are the best way to tackle matrix effects, but no such internal standards were commercially available for the analytes of interest. The thorough search and application of four internal standards (structural analogues) was beneficial and compensates the matrix effect partially (average ME%: 83%). In an attempt to reduce the analysis time Speedisk phenyl columns were applied. Under these conditions matrix effects decreased even more while recoveries were between 91 and 109%. Different kinds of surface water samples were analyzed, and different matrix effects were observed. For this reason, standard addition will be used to perform quantitative analysis.

  4. Nanoparticles facilitate gene delivery to microorganisms via an electrospray process.

    PubMed

    Lee, Yi-Hsuan; Wu, Bing; Zhuang, Wei-Qin; Chen, Da-Ren; Tang, Yinjie J

    2011-02-01

    In this study, we developed a technique for delivering genes to microorganisms via electrospray of gold nanoparticles. During the electrospray process, charged monodisperse nano-droplets (a mixture of pET30a-GFP plasmid and nano-sized gold particles) were accelerated and deposited on a thin layer of non-competent Escherichia coli cells. Via antibiotic selection, transformed cells containing green fluorescent protein appeared on the agar plates. PCR amplification and restriction enzyme analysis further confirmed that pET30a-GFP plasmid had successfully been delivered into the non-competent E. coli cells. The transformation efficiencies were optimized under different electrospray conditions. Among several electrospray buffer solutions, CaCl(2) (0.01M) was found to be the best for gene delivery. Furthermore, gold nanoparticles (NPs, 50 nm diameter) significantly improved plasmid transformation efficiency by 5-7 fold (up to 2×10(6) CFU/μg plasmid) compared with that obtained using naked plasmid. Electronic microscopy images and gel electrophoresis showed that the morphology of plasmids remained unchanged during the electrospray process, but cellular membrane integrity was reduced after being electrosprayed with gold NPs and CaCl(2) buffer solutions. This gene delivery method has the potential to work for many other microorganisms. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Aerodynamic mass spectrometry interfacing of microdevices without electrospray tips.

    PubMed

    Grym, Jakub; Otevrel, Marek; Foret, Frantisek

    2006-10-01

    A new concept for electrospray coupling of microfluidic devices with mass spectrometry was developed. The sampling orifice of the time-of-flight mass spectrometer was modified with an external adapter assisting in formation and transport of the electrosprayed plume from the multichannel polycarbonate microdevice. The compact disk sized microdevice was designed with radial channels extending to the circumference of the disk. The electrospray exit ports were formed by the channel openings on the surface of the disk rim. No additional tips at the channel exits were used. Electrospray was initiated directly from the channel openings by applying high voltage between sample wells and the entrance of the external adapter. The formation of the spatially unstable droplet at the electrospray openings was eliminated by air suction provided by a pump connected to the external adapter. Compared with the air intake through the original mass spectrometer sampling orifice, more than an order of magnitude higher flow rate was achieved for efficient transport of the electrospray plume into the mass spectrometer. Additional experiments with electric potentials applied between the entrance sections of the external adapter and the mass spectrometer indicated that the air flow was the dominant transport mechanism. Basic properties of the system were tested using mathematical modeling and characterized using ESI/TOF-MS measurements of peptide and protein samples.

  6. Atomic data needs for X-ray spectroscopy of photo-ionised plasmas

    NASA Astrophysics Data System (ADS)

    Kaastra, Jelle S.

    2005-05-01

    High-resolution X-ray spectroscopy of Active Galactic Nuclei has become possible thanks to the launch of XMM-Newton and Chandra with their grating spectrometers, and will be explored further after the expected launch of ASTRO-E2 with its XRS detector. In several AGN the X-ray spectra show the signatures of on outflowing, photo-ionised wind. Also several X-ray binaries show a similar imprint of a photo-ionised gas. The clearest signatures are formed by the broad range of absorption lines, mostly from the ground states of a wide range of ionisation states of the abundant elements. In addition to absorption lines due to the valence electrons, the spectra show many inner-shell absorption lines. Examples are the K-shell transitions of the most abundant metal, oxygen, in the 19-23 Å band, and 2p-3d transitions of lowly ionised iron in the 15-17 Å region. These transitions have an extremely important diagnostic value, as other transitions of the same ions frequently occur in the unobservable extreme ultraviolet. Several of these inner-shell transitions, however, lack accurate experimental or theoretical wavelengths, which makes the spectral analysis complicated and ambiguous. This is even more the case for transitions from metastable levels, which can be used as density diagnostics. Finally, attention is payed to the role of atomic data in the photo-ionisation equilibrium calculations. Uncertainties in for example dielectronic recombination rates cause large uncertainties in the predicted absorption line strengths.

  7. Student and intern awareness of ionising radiation exposure from common diagnostic imaging procedures.

    PubMed

    Zhou, G Z; Wong, D D; Nguyen, L K; Mendelson, R M

    2010-02-01

    This study aims to evaluate medical student and intern awareness of ionising radiation exposure from common diagnostic imaging procedures and to suggest how education could be improved. Fourth to sixth year medical students enrolled at a Western Australian university and interns from three teaching hospitals in Perth were recruited. Participants were asked to complete a questionnaire consisting of 26 questions on their background, knowledge of ionising radiation doses and learning preferences for future teaching on this subject. A total of 331 completed questionnaires were received (95.9%). Of the 17 questions assessing knowledge of ionising radiation, a mean score of 6.0 was obtained by respondents (95% CI 5.8-6.2). Up to 54.8% of respondents underestimated the radiation dose from commonly requested radiological procedures. Respondents (11.3 and 25.5%) incorrectly believed that ultrasound and MRI emit ionising radiation, respectively. Of the four subgroups of respondents, the intern doctor subgroup performed significantly better (mean score 6.9, P < 0.0001, 95% CI 6.5-7.3) than each of the three medical student subgroups. When asked for the preferred method of teaching for future radiation awareness, a combination of lectures, tutorials and workshops was preferred. This study has clearly shown that awareness of ionising radiation from diagnostic imaging is lacking among senior medical students and interns. The results highlight the need for improved education to minimise unnecessary exposure of patients and the community to radiation. Further studies are required to determine the most effective form of education.

  8. Destruction of Raman biosignatures by ionising radiation and the implications for life detection on Mars.

    PubMed

    Dartnell, Lewis R; Page, Kristian; Jorge-Villar, Susana E; Wright, Gary; Munshi, Tasnim; Scowen, Ian J; Ward, John M; Edwards, Howell G M

    2012-04-01

    Raman spectroscopy has proven to be a very effective approach for the detection of microorganisms colonising hostile environments on Earth. The ExoMars rover, due for launch in 2018, will carry a Raman laser spectrometer to analyse samples of the martian subsurface collected by the probe's 2-m drill in a search for similar biosignatures. The martian surface is unprotected from the flux of cosmic rays, an ionising radiation field that will degrade organic molecules and so diminish and distort the detectable Raman signature of potential martian microbial life. This study employs Raman spectroscopy to analyse samples of two model organisms, the cyanobacterium Synechocystis sp. PCC 6803 and the extremely radiation resistant polyextremophile Deinococcus radiodurans, that have been exposed to increasing doses of ionising radiation. The three most prominent peaks in the Raman spectra are from cellular carotenoids: deinoxanthin in D. radiodurans and β-carotene in Synechocystis. The degradative effect of ionising radiation is clearly seen, with significant diminishment of carotenoid spectral peak heights after 15 kGy and complete erasure of Raman biosignatures by 150 kGy of ionising radiation. The Raman signal of carotenoid in D. radiodurans diminishes more rapidly than that of Synechocystis, believed to be due to deinoxanthin acting as a superior scavenger of radiolytically produced reactive oxygen species, and so being destroyed more quickly than the less efficient antioxidant β-carotene. This study highlights the necessity for further experimental work on the manner and rate of degradation of Raman biosignatures by ionising radiation, as this is of prime importance for the successful detection of microbial life in the martian near subsurface.

  9. Electrochemical processes in electrospray ionization mass spectrometry

    PubMed

    Mora; Van Berkel GJ; Enke; Cole; Martinez-Sanchez; Fenn

    2000-08-01

    Editorial Comment Last month we presented, as a Special Feature, a set of five articles that constituted a Commentary on the fundamentals and mechanism of electrospray ionization (ESI). These articles produced some lively discussion among the authors on the role of electrochemistry in ESI. Six authors participated in a detailed exchange of views on this topic, the final results of which constitute this month's Special Feature. We particularly hope that younger scientists will find value in this month's Special Feature, not only for the science that it teaches but also what it reveals about the processes by which scientific conclusions are drawn. To a degree, the contributions part the curtains on these processes and show science in action. We sincerely thank the contributors to this discussion. The give and take of intellectual debate is not always easy, and to a remarkable extent this set of authors has maintained good humor and friendships, even when disagreeing strongly on substance. Graham Cooks and Richard Caprioli Copyright 2000 John Wiley & Sons, Ltd.

  10. Micro-electrospray with stainless steel emitters.

    PubMed

    Shui, Wenqing; Yu, Yanling; Xu, Xuejiao; Huang, Zhenyu; Xu, Guobing; Yang, Pengyuan

    2003-01-01

    The physical processes underlying micro-electrospray (micro-ES) performance were investigated using a stainless steel (SS) emitter with a blunt tip. Sheathless micro-ES could be generated at a blunt SS tip without any tapering or sanding if ESI conditions were optimized. The Taylor cone was found to shrink around the inner diameter of the SS tubing, which permitted a low flow rate of 150 nL/min for sheathless microspray on the blunt tip (100 microm i.d. x 400 microm o.d.). It is believed that the wettability and/or hydrophobicity of SS tips are responsible for their micro-ES performance. The outlet orifice was further nipped to reduce the size of the spray cone and limit the flow rate to 50-150 nL/min, resulting in peptide detection down to attomole quantities consumed per spectrum. The SS emitter was also integrated into a polymethylmethacrylate microchip and demonstrated satisfactory performance in the analysis and identification of a myoglobin digest.

  11. Multiplexed electrospray scaling for liquid fuel injection

    NASA Astrophysics Data System (ADS)

    Waits, C. Mike; Hanrahan, Brendan; Lee, Ivan

    2010-10-01

    Evaporation and space-charge requirements are evaluated to understand the effect of device scaling and fuel preheating for a liquid fuel injector using a multiplexed electrospray (MES) configuration in compact combustion applications. This work reveals the influence of the droplet diameter, droplet velocity and droplet surface temperature as well as the surrounding gas temperature on the size and performance of microfabricated MES. Measurements from MES devices are used in the model to accurately account for the droplet diameter versus flow rate relationship, the minimum droplet diameter and the relevant droplet velocities. A maximum extractor electrode to ground electrode distance of 3.1 mm required to overcome space-charge forces is found to be independent of voltage or droplet velocity for large levels of multiplexing. This maximum distance also becomes the required evaporation length scale which imposes minimum fuel pre-heating requirements for large flow densities. Required fuel preheating is therefore evaluated for both ethanol and 1-butanol with combustor parameters relevant to fuel reformation, thermoelectric conversion, thermophotovoltaic conversion and thermionic conversion.

  12. Electron impact ionisation of encapsulated 99mTc@C 60 and 99mTc@C 70

    NASA Astrophysics Data System (ADS)

    Đustebek, J. B.; Đorđević, V. R.; Cvetićanin, J. M.; Veličković, S. R.; Veljković, M. V.; Nešković, O. M.; Rakočević, Z. L.; Bibić, N. M.

    2010-03-01

    The present study shows simultaneous surface ionisation and electron impact ionisation during the formation and investigation of endohedral fullerenes 99mTc@C 60 and 99mTc@C 70. The endohedral fullerenes were generated using a mass spectrometer with a triple rhenium filament as an ion source. The ionisation energies (IE) determined were: 8.52 ± 0.25 eV for 99mTc@C 60 and 9.57 ± 0.25 eV for 99mTc@ C 70.

  13. Assessment of Reproducibility of Laser Electrospray Mass Spectrometry using Electrospray Deposition of Analyte

    NASA Astrophysics Data System (ADS)

    Sistani, Habiballah; Karki, Santosh; Archer, Jieutonne J.; Shi, Fengjian; Levis, Robert J.

    2017-05-01

    A nonresonant, femtosecond (fs) laser is employed to desorb samples of Victoria blue deposited on stainless steel or indium tin oxide (ITO) slides using either electrospray deposition (ESD) or dried droplet deposition. The use of ESD resulted in uniform films of Victoria blue whereas the dried droplet method resulted in the formation of a ring pattern of the dye. Laser electrospray mass spectrometry (LEMS) measurements of the ESD-prepared films on either substrate were similar and revealed lower average relative standard deviations for measurements within-film (20.9%) and between-films (8.7%) in comparison to dried droplet (75.5% and 40.2%, respectively). The mass spectral response for ESD samples on both substrates was linear (R2 > 0.99), enabling quantitative measurements over the selected range of 7.0 × 10-11 to 2.8 × 10-9 mol, as opposed to the dried droplet samples where quantitation was not possible (R2 = 0.56). The limit of detection was measured to be 210 fmol.

  14. Assessment of Reproducibility of Laser Electrospray Mass Spectrometry using Electrospray Deposition of Analyte

    NASA Astrophysics Data System (ADS)

    Sistani, Habiballah; Karki, Santosh; Archer, Jieutonne J.; Shi, Fengjian; Levis, Robert J.

    2017-03-01

    A nonresonant, femtosecond (fs) laser is employed to desorb samples of Victoria blue deposited on stainless steel or indium tin oxide (ITO) slides using either electrospray deposition (ESD) or dried droplet deposition. The use of ESD resulted in uniform films of Victoria blue whereas the dried droplet method resulted in the formation of a ring pattern of the dye. Laser electrospray mass spectrometry (LEMS) measurements of the ESD-prepared films on either substrate were similar and revealed lower average relative standard deviations for measurements within-film (20.9%) and between-films (8.7%) in comparison to dried droplet (75.5% and 40.2%, respectively). The mass spectral response for ESD samples on both substrates was linear (R2 > 0.99), enabling quantitative measurements over the selected range of 7.0 × 10-11 to 2.8 × 10-9 mol, as opposed to the dried droplet samples where quantitation was not possible (R2 = 0.56). The limit of detection was measured to be 210 fmol.

  15. Secondary Ion Mass Spectrometry Analysis of Renal Cell Carcinoma with Electrospray Droplet Ion Beams

    PubMed Central

    Ninomiya, Satoshi; Yoshimura, Kentaro; Chen, Lee Chuin; Takeda, Sen; Hiraoka, Kenzo

    2017-01-01

    Tissue samples from renal cell carcinoma patients were analyzed by electrospray droplet ion beam-induced secondary ion mass spectrometry (EDI/SIMS). Positively- and negatively-charged secondary ions were measured for the cancerous and noncancerous regions of the tissue samples. Although specific cancerous species could not be found in both the positive and negative secondary ion spectra, the spectra of the cancerous and noncancerous tissues presented different trends. For instance, in the m/z range of 500–800 of the positive secondary ion spectra for the cancerous tissues, the intensities for several m/z values were lower than those of the m/z+2 peaks (indicating one double bond loss for the species), whereas, for the noncancerous tissues, the inverse trend was obtained. The tandem mass spectrometry (MS/MS) was also performed on the tissue samples using probe electrospray ionization (PESI), and some molecular ions produced by PESI were found to be fragmented into the ions observed in EDI/SIMS analysis. When the positive secondary ion spectra produced by EDI/SIMS were analyzed by principal component analysis, the results for cancerous and noncancerous tissues were separated. The EDI/SIMS method can be applied to distinguish between a cancerous and a noncancerous area with high probability. PMID:28149705

  16. Electrospray methodologies for characterization and deposition of nanoparticles

    NASA Astrophysics Data System (ADS)

    Modesto Lopez, Luis Balam

    Electrospray is an aerosolization method that generates highly charged droplets from solutions or suspensions and, after a series of solvent evaporation -- droplet fission cycles, it results in particles carrying multiple charges. Highly charged particles are used in a variety of applications, including particle characterization, thin film deposition, nanopatterning, and inhalation studies among several others. In this work, a soft X-ray photoionization was coupled with an electrospray to obtain monodisperse, singly charged nanoparticles for applications in online size characterization with electrical mobility analysis. Photoionization with the soft X-ray charger enhanced the diffusion neutralization rate of the highly charged bacteriophages, proteins, and solid particles. The effect of nanoparticle surface charge and nanoparticle agglomeration in liquids on the electrospray process was studied experimentally and a modified expression to calculate the effective electrical conductivity of nanosuspensions was proposed. The effective electrical conductivity of TiO2 nanoparticle suspensions is strongly dependent on the electrical double layer and the agglomeration dynamics of the particles; and such dependence is more remarkable in liquids with low ionic strength. TiO2 nanoparticle agglomerates with nearly monodisperse sizes in the nanometer and submicrometer ranges were generated, by electrospraying suspensions with tuned effective electrical conductivity, and used to deposit photocatalytic films for water-splitting. Nanostructured films of iron oxide with uniform distribution of particles over the entire deposition area were formed with an electrospray system. The micro-Raman spectra of the iron oxide films showed that transverse and longitudinal optical modes are highly sensitive to the crystallize size of the electrospray-deposited films. The fabrication of films of natural light-harvesting complexes, with the aim of designing biohybrid photovoltaic devices, was

  17. Electrospray ionization mass spectrometric studies of some imidazole amidoximes and nitrolic acids and their esters.

    PubMed

    Oresmaa, Larisa; Aulaskari, Paula; Vainiotalo, Pirjo

    2006-01-01

    The fragmentations of the [M+H]+ ions of imidazole amidoximes, and nitrolic acids and their esters, were studied by collision-induced dissociation experiments and by determining the accurate masses of the product ions on an electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer. The fragmentation pathways of the amidoximes varied with the substituent in the imidazole ring at position 1N, allowing two regioisomers to be distinguished. Nitrolic acids decompose in solution to nitrile oxides, and the studied nitrolic acid behaved in the same way in the gas phase. The esters decompose similarly to their parent compounds.

  18. Fabrication of superoleophobic surfaces by mask-assisted electrospray

    NASA Astrophysics Data System (ADS)

    Al-Milaji, Karam Nashwan; Zhao, Hong

    2017-02-01

    Electrospraying technique has been demonstrated to fabricate superhydrophobic surfaces with random hierarchical roughness. Yet, it has never been employed to generate superoleophobic surfaces with patterned multiscale roughness. Here, we report a versatile approach to fabricate superoleophobic surfaces with patterned multiscale roughness using a mask-assisted electrospray technique. Superoleophobic surfaces with random hierarchical roughness by conventional electrospray without mask were also investigated for comparison purposes. Surfaces with patterned multiscale roughness were obtained by focusing the electrosprayed deposition through a mesh mask, followed by overlaying a random hierarchical roughness of electrosprayed SiO2. All the textured surfaces were treated with a low surface energy fluoropolymer to render superhydrophobicity and superoleophobicity. Superior repellency against water and hexadecane (27.5 mN/m) has been demonstrated on the surfaces with random hierarchical roughness and patterned multiscale roughness (contact angles of ∼170° and sliding angles of less than 1°). On the random hierarchical surfaces, the intrinsic re-entrant and multi-tier overhang structures in the SiO2 agglomerates enable non-wetting of low surface tension liquids. While on the surfaces with patterned roughness, the dome shape of micropillars plays a critical role in enabling superoleophobicity. The electric field focusing effect exerted by the mask is verified by COMSOL Multiphysics simulation.

  19. Internal energy and fragmentation of ions produced in electrospray sources.

    PubMed

    Gabelica, Valérie; De Pauw, Edwin

    2005-01-01

    This review addresses the determination of the internal energy of ions produced by electrospray ionization (ESI) sources, and the influence of the internal energy on analyte fragmentation. A control of the analyte internal energy is crucial for several applications of electrospray mass spectrometry, like structural studies, construction of reproducible and exportable spectral libraries, analysis of non-covalent complexes. Sections II and III summarize the Electrospray mechanisms and source design considerations which are relevant to the problem of internal energy, and Section IV gives an overview of the inter-relationships between ion internal energy, reaction time scale, and analyte fragmentation. In these three sections we tried to make the most important theoretical elements understandable by all ESI users, and their understanding requires a minimal background in physical chemistry. We then present the different approaches used to experimentally determine the ion internal energy, as well as various attempts in modeling the internal energy uptake in electrospray sources. Finally, a tentative comparison between electrospray and other ionization sources is made. As the reader will see, although many reports appeared on the subject, the knowledge in the field of internal energy of ions produced by soft ionization sources is still scarce, because of the complexity of the system, and this is what makes this area of research so interesting. The last section presents some perspectives for future research.

  20. Encapsulating darunavir nanocrystals within Eudragit L100 using coaxial electrospraying.

    PubMed

    Nguyen, Duong Nhat; Clasen, Christian; Van den Mooter, Guy

    2017-04-01

    Electrospraying is renowned for its simplicity and versatility, and which can effectively produce particles with well-controlled size, size distribution, particle shape, morphology and microstructure at the nano/microscale. In this study, coaxial electrospraying was used to investigate its feasibility for preparing nanoparticles made up of nanocrystals encapsulated within a polymer shell. Firstly, aqueous nanosuspensions of darunavir were prepared by wet media milling. Then the nanosuspension and solutions of an enteric polymer, Eudragit L100, were used as the inner/core liquid and outer/shell liquid in a coaxial electrospraying setup, respectively. As long as a sufficiently high voltage was applied, a stable Taylor cone-jet mode was obtained to produce very fine core-shell structure nanoparticles with high darunavir encapsulation efficiency of approximately 90%. The influence of the starting nanosuspension and the flow rates on the characteristics of the final electrosprayed particles was also evaluated. Using an optimized nanosuspension with reasonable size, size distribution and flow rates, the enteric coating layer reduced the percentage of DRV release in acidic medium in the in vitro dissolution test to ca. 20%. This study indicates that coaxial electrospraying is a potential and unique technique for encapsulating drug nanocrystals within a polymeric shell. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Increasing Protein Charge State When Using Laser Electrospray Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Karki, Santosh; Flanigan, Paul M.; Perez, Johnny J.; Archer, Jieutonne J.; Levis, Robert J.

    2015-05-01

    Femtosecond (fs) laser vaporization is used to transfer cytochrome c, myoglobin, lysozyme, and ubiquitin from the condensed phase into an electrospray (ES) plume consisting of a mixture of a supercharging reagent, m-nitrobenzyl alcohol ( m-NBA), and trifluoroacetic acid (TFA), acetic acid (AA), or formic acid (FA). Interaction of acid-sensitive proteins like cytochrome c and myoglobin with the highly charged ES droplets resulted in a shift to higher charge states in comparison with acid-stable proteins like lysozyme and ubiquitin. Laser electrospray mass spectrometry (LEMS) measurements showed an increase in both the average charge states (Zavg) and the charge state with maximum intensity (Zmode) for acid-sensitive proteins compared with conventional electrospray ionization mass spectrometry (ESI-MS) under equivalent solvent conditions. A marked increase in ion abundance of higher charge states was observed for LEMS in comparison with conventional electrospray for cytochrome c (ranging from 19+ to 21+ versus 13+ to 16+) and myoglobin (ranging from 19+ to 26+ versus 18+ to 21+) using an ES solution containing m-NBA and TFA. LEMS measurements as a function of electrospray flow rate yielded increasing charge states with decreasing flow rates for cytochrome c and myoglobin.

  2. How do air ions reflect variations in ionising radiation in the lower atmosphere in a boreal forest?

    NASA Astrophysics Data System (ADS)

    Chen, Xuemeng; Kerminen, Veli-Matti; Paatero, Jussi; Paasonen, Pauli; Manninen, Hanna E.; Nieminen, Tuomo; Petäjä, Tuukka; Kulmala, Markku

    2016-11-01

    Most of the ion production in the atmosphere is attributed to ionising radiation. In the lower atmosphere, ionising radiation consists mainly of the decay emissions of radon and its progeny, gamma radiation of the terrestrial origin as well as photons and elementary particles of cosmic radiation. These types of radiation produce ion pairs via the ionisation of nitrogen and oxygen as well as trace species in the atmosphere, the rate of which is defined as the ionising capacity. Larger air ions are produced out of the initial charge carriers by processes such as clustering or attachment to pre-existing aerosol particles. This study aimed (1) to identify the key factors responsible for the variability in ionising radiation and in the observed air ion concentrations, (2) to reveal the linkage between them and (3) to provide an in-depth analysis into the effects of ionising radiation on air ion formation, based on measurement data collected during 2003-2006 from a boreal forest site in southern Finland. In general, gamma radiation dominated the ion production in the lower atmosphere. Variations in the ionising capacity came from mixing layer dynamics, soil type and moisture content, meteorological conditions, long-distance transportation, snow cover attenuation and precipitation. Slightly similar diurnal patterns to variations in the ionising capacity were observed in air ion concentrations of the cluster size (0.8-1.7 nm in mobility diameters). However, features observed in the 0.8-1 nm ion concentration were in good connection to variations of the ionising capacity. Further, by carefully constraining perturbing variables, a strong dependency of the cluster ion concentration on the ionising capacity was identified, proving the functionality of ionising radiation in air ion production in the lower atmosphere. This relationship, however, was only clearly observed on new particle formation (NPF) days, possibly indicating that charges after being born underwent different

  3. Exploring the Powerful Ionised Wind in the Seyfert Galaxy PG1211+143

    NASA Astrophysics Data System (ADS)

    Pounds, Ken

    2013-10-01

    Highly-ionised high-speed winds in AGN (UFOs) were first detected with XMM-Newton a decade ago, and are now established as a key factor in the study of SMBH accretion, and in the growth and metal enrichment of their host galaxies. However, information on the ionisation and dynamical structure, and the ultimate fate of UFOs remains very limited. We request a 600ks extended XMM-Newton study of the prototype UFO PG1211+143 in AO-13, to obtain high quality EPIC and RGS spectra, to map the flow structure and variability, while seeking evidence for the anticipated interaction with the ISM and possible conversion of the energetic wind to a momentum-driven flow.

  4. The nature of the ionised nebula surrounding the red supergiant W26

    NASA Astrophysics Data System (ADS)

    Wesson, Roger

    2015-08-01

    The red supergiant W26 in the massive star cluster Westerlund 1 is surrounded by a compact ionised nebula. This is unique among RSGs, and the excitation mechanism of the nebula is not yet known - it may be ionised by an unseen compact companion, or by a nearby blue supergiant. We present new observations of the nebula: high resolution spatially resolved spectra taken with FLAMES at the VLT show that the nebula is a ring, with velocities consistent with that expected for red supergiant ejecta, and ruling out the possibility of a Luminous Blue Variable-type eruption preceding the RSG phase as the origin of the nebula. A triangular patch of nebulosity outside the ring appears to be associated with W26, and may be material stripped from the expanding ring by the cumulative cluster wind and radiation field.

  5. Angular distribution of electrons in multiphoton ionisation of polarised Lithium atoms

    NASA Astrophysics Data System (ADS)

    Klimova, Yu. A.; Marmo, S. I.; Meremianin, A. V.

    2013-09-01

    The asymmetry of the angular distributions of photoelectrons in the photoionisation of polarised alkali atoms is investigated. The general formulas for the amplitude of the multiphoton ionisation of np-states are given. In these formulas the dynamical and kinematical factors are explicitly separated. Our calculations within Fues model potential approach demonstrate that, under the experimental conditions essentially similar to those employed in [M. Schuricke, Ganjun Zhu, J. Steinmann, K. Simeonidis, I. Ivanov, A. Kheifets, A.N. Grum-Grzhimailo, K. Bartschat, A. Dorn, J. Ullrich, Phys. Rev. A 83 (2011) 023413(11)], the relative magnitude of the linear magnetic dichroism in three-photon ionisation of Li can be as large as 30%.

  6. WE-G-BRA-06: Calibrating an Ionisation Chamber: Gaining Experience Using a Dosimetry 'flight Simulator'.

    PubMed

    Beavis, A; Saunderson, J; Ward, J

    2012-06-01

    Recently there has been great interest in the use of simulation training, with the view to enhance safety within radiotherapy practice. We have developed a Virtual Environment for Radiotherapy Training (VERT) which facilitates this, including the simulation of a number of 'Physics practices'. One such process is the calibration of an ionisation chamber for use in Linac photon beams. The VERT system was used to provide a life sized 3D virtual environment within which we were able to simulate the calibration of a departmental chamber for 6MV and 15 MV beams following the UK 1990 Code of Practice. The characteristics of the beams are fixed parameters in the simulation, whereas default (Absorbed dose to water) correction factors of the chambers are configurable thereby dictating their response in the virtual x-ray beam. When the simulation is started, a random, realistic temperature and pressure is assigned to the bunker. Measurement and chamber positional errors are assigned to the chambers. A virtual water phantom was placed on the Linac couch and irradiated through the side using a 10 × 10 field. With a chamber at the appropriate depths and irradiated iso-centrically, the Quality Indices (QI) of the beams were obtained. The two chambers were 'inter-compared', allowing the departmental chamber calibration factor to be calculated from that of the reference chamber. For the virtual 6/15 MV beams, the QI were found to be 0.668/ 0.761 and the inter-comparison ratios 0.4408/ 0.4402 respectively. The departmental chamber calibration factors were calculated; applying these and appropriate environmental corrections allowed the output of the Linac to be confirmed. We have shown how a virtual training environment can be used to demonstrate practical processes and reinforce learning. The UK CoP was used here, however any relevant protocol could be demonstrated. Two of the authors (Beavis and Ward) are Founders of Vertual Ltd, a spin-out company created to commercialise the

  7. Correlation of the ionisation response at selected points of IC sensitive regions with SEE sensitivity parameters under pulsed laser irradiation

    NASA Astrophysics Data System (ADS)

    Gordienko, A. V.; Mavritskii, O. B.; Egorov, A. N.; Pechenkin, A. A.; Savchenkov, D. V.

    2014-12-01

    The statistics of the ionisation response amplitude measured at selected points and their surroundings within sensitive regions of integrated circuits (ICs) under focused femtosecond laser irradiation is obtained for samples chosen from large batches of two types of ICs. A correlation between these data and the results of full-chip scanning is found for each type. The criteria for express validation of IC single-event effect (SEE) hardness based on ionisation response measurements at selected points are discussed.

  8. Occupational exposure to ionising radiation and mortality among workers of the former Spanish Nuclear Energy Board.

    PubMed Central

    Rodríguez Artalejo, F; Castaño Lara, S; de Andrés Manzano, B; García Ferruelo, M; Iglesias Martín, L; Calero, J R

    1997-01-01

    OBJECTIVES: Firstly, to ascertain whether mortality among workers of the former Spanish Nuclear Energy Board (Junta de Energía Nuclear-JEN) was higher than that for the Spanish population overall; and secondly, if this were so, to ascertain whether this difference was associated with exposure to ionising radiation. METHODS: A retrospective follow up of a cohort of 5657 workers was carried out for the period 1954-92. Cohort mortality was compared with that for the Spanish population overall, with standardised mortality ratios (SMRs) adjusted for sex, age, and calendar period. Also, Poisson models were used to analyse mortality from lung cancer in the cohort by level of exposure to ionising radiation. RESULTS: Workers' median and mean cumulative exposures were 4.04 and 11.42 mSv, respectively. Mean annual exposure was 1.33 mSv. Excess mortality due to bone tumours was found for the cohort as a whole (six deaths observed; SMR 2.95; 95% confidence interval (95% CI) 1.08 to 6.43). Among miners, excess mortality was found for non-malignant respiratory diseases (SMR 2.94; 95% CI 2.27 to 3.75), and for lung cancer bordering on statistical significance (SMR 1.50; 95% CI 0.96 to 2.23; P = 0.055). Relative risks of dying of lung cancer from ionising radiation in the dose quartiles 2, 3, and 4 versus the lowest dose quartile, were 1.00, 1.64, and 0.94, respectively. CONCLUSIONS: Excess mortality from lung cancer was found among JEN miners. Nevertheless, no clear relation was found between mortality from lung cancer and level of exposure to ionising radiation in the JEN cohort. Continued follow up of the cohort is required to confirm excess mortality from bone tumours. PMID:9155782

  9. Ionisation and discharge in cloud-forming atmospheres of brown dwarfs and extrasolar planets

    NASA Astrophysics Data System (ADS)

    Helling, Ch; Rimmer, P. B.; Rodriguez-Barrera, I. M.; Wood, Kenneth; Robertson, G. B.; Stark, C. R.

    2016-07-01

    Brown dwarfs and giant gas extrasolar planets have cold atmospheres with rich chemical compositions from which mineral cloud particles form. Their properties, like particle sizes and material composition, vary with height, and the mineral cloud particles are charged due to triboelectric processes in such dynamic atmospheres. The dynamics of the atmospheric gas is driven by the irradiating host star and/or by the rotation of the objects that changes during its lifetime. Thermal gas ionisation in these ultra-cool but dense atmospheres allows electrostatic interactions and magnetic coupling of a substantial atmosphere volume. Combined with a strong magnetic field \\gg {{B}\\text{Earth}} , a chromosphere and aurorae might form as suggested by radio and x-ray observations of brown dwarfs. Non-equilibrium processes like cosmic ray ionisation and discharge processes in clouds will increase the local pool of free electrons in the gas. Cosmic rays and lighting discharges also alter the composition of the local atmospheric gas such that tracer molecules might be identified. Cosmic rays affect the atmosphere through air showers in a certain volume which was modelled with a 3D Monte Carlo radiative transfer code to be able to visualise their spacial extent. Given a certain degree of thermal ionisation of the atmospheric gas, we suggest that electron attachment to charge mineral cloud particles is too inefficient to cause an electrostatic disruption of the cloud particles. Cloud particles will therefore not be destroyed by Coulomb explosion for the local temperature in the collisional dominated brown dwarf and giant gas planet atmospheres. However, the cloud particles are destroyed electrostatically in regions with strong gas ionisation. The potential size of such cloud holes would, however, be too small and might occur too far inside the cloud to mimic the effect of, e.g. magnetic field induced star spots.

  10. Occupational exposure to ionising radiation and mortality among workers of the former Spanish Nuclear Energy Board.

    PubMed

    Rodríguez Artalejo, F; Castaño Lara, S; de Andrés Manzano, B; García Ferruelo, M; Iglesias Martín, L; Calero, J R

    1997-03-01

    Firstly, to ascertain whether mortality among workers of the former Spanish Nuclear Energy Board (Junta de Energía Nuclear-JEN) was higher than that for the Spanish population overall; and secondly, if this were so, to ascertain whether this difference was associated with exposure to ionising radiation. A retrospective follow up of a cohort of 5657 workers was carried out for the period 1954-92. Cohort mortality was compared with that for the Spanish population overall, with standardised mortality ratios (SMRs) adjusted for sex, age, and calendar period. Also, Poisson models were used to analyse mortality from lung cancer in the cohort by level of exposure to ionising radiation. Workers' median and mean cumulative exposures were 4.04 and 11.42 mSv, respectively. Mean annual exposure was 1.33 mSv. Excess mortality due to bone tumours was found for the cohort as a whole (six deaths observed; SMR 2.95; 95% confidence interval (95% CI) 1.08 to 6.43). Among miners, excess mortality was found for non-malignant respiratory diseases (SMR 2.94; 95% CI 2.27 to 3.75), and for lung cancer bordering on statistical significance (SMR 1.50; 95% CI 0.96 to 2.23; P = 0.055). Relative risks of dying of lung cancer from ionising radiation in the dose quartiles 2, 3, and 4 versus the lowest dose quartile, were 1.00, 1.64, and 0.94, respectively. Excess mortality from lung cancer was found among JEN miners. Nevertheless, no clear relation was found between mortality from lung cancer and level of exposure to ionising radiation in the JEN cohort. Continued follow up of the cohort is required to confirm excess mortality from bone tumours.

  11. Migration to new ampoule types for the NPL secondary standard ionisation chambers.

    PubMed

    Baker, M; Fenwick, A; Ferreira, K; Keightley, J; Johansson, L; Collins, S

    2014-05-01

    As the pre-calibrated sample containers used for activity assay in the two NPL secondary standards ionisation chambers are being phased out, suitable replacements have been identified. Characterisation checks have been carried out on the new ISO ampoules and a long-term recalibration schedule has been devised. Around 40 calibration factors have been determined so far and comparison of ion chamber responses for the two ampoule types showed variations of up to 7% for low energy photon emitting radionuclides.

  12. Ab-initio surface hopping and multiphoton ionisation study of the photodissociation dynamics of CS2

    NASA Astrophysics Data System (ADS)

    Bellshaw, Darren; Horke, Daniel A.; Smith, Adam D.; Watts, Hannah M.; Jager, Edward; Springate, Emma; Alexander, Oliver; Cacho, Cephise; Chapman, Richard T.; Kirrander, Adam; Minns, Russell S.

    2017-09-01

    New ab initio surface hopping simulations of the excited state dynamics of CS2 including spin-orbit coupling are compared to new experimental measurements using a multiphoton ionisation probe in a photoelectron spectroscopy experiment. The calculations highlight the importance of the triplet states even in the very early time dynamics of the dissociation process and allow us to unravel the signatures in the experimental spectrum, linking the observed changes to both electronic and nuclear degrees of freedom within the molecule.

  13. Novel characterisation of minor α-linolenic acid isomers in linseed oil by gas chromatography and covalent adduct chemical ionisation tandem mass spectrometry.

    PubMed

    Gómez-Cortés, P; Brenna, J T; Lawrence, P; de la Fuente, M A

    2016-06-01

    Discrimination between polyunsaturated fatty acid isomers with three double bonds is a great challenge, due to structural similarities and similar polarities. In this study, we report the identification of four minor geometrical isomers of α-linolenic acid (ALA) present in linseed oil samples: (9E,12Z,15E)-, (9Z,12Z,15E)-, (9Z,12E,15Z)- and (9E,12Z,15Z)-octadeca-9,12,15-trienoic acids, chromatographically resolved by gas chromatography (GC) using a new and highly polar ionic phase column (SLB-IL111). Gas chromatography-electron ionisation mass spectrometry (GC-EIMS) determined that the four unknown compounds were C18:3 n-3 isomers. The positional 9-12-15 C18:3 configuration was achieved by covalent adduct chemical ionisation tandem mass spectrometry (CACI-MS/MS) while geometrical configuration was established with analytical standards based on relative retention. We hypothesised that these isomers are formed during linseed oil deodorisation and postulate preferred and unfavoured isomerisation pathways of ALA.

  14. Changes in plasma characteristics caused by easily ionisable elements in hollow cathode discharge emission spectrography.

    PubMed

    Szilvássy-Vámos, Z; Gyódrfi-Buzási, A; Pásztor, Z

    1991-11-01

    The effect of several concomitant easily ionisable elements (EIE's), Li, Na, K, Rb and Cs on the line intensity of Sr II (first ionised state) and Al I and He I (atomic states) has been studied by atomic emission spectrometry (AES) hollow cathode (HCD) analysis. The spectral line intensities emitted by Sr II, Al I and He I have been measured while varying the volume of the EIE's concentrations, ranging from 0.1 mg ml to 10 mg ml. In the presence of EIE's at higher concentrations than 0.5% a considerable decrease of the line intensities of Sr II at 430.54 nm and 407.71 nm was observed, together with a gradual decrease in the line intensities of both Al I 494.40 nm and 396.15 nm, and He I 412.1 nm. It is demonstrated in the present experiments with a water-cooled HCD source that interference effects caused by EIE's are observed when the ratio of the number of gas atoms (n(g)) and atoms with low ionisation energy (n(a))n(g)/n(a)is lower than 10(12).

  15. Examining Pre-Service Teachers' Use of Atomic Models in Explaining Subsequent Ionisation Energy Values

    NASA Astrophysics Data System (ADS)

    Wheeldon, Ruth

    2012-06-01

    Chemistry students' explanations of ionisation energy phenomena often involve a number of non-scientific or inappropriate ideas being used to form causality arguments. Research has attributed this to many science teachers using these ideas themselves (Tan and Taber, in J Chem Educ 86(5):623-629, 2009). This research extends this work by considering which atomic models are used in pre-service teachers' explanations and how that relates to the causality ideas expressed. Thirty-one pre-service teachers were interviewed. Each was asked to describe and explain four different atomic representations (Rutherford, Electron cloud micrograph, Bohr and Schrödinger types) in as much detail as they could. They also provided an explanation for the subsequent ionisation energy values for an oxygen atom and identified which representations were helpful in explaining the values. Significantly, when pre-service teachers only used Bohr type representations, they did not use repelling electron ideas in their explanations. However, arguments that were based on electron-electron repulsion used features from Schrödinger type atoms. These findings suggest that many pre-service teachers need to develop their atomic modelling skills so that they select and use models more expertly and that subsequent ionisation explanations offer a context in which to explore different atomic models' limitations and their deployment as explanatory resources.

  16. Is copper-silver ionisation safe and effective in controlling legionella?

    PubMed

    Cachafeiro, S Perez; Naveira, I Mato; García, I González

    2007-11-01

    Copper-silver ionisation is gaining popularity worldwide as a water disinfection method. We review the literature that supports the effectiveness and safety of the copper-silver ionisation pertaining to legionella control in water distribution systems. A search between January 1997 and January 2007 was conducted in relevant health databases: Medline, Embase, NHS CRD, Cochrane Library Plus, Web of Knowledge, IME (Spanish Medical Index) and IBECS (Health Sciences Bibliographic Index). Ten published studies were selected according to inclusion and exclusion criteria previously established; most of these were experimental. Legionella levels decrease with the application of any of the procedures used in these studies and the procedures can be combined to obtain better outcomes. No studies containing an economic evaluation were found. We conclude that copper-silver ionisation is an effective method to control legionella, bearing in mind that eradication cannot be achieved by any method in isolation. Maintaining high temperatures in the water system can maximise effectiveness of the method. Copper-silver appears to be safe, as long as ion levels are monitored and kept within international recommended levels. More studies with concurrent control group, long follow-up and economic evaluation are required to properly assess this procedure.

  17. A Carbon Nano Tube electron impact ionisation source for low-power, compact spacecraft mass spectrometers

    NASA Astrophysics Data System (ADS)

    Sheridan, S.; Bardwell, M. W.; Morse, A. D.; Morgan, G. H.

    2012-04-01

    A novel ionisation source which uses commercially available Carbon Nano Tube devices is demonstrated as a replacement for a filament based ionisation source in an ion trap mass spectrometer. The carbon nanotube ion source electron emission was characterised and exhibited typical emission of 30 ± 1.7 μA with an applied voltage differential of 300 V between the carbon nanotube tips and the extraction grid. The ion source was tested for longevity and operated under a condition of continuous emission for a period of 44 h; there was an observed reduction in emission current of 26.5% during operation. Spectra were generated by installing the ion source into a Finnigan Mat ITD700 ion trap mass spectrometer; the spectra recorded showed all of the characteristic m/z peaks from m/z 69 to m/z 219. Perfluorotributylamine spectra were collected and averaged contiguously for a period of 48 h with no significant signal loss or peak mass allocation shift. The low power requirements and low mass of this novel ionisation source are considered be of great value to future space missions where mass spectrometric technology will be employed.

  18. Field calibration studies for ionisation chambers in mixed high-energy radiation fields.

    PubMed

    Theis, C; Forkel-Wirth, D; Fuerstner, M; Mayer, S; Otto, Th; Roesler, S; Vincke, H

    2007-01-01

    The monitoring of ambient doses at work places around high-energy accelerators is a challenging task due the complexity of the mixed stray radiation fields encountered. At CERN, mainly Centronics IG5 high-pressure ionisation chambers are used to monitor radiation exposure in mixed fields. The monitors are calibrated in the operational quantity ambient dose equivalent H*(10) using standard, source-generated photon- and neutron fields. However, the relationship between ionisation chamber reading and ambient dose equivalent in a mixed high-energy radiation field can only be assessed if the spectral response to every component and the field composition is known. Therefore, comprehensive studies were performed at the CERN-EU high-energy reference field facility where the spectral fluence for each particle type has been assessed with Monte Carlo simulations. Moreover, studies have been performed in an accessible controlled radiation area in the vicinity of a beam loss point of CERN's proton synchrotron. The comparison of measurements and calculations has shown reasonable agreement for most exposure conditions. The results indicate that conventionally calibrated ionisation chambers can give satisfactory response in terms of ambient dose equivalent in stray radiation fields at high-energy accelerators in many cases. These studies are one step towards establishing a method of 'field calibration' of radiation protection instruments in which Monte Carlo simulations will be used to establish a correct correlation between the response of specific detectors to a given high-energy radiation field.

  19. Size and distribution controllable silica microballs fabricated by electrospraying

    NASA Astrophysics Data System (ADS)

    Xu, Bojing; Wu, Pan; Jiang, Qi; Gu, Wenhua

    2015-10-01

    Silica microballs have a wide range of applications in the field of optics, electronics, biotechnology chemical industry, and so on. In this work, a new approach, electrospraying, was used to coat the silica microballs onto the glass substrate, and the coating results were compared to spin-coating and dip-coating. Good microball size control could be achieved using the electrospraying method. X-Ray Diffraction (XRD) results showed that amorphous silica microballs were obtained. From Scanning Electron Microscopy (SEM) images, we can see that uniform microball size was achieved. In general, the results are better than what can be achieved by spin-coating, and comparable to that of dip-coating. However, electrospraying has great potential in mass production, especially for large-area fabrication.

  20. Method for Continuous Monitoring of Electrospray Ion Formation

    NASA Astrophysics Data System (ADS)

    Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

    2017-07-01

    A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes.

  1. Method for Continuous Monitoring of Electrospray Ion Formation.

    PubMed

    Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

    2017-07-20

    A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes. Graphical Abstract ᅟ.

  2. Method for Continuous Monitoring of Electrospray Ion Formation

    NASA Astrophysics Data System (ADS)

    Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

    2017-10-01

    A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes. [Figure not available: see fulltext.

  3. Bio-electrosprayed living composite matrix implanted into mouse models.

    PubMed

    Jayasinghe, Suwan N; Warnes, Gary; Scotton, Chris J

    2011-10-10

    We show that composite de novo structures can be generated using bio-electrosprays. Mouse lung fibroblasts are bio-electrosprayed directly with a biopolymer to form cell-bearing matrices, which are viable even when implanted subcutaneously into murine hosts. Generated cell-bearing matrices are assessed in-vitro and found to undergo all expected cellular behaviour. Subsequent in-vivo studies demonstrate the implanted living matrices integrating as expected with the surrounding microenvironment. The in-vitro and in-vivo studies elucidate and validate the ability for either bio-electrosprays or cell electrospinning to form a desired living architecture for undergoing investigation for repairing, replacing and rejuvenating damaged and/or ageing tissues.

  4. Jean-Antoine Nollet: The father of experimental electrospray.

    PubMed

    Dumont, Quentin; Cole, Richard B

    2014-01-01

    The development of electrospray ionization mass spectrometry (ESI-MS) was a 20th century occurrence that underwent rapid acceleration especially in the 1990's. However, long prior to its coupling with mass spectrometry, the electrification of liquids had been studied in a variety of contexts. Although initial reports describing cone formation upon electrification of water drops came out of England, the first true experiments investigating the electrospray phenomenon were performed in the middle of the 18th century by Abbé Jean-Antoine Nollet. The current report, associated with the French Regional Issue of Mass Spectrometry Reviews, examines the contributions of Abbé Nollet to the earliest understanding of the electrospray phenomenon. A description of his accomplishments is placed in the context of the societal and scientific developments of the "Age of Enlightenment" out of which Jean-Antoine Nollet arose. © 2013 Wiley Periodicals, Inc.

  5. The electrospray and its application to targeted drug inhalation.

    PubMed

    Gomez, Alessandro

    2002-12-01

    This review explains the fundamentals of electrostatic spray (electrospray) atomization, with emphasis on operation in the so called cone-jet mode, which produces droplets with a very narrow size distribution. Since the control of droplet size is key to maximizing distal lung deposition, the electrospray should be well-suited to targeted drug inhalation. Electrospray droplets are a few micrometers in diameter, but they originate from a much larger nozzle, which allows nebulization of suspensions without clogging. Also discussed are: the physical principles of the break-up of the liquid ligament; droplet dispersion by Coulombic forces; and the most important scaling law linking the droplet size to liquid flow rate and liquid physical properties. The effects of the most critical of those properties may result in some restrictions on drug formulation. Droplets produced by electrospray are electrically charged, so to prevent electrostatic image forces from causing upper respiratory tract deposition. The charge is neutralized by generating a corona discharge of opposite polarity. Briefly discussed are the main differences between the laboratory systems (with which the electrospray has been quantitatively characterized during research in the past 10 years) and commercial electrospray inhalers under development at BattellePharma. Some remarkable miniaturization has incorporated liquid pump, power supply, breath activation, and dose counter into a palm-size portable device. The maximum flow rates dispersed from these devices are in the range of 8-16 microL/s, which makes them suitable for practical drug inhalation therapy. Fabrication is economically competitive with inexpensive nebulizers. Dramatic improvements in respirable dose efficiency (up to 78% by comparison with commercial metered-dose inhalers and dry powder inhalers) should ensure the commercialization of this promising technology for targeted drug inhalation.

  6. Generating electrospray from microchip devices using electroosmotic pumping

    SciTech Connect

    Ramsey, R.S.; Ramsey, J.M.

    1997-03-15

    A method of generating electrospray from solutions emerging from small channels etched on planer substrates in described. The fluids are delivered using electroosmotically induced pressures and are sprayed electrostatically from the terminus of a channel by applying an electrical potential of sufficient amplitude to generate the electrospray between the microchip and a conductor spaced from the channel terminus. No major modification of the microchip is required other than to expose a channel opening. The principles that regulate the fluid delivery are described and demonstrated. A spectrum for a test compound, tetrabutylammonium iodide, that was continuously electrophoresed was obtained by coupling the microchip to an ion trap mass spectrometer. 35 refs., 6 figs.

  7. Electrospray formation of ring-shaped silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Uchida, Kazuhiro; Higashi, Kazuhiko; Hishida, Koichi; Hotta, Atsushi; Miki, Norihisa

    2015-02-01

    Electrospray is one of the processes employed for the production of silica nanoparticles (NPs). We have experimentally determined that not only spherical but also ring-shaped NPs can be manufactured by electrospray, and that the shape of the NPs is dependent on ambient humidity and the substrate on which the NPs are deposited. Although the effect of humidity that reflects the evaporation characteristics of the suspension during flight has been reported, we have experimentally determined that the affinity of the sol suspension and the substrate play a crucial role in the formation of torus silica NPs.

  8. Applications of electrospinning/electrospraying in drug delivery.

    PubMed

    Jahangiri, Azin; Adibkia, Khosro

    2016-01-01

    During recent years, nanoscaled materials have gained much attention because of their applications in the field of pharmaceutical and biomedical sciences. Electrospinning/electrospraying, as simple, effective and single-step methods, are used in the preparation of nanostructured materials (nanofibers and nanobeads). They offer an opportunity for direct encapsulation of the different types of drug molecules. The generated nanomaterials possess high surface area with porous characteristics, and the liberation of the loaded drugs follows a controlled-release pattern. Because of their wide applications in medical/pharmaceutical researches, the aim of this editorial is to highlight the importance of electrospinning/electrospraying technologies in drug delivery.

  9. Applications of electrospinning/electrospraying in drug delivery

    PubMed Central

    Jahangiri, Azin; Adibkia, Khosro

    2016-01-01

    During recent years, nanoscaled materials have gained much attention because of their applications in the field of pharmaceutical and biomedical sciences. Electrospinning/electrospraying, as simple, effective and single-step methods, are used in the preparation of nanostructured materials (nanofibers and nanobeads). They offer an opportunity for direct encapsulation of the different types of drug molecules. The generated nanomaterials possess high surface area with porous characteristics, and the liberation of the loaded drugs follows a controlled-release pattern. Because of their wide applications in medical/pharmaceutical researches, the aim of this editorial is to highlight the importance of electrospinning/electrospraying technologies in drug delivery. PMID:27340617

  10. Plume collimation for laser ablation electrospray ionization mass spectrometry

    DOEpatents

    Vertes, Akos; Stolee, Jessica A.

    2016-06-07

    In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.

  11. Plume collimation for laser ablation electrospray ionization mass spectrometry

    DOEpatents

    Vertes, Akos; Stolee, Jessica A.

    2014-09-09

    In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.

  12. Low pressure electrospray ionization system and process for effective transmission of ions

    DOEpatents

    Tang, Keqi [Richland, WA; Page, Jason S [Kennewick, WA; Kelly, Ryan T [West Richland, WA; Smith, Richard D [Richland, WA

    2012-05-08

    Systems and methods that provide up to complete transmission of ions between coupled stages with low effective ion losses. An "interfaceless" electrospray ionization system is further described that operates an electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer. Furthermore, chambers maintained at different pressures can allow for more optimal operating conditions for an electrospray emitter and an ion guide.

  13. 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.

  14. Headspace analysis of new psychoactive substances using a Selective Reagent Ionisation-Time of Flight-Mass Spectrometer

    PubMed Central

    Acton, W. Joe; Lanza, Matteo; Agarwal, Bishu; Jürschik, Simone; Sulzer, Philipp; Breiev, Kostiantyn; Jordan, Alfons; Hartungen, Eugen; Hanel, Gernot; Märk, Lukas; Mayhew, Chris A.; Märk, Tilmann D.

    2014-01-01

    The rapid expansion in the number and use of new psychoactive substances presents a significant analytical challenge because highly sensitive instrumentation capable of detecting a broad range of chemical compounds in real-time with a low rate of false positives is required. A Selective Reagent Ionisation-Time of Flight-Mass Spectrometry (SRI-ToF-MS) instrument is capable of meeting all of these requirements. With its high mass resolution (up to m/Δm of 8000), the application of variations in reduced electric field strength (E/N) and use of different reagent ions, the ambiguity of a nominal (monoisotopic) m/z is reduced and hence the identification of chemicals in a complex chemical environment with a high level of confidence is enabled. In this study we report the use of a SRI-ToF-MS instrument to investigate the reactions of H3O+, O2+, NO+ and Kr+ with 10 readily available (at the time of purchase) new psychoactive substances, namely 4-fluoroamphetamine, methiopropamine, ethcathinone, 4-methylethcathinone, N-ethylbuphedrone, ethylphenidate, 5-MeO-DALT, dimethocaine, 5-(2-aminopropyl)benzofuran and nitracaine. In particular, the dependence of product ion branching ratios on the reduced electric field strength for all reagent ions was investigated and is reported here. The results reported represent a significant amount of new data which will be of use for the development of drug detection techniques suitable for real world scenarios. PMID:25844048

  15. Aqueous phototransformation of zinc pyrithione Degradation kinetics and byproduct identification by liquid chromatography--atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Sakkas, V A; Shibata, K; Yamaguchi, Y; Sugasawa, S; Albanis, T

    2007-03-16

    The photochemical behavior of the antifouling agent zinc pyrithione (ZnPT) was studied in aqueous media of different composition under simulated solar irradiation using a xenon light source. The influence of important constituents of natural water (dissolved organic matter and nitrate) was also examined using a multivariate kinetic model. It was found that photodegradation proceeds via a pseudo first-order reaction. Kinetic experiments were monitored by LC-MS and photolytic half-lives ranging between 9.2 and 15.1 min have been observed. The increasing concentration of dissolved organic matter (DOM) accelerates the photolysis reaction, while the effect of nitrate ions was also positive since it increased the degradation rate, but to a lesser extent. Irradiation of the aqueous ZnPT solutions gave rise to several transformation products that were isolated by means of solid-phase extraction using poly(styrene-divinylbenzene) extraction disks. These byproducts were identified using liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry. Besides 2-pyridinesulfonic-acid, other degradation products formed included pyridine-N-oxide, 2-mercaptopyridine, 2,2'-dithiobis(pyridine-N-oxide), 2,2-dipyridyl disulfide and the pyridine/pyrithione mixed disulfide, 2,2'-dithiobispyridine mono-N-oxide (PPMD).

  16. Thin-layer chromatography-matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry using particle suspension matrices.

    PubMed

    Crecelius, Anna; Clench, Malcolm R; Richards, Don S; Parr, Vic

    2002-06-07

    Particle suspension matrices have been successfully utilized for the analysis of tetracycline antibiotics by thin-layer chromatography-matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry (TLC-MALDI-TOF-MS). Particles of different materials and sizes have been investigated (Co-UFP, TiN, TiO2, Graphite and Silicon) by applying particle suspensions to eluted TLC plates. Mass spectra and mass chromatograms have been recorded directly from the TLC plates. Strong cationization by sodium and potassium was obtained in the positive ion mode, with [M+Na-NH3]+ ions being the predominant signals. The TLC-MALDI mass spectra recorded from graphite suspensions showed the lowest background noise and the highest peak intensities from the range of suspension matrices studied. The mass accuracy from graphite films was improved by adding the peptide Phe-Phe to the graphite suspensions. This allowed internal recalibration of the TLC-MALDI mass spectra acquired during a run. One major potential advantage of TLC-MALDI-TOF-MS has been demonstrated in the analysis of chlortetracycline and tetracycline in a mixture of oxytetracycline, chlortetracycline, tetracycline and minocycline. Examination of the TLC plate prior to MALDI analysis showed only an unresolved spot for chlortetracycline and tetracycline. However by investigation of the MALDI mass spectra and plotting of single ion chromatograms separate peaks for chlortetracycline and tetracycline could be obtained.

  17. Chemical derivatization for electrospray ionization mass spectrometry. 1. Alkyl halides, alcohols, phenols, thiols, and amines

    SciTech Connect

    Quirke, J.M.E.; Adams, C.L.; Van Berkel, G.J. )

    1994-04-15

    Derivatization strategies and specific derivatization reactions for conversion of simple alkyl halides, alcohols, phenols, thiols, and amines to ionic or solution-ionizable derivatives, that is [open quotes]electrospray active[close quotes] (ES-active) forms of the analyte, are presented. Use of these reactions allows detection of analytes among those listed that are not normally amenable to analysis by electrospray ionization mass spectrometry (ES-MS). In addition, these reactions provide for analysis specificity and flexibility through functional group specific derivatization and through the formation of derivatives that can be detected in positive ion or in negative ion mode. For a few of the functional groups, amphoteric derivatives are formed that can be analyzed in either positive or negative ion modes. General synthetic strategies for transformation of members of these five compound classes to ES-active species are presented along with illustrative examples of suitable derivatives. Selected derivatives were prepared using model compounds and the ES mass spectra obtained for these derivatives are discussed. The analytical utility of derivatization for ES-MS analysis is illustrated in three experiments: (1) specific detection of the major secondary alcohol in oil of peppermint, (2) selective detection of phenols within a synthetic mixture of phenols, and (3) identification of the medicinal amines within a commercially available cold medication as primary, secondary or tertiary. 65 refs., 3 figs., 3 tabs.

  18. Efficacy of point-of-entry copper--silver ionisation system in eradicating Legionella pneumophila in a tropical tertiary care hospital: implications for hospitals contaminated with Legionella in both hot and cold water.

    PubMed

    Chen, Y S; Lin, Y E; Liu, Y-C; Huang, W K; Shih, H Y; Wann, S R; Lee, S S; Tsai, H C; Li, C H; Chao, H L; Ke, C M; Lu, H H; Chang, C L

    2008-02-01

    A medical centre in Southern Taiwan experienced an outbreak of nosocomial Legionnaires' disease, with the water distribution system thought to be the source of the infection. Even after two superheats and flush, the rate of Legionella positivity in distal sites in hospital wards and intensive care units (ICUs) was 14% and 66%, respectively. Copper-silver ionisation was therefore implemented in an attempt to control Legionella colonisation in both hot- and cold-water systems. Environmental cultures and ion concentration testing were performed to evaluate the efficacy of ionisation. When the system was activated, no significant change in rate of Legionella positivity in the hospital wards (20% vs baseline of 30%) and ICUs (28% vs baseline of 34%) of the test buildings over a three-month period was found, although all Legionella positivity rates were below 30%, an arbitrary target for Legionnaires' disease prevention. When ion concentrations were increased from month 4 to month 7, however, the rate of Legionella positivity decreased significantly to 5% (mean) in hospital wards (P=0.037) and 16% (mean) in ICUs (P=0.037). Legionella positivity was further reduced to 0% in hospital wards and 5% (mean) in ICUs while 50% sites were still positive for Legionella in a control building. Although Legionella was not completely eradicated during the study period, no culture- or urine-confirmed hospital-acquired Legionnaires' disease was reported. Ionisation was effective in controlling Legionella for both hot and cold water, and may be an attractive alternative as a point-of-entry systematic disinfection solution for Legionella.

  19. Rapid separation of phosphopeptides by microchip electrophoresis-electrospray ionization mass spectrometry.

    PubMed

    Ollikainen, Elisa; Bonabi, Ashkan; Nordman, Nina; Jokinen, Ville; Kotiaho, Tapio; Kostiainen, Risto; Sikanen, Tiina

    2016-04-01

    Protein phosphorylation is a significant biological process, but separation of phosphorylated peptide isomers is often challenging for many analytical techniques. We developed a microchip electrophoresis (MCE) method for rapid separation of phosphopeptides with on-chip electrospray ionization (ESI) facilitating online sample introduction to the mass spectrometer (MS). With the method, two monophosphorylated positional isomers of insulin receptor peptide (IR1A and IR1B) and a triply phosphorylated insulin receptor peptide (IR3), all with the same amino acid sequence, were separated from the nonphosphorylated peptide (IR0) in less than one minute. For efficient separation of the positional peptide isomers from each other derivatization with 9-fluorenylmethyl reagents (either chloroformate, Fmoc-Cl, or N-succinimidyl carbonate, Fmoc-OSu) was required before the analysis. The derivatization improved not only the separation of the monophosphorylated positional peptide isomers in MCE, but also identification of the phosphorylation site based on MS/MS.

  20. What Protein Charging (and Supercharging) Reveal about the Mechanism of Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Ogorzalek Loo, Rachel R.; Lakshmanan, Rajeswari; Loo, Joseph A.

    2014-10-01

    Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range, and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate with those observed by ESI-MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase, the extent of charging. This region incorporates properties (e.g., basicities) intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging ("supercharging") such as m-NBA, sulfolane, and 3-nitrobenzonitrile increase analyte charge from "denaturing" and "native" solvent systems. It is suggested that additives' Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carrying fewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte).

  1. What Protein Charging (and Supercharging) Reveal about the Mechanism of Electrospray Ionization

    PubMed Central

    Loo, Rachel R. Ogorzalek; Lakshmanan, Rajeswari

    2014-01-01

    Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate to those observed by ESI– MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase the extent of charging. This region incorporates properties, e.g., basicities, intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging (“supercharging”) such as m–NBA, sulfolane, and 3–nitrobenzonitrile increase analyte charge from “denaturing” and “native” solvent systems. It is suggested that additives’ Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carryingfewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte). PMID:25135609

  2. Preparation and characterization of polycaprolactone microspheres by electrospraying

    PubMed Central

    Zhou, Feng-Lei; Hubbard Cristinacce, Penny L.; Eichhorn, Stephen J.; Parker, Geoff J. M.

    2016-01-01

    ABSTRACT The ability to reproducibly produce and effectively collect electrosprayed polymeric microspheres with controlled morphology and size in bulk form is challenging. In this study, microparticles were produced by electrospraying polycaprolactone (PCL) of various molecular weights and solution concentrations in chloroform, and by collecting materials on different substrates. The resultant PCL microparticles were characterized by optical and electron microscopy to investigate the effect of molecular weight, solution concentration, applied voltage, working distance, and flow rate on their morphology and size. The work demonstrates the key role of a moderate molecular weight and/or solution concentration in the formation of spherical PCL particles via an electrospraying process. Increasing the applied voltage was found to produce smaller and more uniform PCL microparticles. There was a relatively low increase in the particle average size with an increase in the working distance and flow rate. Four types of substrates were adopted to collect electrosprayed PCL particles: a glass slide, aluminium foil, liquid bath, and copper wire. Unlike 2D bulk structures collected on the other substrates, a 3D tubular structure of microspheres was formed on the copper wire which could find application in the construction of 3D tumor mimics. PMID:27928195

  3. Infrared laser-assisted desorption electrospray ionization mass spectrometry.

    PubMed

    Rezenom, Yohannes H; Dong, Jianan; Murray, Kermit K

    2008-02-01

    We have used an infrared laser for desorption of material and ionization by interaction with electrosprayed solvent. Infrared laser-assisted desorption electrospray ionization (IR LADESI) mass spectrometry was used for the direct analysis of water-containing samples under ambient conditions. An ion trap mass spectrometer was modified to include a pulsed Er:YAG laser at 2.94 microm wavelength coupled into a germanium oxide optical fiber for desorption at atmospheric pressure and a nanoelectrospray source for ionization. Analytes in aqueous solution were placed on a stainless steel target and irradiated with the pulsed IR laser. Material desorbed and ablated from the target was ionized by a continuous stream of charged droplets from the electrosprayed solvent. Peptide and protein samples analyzed using this method yield mass spectra similar to those obtained by conventional electrospray. Blood and urine were analyzed without sample pretreatment to demonstrate the capability of IR LADESI for direct analysis of biological fluids. Pharmaceutical products were also directly analyzed. Finally, the role of water as a matrix in the IR LADESI process is discussed.

  4. Metal-insulator-metal capacitor using electrosprayed nanoparticles

    NASA Astrophysics Data System (ADS)

    Véliz, Bremnen; Bermejo, Sandra; Coll, Arnau; Castañer, Luis

    2014-07-01

    An electrospray technique has been used to deposit SiO2 nanoparticles as insulator layer of a metal-insulator-metal device. Impedance spectroscopy measurements show that a 4.4 factor increase in capacitance is achieved compared to a continuous dielectric layer of the same permittivity and dimensions.

  5. 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…

  6. 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…

  7. Quantification of ethylenediamine-N,N'-bis(hydroxysulfophenylacetic) acid regioisomers and structural characterisation of its related polycondensation products by porous graphitic carbon high-performance liquid chromatography coupled to electrospray tandem mass spectrometry.

    PubMed

    Biasone, Alessandro; Cianci, Giusto; Di Tommaso, Donata; Piaggesi, Alberto; D'Alessandro, Nicola

    2013-10-18

    Among the commercial ethylenediamine-N,N'-bis(2-hydroxy)phenylacetic acid/iron(III) derivatives, ethylenediamine-N,N'-bis(2-hydroxy-5-sulphophenylacetic) acid/iron(III) (EDDHSA/Fe) represents one of the promising chelates for the treatment of chlorotic plants. Industrial synthesis of EDDHSA/Fe leads to relevant amounts of o,o-EDDHSA condensation products (o,o-EDDHSAcps) and other secondary products that might have important relevance from the agronomic point of view. However, their chemical structures have remained unknown to date. Analysis of iron complexes by ion-pair reversed-phase chromatography, coupled with electrospray tandem mass spectrometry revealed the presence of the meso-o,o-EDDHSA/Fe, rac-o,o-EDDHSA/Fe, o,p-EDDHSA/Fe regioisomers, the hydroxyl derivative of o,o-EDDHSA/Fe, and the three main EDDHSA condensation products chelating the iron(III) (EDDHSAcps/nFe). However, the chromatographic peaks of EDDHSAcps/Fe are not well resolved due to the large numbers of stereoisomers and the poor efficiency of the ion-pair reversed-phase separation method. An alternative chromatographic method is based on porous graphitic carbon (PGC) separation after pre-column decomplexation of the chelates with trifluoracetic acid, which was developed to allow detection of EDDHSA stereo/regioisomers, EDDHSAcps, and low-molecular-weight by-products. This extensive PGC-HPLC-ESI-MS/MS investigation provides quantitative determination of meso-o,o-EDDHSA, rac-o,o-EDDHSA and o,p-EDDHSA, in addition to characterisation of EDDHSAcps and the low-molecular-weight by-products. PGC separation coupled to a triple quadrupole ESI-MS detector allowed characterisation of free ligands using collision-induced dissociation experiments in positive and negative ionisation mode, providing comparative evaluation of EDDHSAcps in three commercial samples. For detection, the PGC-HPLC-ESI-MS/MS is the best method according to the limit of quantification and limit of detection (picomolar and sub

  8. Automated Sampling and Imaging of Analytes Separated on Thin-Layer Chromatography Plates Using Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J; Kertesz, Vilmos

    2006-01-01

    Modest modifications to the atmospheric sampling capillary of a commercial electrospray mass spectrometer and upgrades to an in-house developed surface positioning control software package (HandsFree TLC/MS ) were used to enable the automated sampling and imaging of analytes on and/or within large area surface substrates using desorption electrospray ionization mass spectrometry. Sampling and imaging of rhodamine dyes separated on TLC plates were used to illustrate some of the practical applications of this system. Examples are shown for user-defined spot sampling from separated bands on a TLC plate (one or multiple spots), scanning of a complete development lane (one or multiple lanes), or imaging of analyte bands in a development lane (i.e. multiple lane scans with close spacing). The post data processing and data display aspects of the software system are also discussed.

  9. Structural analysis of chromophore-labeled disaccharides and oligosaccharides by electrospray ionization mass spectrometry and high-performance liquid chromatography/electrospray ionization mass spectrometry.

    PubMed

    Li, D T; Her, G R

    1998-07-01

    Disaccharides and linear oligosaccharides were labeled with p-aminobenzoic ethyl ester (ABEE) chromophore and analyzed by negative ion electrospray ionization mass spectrometry (ESIMS). The formation of glycosylamines rather than reductive amination in the labeling reaction produced many characteristic fragment ions under in source collision-induced dissociation (CID). These ions provided unambiguous assignment of the position of the glycosidic linkages. This approach was extended to the analysis of linkages and the sequence of the linkages of several linear oligosaccharides. Additionally, the anomeric configuration of ABEE-labeled 1-3-, 1-4- and 1-6-linked glucose disaccharides could be differentiated according to the relative abundance of characteristic ions. Disaccharides with the same linkage but different monosaccharide compositions could be analyzed by on-line coupling of high-performance liquid chromatography with ESIMS.

  10. Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

    NASA Astrophysics Data System (ADS)

    Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

    2017-06-01

    Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. [Figure not available: see fulltext.

  11. Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens.

    PubMed

    Swanson, Kenneth D; Spencer, Sandra E; Glish, Gary L

    2016-11-28

    Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H](+). These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. Graphical Abstract ᅟ.

  12. Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

    NASA Astrophysics Data System (ADS)

    Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

    2016-11-01

    Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures.

  13. KINETIC SIMULATIONS OF THERMOLUMINESCENCE DOSE RESPONSE: LONG OVERDUE CONFRONTATION WITH THE EFFECTS OF IONISATION DENSITY.

    PubMed

    Horowitz, Y S; Eliyahu, I; Oster, L

    2016-12-01

    The reader will time-travel through almost seven decades of kinetic models and mathematical simulations of thermoluminescence (TL) characteristics based on the band-gap theory of the solid state. From post-World-War II, ideas concerning electron trapping mechanisms to the highly idealised one trap-one recombination (OTOR) model first elaborated in 1956 but still in 'high gear' today. The review caresses but purposely avoids in-depth discussion of the endless stream of papers discussing the intricacies of glow peak shapes arising from first-order, second-order, mixed-order and general-order kinetics predominantly based on non-interacting systems, and then on to the more physically realistic scenarios that have attempted to analyse complex systems involving ever greater numbers of interacting trapping centres, luminescent centres and non-luminescent centres. The review emphasises the difficulty the band-gap models have in the simulation of dose response linear/supralinear behaviour and especially the dependence of the supralinearity on ionisation density. The significance of the non-observation of filling-rate supralinearity in the absorption stage is emphasised since it removes from consideration the possibility of TL supralinearity arising from irradiation stage supralinearity. The importance of the simultaneous action of both localised and delocalised transitions has gradually penetrated the mindset of the community of kinetic researchers, but most simulations have concentrated on the shape of glow peaks and the extraction of the glow peak parameters, E (the thermal activation energy) and s (the attempt-to-escape frequency). The simulation of linear/supralinear dose response and its dependence on ionisation density have been largely avoided until recently due to the fundamental schism between the effects of ionisation density and some basic assumptions of the band-gap model. The review finishes with an in-depth presentation and discussion of the most recent

  14. Monte Carlo configuration interaction applied to multipole moments, ionisation energies and electron affinities.

    PubMed

    Coe, Jeremy P; Taylor, Daniel J; Paterson, Martin J

    2013-05-15

    The method of Monte Carlo configuration interaction (MCCI) (Greer, J. Chem. Phys. 1995a, 103, 1821; Tong, Nolan, Cheng, and Greer, Comp. Phys. Comm. 2000, 142, 132) is applied to the calculation of multipole moments. We look at the ground and excited state dipole moments in carbon monoxide. We then consider the dipole of NO, the quadrupole of N2 and of BH. An octupole of methane is also calculated. We consider experimental geometries and also stretched bonds. We show that these nonvariational quantities may be found to relatively good accuracy when compared with full configuration interaction results, yet using only a small fraction of the full configuration interaction space. MCCI results in the aug-cc-pVDZ basis are seen to generally have reasonably good agreement with experiment. We also investigate the performance of MCCI when applied to ionisation energies and electron affinities of atoms in an aug-cc-pVQZ basis. We compare the MCCI results with full configuration interaction quantum Monte Carlo (Booth and Alavi, J. Chem. Phys. 2010, 132, 174104; Cleland, Booth, and Alavi, J. Chem. Phys. 2011, 134, 024112) and "exact" nonrelativistic results (Booth and Alavi, J. Chem. Phys. 2010, 132, 174104; Cleland, Booth, and Alavi, J. Chem. Phys. 2011, 134, 024112). We show that MCCI could be a useful alternative for the calculation of atomic ionisation energies however electron affinities appear much more challenging for MCCI. Due to the small magnitude of the electron affinities their percentage errors can be high, but with regards to absolute errors MCCI performs similarly for ionisation energies and electron affinities.

  15. Comparison of low and high dose ionising radiation using topological analysis of gene coexpression networks.

    PubMed

    Ray, Monika; Yunis, Reem; Chen, Xiucui; Rocke, David M

    2012-05-17

    The growing use of imaging procedures in medicine has raised concerns about exposure to low-dose ionising radiation (LDIR). While the disastrous effects of high dose ionising radiation (HDIR) is well documented, the detrimental effects of LDIR is not well understood and has been a topic of much debate. Since little is known about the effects of LDIR, various kinds of wet-lab and computational analyses are required to advance knowledge in this domain. In this paper we carry out an "upside-down pyramid" form of systems biology analysis of microarray data. We characterised the global genomic response following 10 cGy (low dose) and 100 cGy (high dose) doses of X-ray ionising radiation at four time points by analysing the topology of gene coexpression networks. This study includes a rich experimental design and state-of-the-art computational systems biology methods of analysis to study the differences in the transcriptional response of skin cells exposed to low and high doses of radiation. Using this method we found important genes that have been linked to immune response, cell survival and apoptosis. Furthermore, we also were able to identify genes such as BRCA1, ABCA1, TNFRSF1B, MLLT11 that have been associated with various types of cancers. We were also able to detect many genes known to be associated with various medical conditions. Our method of applying network topological differences can aid in identifying the differences among similar (eg: radiation effect) yet very different biological conditions (eg: different dose and time) to generate testable hypotheses. This is the first study where a network level analysis was performed across two different radiation doses at various time points, thereby illustrating changes in the cellular response over time.

  16. IFU Spectroscopy of Southern Planetary Nebulae V: Low-Ionisation Structures

    NASA Astrophysics Data System (ADS)

    Ali, A.; Dopita, M. A.

    2017-08-01

    In this fifth paper of the series, we examine the spectroscopy and morphology of four southern Galactic planetary nebulae Hen 2-141, NGC 5307, IC 2553, and PB 6 using new integral field spectroscopy data. The morphologies and ionisation structures of the sample are given as a set of emission-line maps. In addition, the physical conditions, chemical compositions, and kinematical characteristics of these objects are derived. The results show that PB 6 and Hen 2-141 are of very high excitation classes and IC 2553 and NGC 5307 are mid to high excitation objects. The elemental abundances reveal that PB 6 is of Type I, Hen 2-141 and IC 2553 are of Type IIa, and NGC 5307 is of Type IIb/III. The observations unveil the presence of well-defined low-ionisation structures or `knots' in all objects. The diagnostic diagrams reveal that the excitation mechanism of these knots is probably by photoionisation of dense material by the nebular central stars. The physical analysis of six of these knots show no significant differences with their surrounding nebular gas, except their lower electron densities. In spite of the enhancement of the low-ionisation emission lines of these knots, their chemical abundances are nearly comparable to their surrounding nebulae, with the exception of perhaps slightly higher nitrogen abundances in the NGC 5307 knots. The integrated spectrum of IC 2553 reveals that nearly all key lines that have led researchers to characterise its central star as a weak-emission line star type are in fact of nebular origin.

  17. Impact ionisation spectra from hypervelocity impacts using aliphatic poly(methyl methacrylate) microparticle projectiles.

    PubMed

    Burchell, Mark J; Armes, Steven P

    2011-02-28

    We report impact ionisation spectra from spherical poly(methyl methacrylate) (PMMA) microparticles of 724 nm diameter impacting a rhodium target. These projectiles were coated with an ultrathin (~11 nm) overlayer of polypyrrole, an electrically conducting organic polymer; this enabled the accumulation of sufficient surface charge to allow electrostatic acceleration up to speeds of 4 to 8 km s(-1) using a high-voltage Van de Graaff instrument. A grid above the target (held at 3.33 kV cm(-1) with respect to the target) accelerated the cations that were generated during the hypervelocity impacts, and these ions then drifted to a charge detector. By measuring the collected charge vs. time and assuming only single ionisation events, time-of-flight mass spectra were obtained. Strong signals were observed for cationic species with ions of m/z 41, 65 and 115. There were also minor contributions from cations with masses ranging from m/z 29 to 142. The three major signals are assigned to fragment ions (C(3)H(5)(+), C(4)H(5)O(+)/C(5)H(9)(+) and C(6)H(11)O(2)(+)) which are known to be associated with the decomposition of PMMA. These impact ionisation spectra differ significantly from those reported earlier using polystyrene (PS) microparticles. The aliphatic PMMA microparticles generate small (m/z <100) fragment ions more readily at lower speeds than the predominantly aromatic PS microparticles, where speeds of at least 10 km s(-1) are typically required for substantial yields of low-mass fragment ions. This correlates well with the well-known greater chemical and thermal fragility of PMMA compared to PS. The PMMA microparticles should prove useful synthetic mimics for aliphatic carbonaceous micrometeorites. Copyright © 2011 John Wiley & Sons, Ltd.

  18. Comparison of low and high dose ionising radiation using topological analysis of gene coexpression networks

    PubMed Central

    2012-01-01

    Background The growing use of imaging procedures in medicine has raised concerns about exposure to low-dose ionising radiation (LDIR). While the disastrous effects of high dose ionising radiation (HDIR) is well documented, the detrimental effects of LDIR is not well understood and has been a topic of much debate. Since little is known about the effects of LDIR, various kinds of wet-lab and computational analyses are required to advance knowledge in this domain. In this paper we carry out an “upside-down pyramid” form of systems biology analysis of microarray data. We characterised the global genomic response following 10 cGy (low dose) and 100 cGy (high dose) doses of X-ray ionising radiation at four time points by analysing the topology of gene coexpression networks. This study includes a rich experimental design and state-of-the-art computational systems biology methods of analysis to study the differences in the transcriptional response of skin cells exposed to low and high doses of radiation. Results Using this method we found important genes that have been linked to immune response, cell survival and apoptosis. Furthermore, we also were able to identify genes such as BRCA1, ABCA1, TNFRSF1B, MLLT11 that have been associated with various types of cancers. We were also able to detect many genes known to be associated with various medical conditions. Conclusions Our method of applying network topological differences can aid in identifying the differences among similar (eg: radiation effect) yet very different biological conditions (eg: different dose and time) to generate testable hypotheses. This is the first study where a network level analysis was performed across two different radiation doses at various time points, thereby illustrating changes in the cellular response over time. PMID:22594378

  19. Characterisation of the muon beams for the Muon Ionisation Cooling Experiment

    SciTech Connect

    Adams, D.; et al.,

    2013-10-01

    A novel single-particle technique to measure emittance has been developed and used to characterise seventeen different muon beams for the Muon Ionisation Cooling Experiment (MICE). The muon beams, whose mean momenta vary from 171 to 281 MeV/c, have emittances of approximately 1.5--2.3 \\pi mm-rad horizontally and 0.6--1.0 \\pi mm-rad vertically, a horizontal dispersion of 90--190 mm and momentum spreads of about 25 MeV/c. There is reasonable agreement between the measured parameters of the beams and the results of simulations. The beams are found to meet the requirements of MICE.

  20. The WISSH quasars project. I. Powerful ionised outflows in hyper-luminous quasars

    NASA Astrophysics Data System (ADS)

    Bischetti, M.; Piconcelli, E.; Vietri, G.; Bongiorno, A.; Fiore, F.; Sani, E.; Marconi, A.; Duras, F.; Zappacosta, L.; Brusa, M.; Comastri, A.; Cresci, G.; Feruglio, C.; Giallongo, E.; La Franca, F.; Mainieri, V.; Mannucci, F.; Martocchia, S.; Ricci, F.; Schneider, R.; Testa, V.; Vignali, C.

    2017-02-01

    Models and observations suggest that both the power and effects of AGN feedback should be maximised in hyper-luminous (LBol > 1047 erg s-1) quasars, i.e. objects at the brightest end of the AGN luminosity function. In this paper, we present the first results of a multiwavelength observing programme, focusing on a sample of WISE/SDSS selected hyper-luminous (WISSH) broad-line quasars at z ≈ 1.5-5. The WISSH quasars project has been designed to reveal the most energetic AGN-driven outflows, estimate their occurrence at the peak of quasar activity, and extend the study of correlations between outflows and nuclear properties up to poorly investigated, extreme AGN luminosities, i.e. LBol 1047 - 1048 erg s-1. We present near-infrared, long-slit LBT/LUCI1 spectroscopy of five WISSH quasars at z ≈ 2.3 - 3.5, showing prominent [OIII] emission lines with broad (FWHM 1200-2200 km s-1) and skewed profiles. The luminosities of these broad [OIII] wings are the highest measured so far, with L[OIII]broad ≳ 5 × 1044 erg s-1, and reveal the presence of powerful ionised outflows with associated mass outflow rates Ṁ ≳ 1700M⊙ yr-1 and kinetic powers Ėkin ≳ 1045 erg s-1. Although these estimates are affected by large uncertainties because of the use of [OIII] as a tracer of ionised outflows and the very basic outflow model adopted here, these results suggest that in our hyper-luminous targets the AGN is highly efficient at pushing large amounts of ionised gas outwards. Furthermore, the mechanical outflow luminosities measured for WISSH quasars correspond to higher percentages ( 1-3%) of LBol than those derived for AGN with lower LBol. Our targets host very massive (MBH ≳ 2 × 109M⊙) black holes that are still accreting at a high rate (i.e. a factor of 0.4-3 of the Eddington limit). These findings clearly demonstrate that WISSH quasars offer the opportunity to probe the extreme end of both luminosity and supermassive black holes (SMBH) mass functions and revealing

  1. Current trends in estimating risk of cancer from exposure to low doses of ionising radiation.

    PubMed

    Majer, Marija; Knežević, Zeljka; Saveta, Miljanić

    2014-09-29

    Although ionising radiation has proven beneficial in the diagnosis and therapy of a number of diseases, one should keep in mind that irradiating healthy tissue may increase the risk of cancer. In order to justify an exposure to radiation, both the benefits and the risks must be evaluated and compared. The deleterious effects of medium and high doses are well known, but it is much less clear what effects arise from low doses (below 0.1 Gy), which is why such risk estimates are extremely important. This review presents the current state, important assumptions and steps being made in deriving cancer risk estimates for low dose exposures.

  2. Skin dose measurements using radiochromic films, TLDS and ionisation chamber and comparison with Monte Carlo simulation.

    PubMed

    Alashrah, Saleh; Kandaiya, Sivamany; Maalej, Nabil; El-Taher, A

    2014-12-01

    Estimation of the surface dose is very important for patients undergoing radiation therapy. The purpose of this study is to investigate the dose at the surface of a water phantom at a depth of 0.007 cm as recommended by the International Commission on Radiological Protection and International Commission on Radiation Units and Measurement with radiochromic films (RFs), thermoluminescent dosemeters and an ionisation chamber in a 6-MV photon beam. The results were compared with the theoretical calculation using Monte Carlo (MC) simulation software (MCNP5, BEAMnrc and DOSXYZnrc). The RF was calibrated by placing the films at a depth of maximum dose (d(max)) in a solid water phantom and exposing it to doses from 0 to 500 cGy. The films were scanned using a transmission high-resolution HP scanner. The optical density of the film was obtained from the red component of the RGB images using ImageJ software. The per cent surface dose (PSD) and percentage depth dose (PDD) curve were obtained by placing film pieces at the surface and at different depths in the solid water phantom. TLDs were placed at a depth of 10 cm in a solid water phantom for calibration. Then the TLDs were placed at different depths in the water phantom and were exposed to obtain the PDD. The obtained PSD and PDD values were compared with those obtained using a cylindrical ionisation chamber. The PSD was also determined using Monte Carlo simulation of a LINAC 6-MV photon beam. The extrapolation method was used to determine the PSD for all measurements. The PSD was 15.0±3.6% for RF. The TLD measurement of the PSD was 16.0±5.0%. The (0.6 cm(3)) cylindrical ionisation chamber measurement of the PSD was 50.0±3.0%. The theoretical calculation using MCNP5 and DOSXYZnrc yielded a PSD of 15.0±2.0% and 15.7±2.2%. In this study, good agreement between PSD measurements was observed using RF and TLDs with the Monte Carlo calculation. However, the cylindrical chamber measurement yielded an overestimate of the PSD

  3. Characterisation of the muon beams for the Muon Ionisation Cooling Experiment

    NASA Astrophysics Data System (ADS)

    Adams, D.; Adey, D.; Alekou, A.; Apollonio, M.; Asfandiyarov, R.; Back, J.; Barber, G.; Barclay, P.; de Bari, A.; Bayes, R.; Bayliss, V.; Bertoni, R.; Blackmore, V. J.; Blondel, A.; Blot, S.; Bogomilov, M.; Bonesini, M.; Booth, C. N.; Bowring, D.; Boyd, S.; Bradshaw, T. W.; Bravar, U.; Bross, A. D.; Capponi, M.; Carlisle, T.; Cecchet, G.; Charnley, G.; Cobb, J. H.; Colling, D.; Collomb, N.; Coney, L.; Cooke, P.; Courthold, M.; Cremaldi, L. M.; DeMello, A.; Dick, A. J.; Dobbs, A.; Dornan, P.; Fayer, S.; Filthaut, F.; Fish, A.; Fitzpatrick, T.; Fletcher, R.; Forrest, D.; Francis, V.; Freemire, B.; Fry, L.; Gallagher, A.; Gamet, R.; Gourlay, S.; Grant, A.; Graulich, J. S.; Griffiths, S.; Hanlet, P.; Hansen, O. M.; Hanson, G. G.; Harrison, P.; Hart, T. L.; Hartnett, T.; Hayler, T.; Heidt, C.; Hills, M.; Hodgson, P.; Hunt, C.; Iaciofano, A.; Ishimoto, S.; Kafka, G.; Kaplan, D. M.; Karadzhov, Y.; Kim, Y. K.; Kolev, D.; Kuno, Y.; Kyberd, P.; Lau, W.; Leaver, J.; Leonova, M.; Li, D.; Lintern, A.; Littlefield, M.; Long, K.; Lucchini, G.; Luo, T.; Macwaters, C.; Martlew, B.; Martyniak, J.; Middleton, S.; Moretti, A.; Moss, A.; Muir, A.; Mullacrane, I.; Nebrensky, J. J.; Neuffer, D.; Nichols, A.; Nicholson, R.; Nugent, J. C.; Onel, Y.; Orestano, D.; Overton, E.; Owens, P.; Palladino, V.; Palmer, R. B.; Pasternak, J.; Pastore, F.; Pidcott, C.; Popovic, M.; Preece, R.; Prestemon, S.; Rajaram, D.; Ramberger, S.; Rayner, M. A.; Ricciardi, S.; Richards, A.; Roberts, T. J.; Robinson, M.; Rogers, C.; Ronald, K.; Rubinov, P.; Rucinski, R.; Rusinov, I.; Sakamoto, H.; Sanders, D. A.; Santos, E.; Savidge, T.; Smith, P. J.; Snopok, P.; Soler, F. J. P.; Stanley, T.; Summers, D. J.; Takahashi, M.; Tarrant, J.; Taylor, I.; Tortora, L.; Torun, Y.; Tsenov, R.; Tunnell, C. D.; Vankova, G.; Verguilov, V.; Virostek, S. P.; Vretenar, M.; Walaron, K.; Watson, S.; White, C.; Whyte, C. G.; Wilson, A.; Wisting, H.; Zisman, M. S.

    2013-10-01

    A novel single-particle technique to measure emittance has been developed and used to characterise seventeen different muon beams for the Muon Ionisation Cooling Experiment (MICE). The muon beams, whose mean momenta vary from 171 to 281 MeV/ c, have emittances of approximately 1.2-2.3 π mm-rad horizontally and 0.6-1.0 π mm-rad vertically, a horizontal dispersion of 90-190 mm and momentum spreads of about 25 MeV/ c. There is reasonable agreement between the measured parameters of the beams and the results of simulations. The beams are found to meet the requirements of MICE.

  4. EVOLUTION OF THE IEC AND EN STANDARDS FOR INDIVIDUAL MONITORING OF IONISING RADIATION.

    PubMed

    Voytchev, M; Behrens, R; Ambrosi, P; Radev, R; Chiaro, P

    2016-09-01

    This article presents the evolution of the International Electrotechnical Commission (IEC) and the European standards for individual monitoring of ionising radiation issued, respectively, from the committees IEC/Sub Committee 45B and European Committee for Electro-technical Standardization/Technical Committee 45B 'Radiation protection instrumentation'. Standards for passive individual photon and beta dosimetry systems as well as those for active individual monitors are discussed. A neutron ambient dose equivalent (rate) meter standard and a technical report concerning the determination of uncertainty in measurement are also covered. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. Importance of direct anthropogenic emissions of formic acid measured by a chemical ionisation mass spectrometer (CIMS) during the Winter ClearfLo Campaign in London, January 2012

    NASA Astrophysics Data System (ADS)

    Bannan, Thomas J.; Bacak, Asan; Muller, Jennifer B. A.; Booth, A. Murray; Jones, Benjamin; Le Breton, Michael; Leather, Kimberley E.; Ghalaieny, Mohamed; Xiao, Ping; Shallcross, Dudley E.; Percival, Carl J.

    2014-02-01

    Formic acid, an ubiquitous trace gas in the atmosphere, was measured using a chemical ionisation mass spectrometer (CIMS) during the winter ClearfLo campaign in London, 2012. Daily calibrations of formic acid gave sensitivities of 3 ion counts s-1 pptv-1 for the complete campaign and a limit of detection of 2 ppt. No correlation with nitric acid was observed, R2 of 0.137, indicating no significant secondary source of formic acid. However, a strong positive correlation with NOx, CO, and production in line with rush hour periods indicated a direct anthropogenic emission of formic acid from vehicle emissions. Peaks of 6.7 ppb of formic acid were observed with a mean of 610 ppt. Global models indicated that this emission source dominates in the northern hemisphere where global models underestimate formic acid most significantly, thus increasing the accuracy of modelling of global formic acid emissions.

  6. Insights into the mechanism of protein electrospray ionization from salt adduction measurements.

    PubMed

    Yue, Xuanfeng; Vahidi, Siavash; Konermann, Lars

    2014-08-01

    The mechanisms whereby protein ions are liberated from charged droplets during electrospray ionization (ESI) remain under investigation. Compact conformers electrosprayed from aqueous solution in positive ion mode likely follow the charged residue model (CRM), which envisions analyte release after solvent evaporation to dryness. The concentration of nonvolatile salts such as NaCl increases sharply within vanishing CRM droplets, promoting nonspecific pairing of Cl(-) and Na(+) with charged groups on the protein surface. For unfolded proteins, it has been proposed that ion formation occurs via the chain ejection model (CEM). During the CEM proteins are expelled from the droplet long before complete solvent evaporation has taken place. Here we examine whether salt adduction levels support the view that folded and unfolded proteins follow different ESI mechanisms. Solvent evaporation during the CEM is expected to be less extensive and, hence, the salt concentration at the point of protein release should be substantially lower than for the CRM. CEM ions should therefore exhibit lower adduction levels than CRM species. We explore the adduction behavior of several proteins that were chosen to allow comparative studies on folded and unfolded structures in the same solution. In-source activation eliminates chloride adducts via HCl release, generating protein ions that are heterogeneously charged because of sodiation and protonation. Sodiation levels measured under such conditions provide estimates of the salt adduction behavior experienced by the "nascent" analyte ions. Sodiation levels are significantly reduced for unfolded proteins, supporting the view that these species are indeed formed via the CEM.

  7. Electrospray ionization mass spectrometric studies on the characteristic fragmentation of Asp/cyclen conjugates.

    PubMed

    Ma, Chunying; Li, Chao; Luan, Xingrong; Zhang, Jin; Qiao, Renzhong; Zhao, Yufen

    2014-03-30

    Differentiation and structural characterization of Asp/cyclen conjugates by electrospray ionization tandem mass spectrometry (ESI-MS(n)) are significantly important for their biomedical application. Hence, the present study is conducted. The fragmentations of Asp/cyclen conjugates generated by positive ion mode electrospray ionization were examined here by low-energy collision-induced dissociation (CID). ESI-MS(n) spectra of cyclen were acquired to confirm cyclen contraction products derived from the studied compounds. The fragments derived from the Asp/cyclen conjugates were proved by deuterium-exchange experiments. Asp/cyclen conjugates displayed characteristic dissociation pathways, including cleavages of amide bonds, loss of NH3 and cyclen contraction pathways. It was observed that cleavages of C-terminal amide bonds generated b2 and b2  + H2O ions from the protonated CyclenAspAspAsp and a b1  + H2O ion from the protonated CyclenAspAsp. In addition, various cyclen contraction products were also observed. In ESI-MS(n) spectra of studied compounds, fragments of bn-1  + H2O or cyclic anhydride were generated due to facile mobilization of C-terminal or side-chain COOH protons. In addition, the cyclen contraction products were detected. These results might provide sufficient information for the identification of Asp/cyclen conjugates by mass spectrometry. Copyright © 2014 John Wiley & Sons, Ltd.

  8. Effect of instrument tuning on the detectabilityof biopolymers in electrospray ionization mass spectrometry.

    PubMed

    Oberacher, Herbert; Walcher, Wolfgang; Huber, Christian G

    2003-01-01

    Electrospray ionization mass spectrometry of multiply charged biopolymer ions of different molecular size revealed a strong influence of tuning parameters on their detectability in quadrupole ion trap and triple quadrupole mass spectrometers. Hence, after optimizing the ion optical parameters with the signal of the 4- charge state of (dT)(24) (low charge state tuning), a tenfold increase in the signal-to-noise ratio for a mixture of oligodeoxythymidylic acids (n = 12-18) was obtained compared with the results achieved with tune parameters optimized with a synthetic 80-mer oligodeoxynucleotide. By contrast, a detection limit in the upper femtomole region could only be reached for a 104-mer oligodeoxynucleotide utilizing the 24- charge state of the 80-mer (high charge state tuning). The same effect was observed for proteins investigated in the positive ion mode using low and high charge states of cytochrome c and carbonic anhydrase, respectively, for instrument tuning. By comparing the settings for low and high charge state tuning, it became obvious that the most significant difference was observed in the potential applied to the heated metal capillary used to transfer ions from the atmospheric pressure to the vacuum region of the ion source. Taking advantage of the optimized tuning procedure, the molecular mass of a 61 base pair product of polymerase chain reaction was accurately determined by electrospray ionization mass spectrometry on-line interfaced to ion-pair reversed-phase high-performance liquid chromatography. Copyright 2003 John Wiley & Sons, Ltd.

  9. Mass determination of megadalton-DNA Electrospray Ions usingCharge Detection Mass Spectrometry

    SciTech Connect

    Schultz, Jocelyn C.; Hack, Christopher; Benner, Henry W.

    1997-10-01

    Charge detection mass spectrometry (CD-MS) has been used to determine the mass of double-stranded, circular DNA and single-stranded, circular DNA in the range of 2500 to 8000 base pairs (1.5-5.0 MDa). Simultaneous measurement of the charge and velocity of an electrostatically accelerated ion allows a mass determination of the ion, with instrument calibration determined independently of samples. Positive ion mass spectra of electrosprayed commercial DNA samples supplied in tris(hydroxymethyl)ethylenediamine tetraacetic acid buffer, diluted in 50 vol. percent acetonitrile, were obtained without cleanup of the sample. ACD mass spectrum constructed from 3000 ion measurements takes 10 min to acquire and yields the DNA molecular mass directly (mass resolution = 6). The data collected represent progress toward a more automatable alternative to sizing of DNA by gel electrophoresis. In addition to the mass spectra, CD-MS generates charge versus mass plots, which provide another means to investigate the creation and fate of large electrospray ions.

  10. Using photo-ionisation models to derive carbon and oxygen gas-phase abundances in the rest UV

    NASA Astrophysics Data System (ADS)

    Pérez-Montero, Enrique; Amorín, Ricardo

    2017-01-01

    We present a new method to derive oxygen and carbon abundances using the ultraviolet (UV) lines emitted by the gas-phase ionised by massive stars. The method is based on the comparison of the nebular emission-line ratios with those predicted by a large grid of photo-ionisation models. Given the large dispersion in the O/H - C/O plane, our method firstly fixes C/O using ratios of appropriate emission lines and, in a second step, calculates O/H and the ionisation parameter from carbon lines in the UV. We find abundances totally consistent with those provided by the direct method when we apply this method to a sample of objects with an empirical determination of the electron temperature using optical emission lines. The proposed methodology appears as a powerful tool for systematic studies of nebular abundances in star-forming galaxies at high redshift.

  11. Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemica lionization

    SciTech Connect

    Ovchinnikova, Olga S; Van Berkel, Gary J

    2010-01-01

    An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

  12. Eliminating the interferences from TRIS buffer and SDS in protein analysis by fused-droplet electrospray ionization mass spectrometry.

    PubMed

    Shieh, I-Fan; Lee, Chi-Yang; Shiea, Jentaie

    2005-01-01

    Multiply charged protein ions were detected from the solutions containing a high concentration of tris(hydroxymethyl) aminomethane buffer (TRIS) and sodium dodecyl sulfate (SDS) using fused-droplet electrospray ionization mass spectrometry (FD-ESI/MS). The sample aerosols were generated at ambient temperature with a pneumatic nebulizer commonly used to produce sample aerosols in an atmospheric pressure chemical ionization (APCI) source. The aerosols were carried by nitrogen gas to the tip of a capillary where charged methanol droplets had been continuously generated by electrospraying an acidic methanol solution. The neutral sample aerosols then fused with the charged methanol droplets and electrospray ionization proceeded from the newly formed fused droplets to generate multiply charged protein ions. Because of its low solubility in methanol, TRIS molecules (concentration as high as 1 M) were efficiently excluded from the newly formed droplets and the protein ion signals were detected and observed in the mass spectra. To remove the interferences from SDS, equal moles of positively charged cetyltrimethylammonium bromide (CTAB) was added into the SDS containing sample solution to form the dodecyl sulfate-cetyltrimethylammonium ion pair (DS-CTA). The DS-CTA ion pair has a low polarity and solubility in methanol and is excluded from the fused droplet. Protein ions were still detected from the solution containing 10(-2) M of SDS.

  13. Ion-exchange chromatography/electrospray mass spectrometry for the identification of organic and inorganic species in topiramate tablets.

    PubMed

    Xiang, X; Ko, C Y; Guh, H Y

    1996-11-01

    An ion-exchange chromatograph/electrospray ionization mass spectrometer (IC/ESI-MS) was used successfully to identify organic and inorganic species present in topiramate tablets. An ion suppressor is placed between the column and detectors to replace sodium ions in the mobile phase with hydrogen ions supplied by the suppressor. The ensuing combination of the hydrogen ions with the mobile phase hydroxide ions produces water and thus allows simultaneous ion detection by an ion conductivity detector and a mass spectrometer. Analytes, including lactate, glycolate, chloride, formate, sulfate, and oxalate, were unambiguously identified by matching the mass spectra and retention times with those of the authentic compounds. Due to its capability of detecting positive and negative as well as neutral species, ESI-MS provides valuable information which is not available with ion conductivity detection alone. Though the coupling of ion-exchange chromatography to mass spectrometry has been reported previously, this is the first demonstration of IC/ESI-MS for the identification of unknown species in real samples. Finally, with the use of deuterium/carbon-13 labeling and MS/MS techniques, we have confirmed that oxalic acid (HOOC-COOH) is formed from formic acid (HCOOH) at the electrospray interface in the presence of the electric field. This observation not only confirms the identity of an unknown peak, but it also provides new insight into chemistry that can take place during electrospray ionization.

  14. Validated method for determination of ultra-trace closantel residues in bovine tissues and milk by solid-phase extraction and liquid chromatography-electrospray ionization-tandem mass spectrometry.

    PubMed

    Sun, Hanwen; Wang, Fengchi; Ai, Lianfeng

    2007-12-21

    A liquid chromatographic-electrospray ionisation-tandem mass spectrometry method (LC-ESI-MS/MS) with solid extraction was developed and validated for the detection and determination of closantel residues in bovine tissues and milk. An acetonitrile-acetone mixture (80:20, v/v) was used for one-stage extraction of closantel residues in bovine tissues and milk samples, and the extract was cleaned by solid phase extraction with Oasis MAX cartridges. The mass spectrometer was operated in multiple reactions monitoring mode with negative electrospray interface. The limits of detection in different matrices were in the range of 0.008-0.009 microg/kg. The overall recoveries for bovine muscle, liver, kidney and milk samples spiked at four levels including MRL were in the range of 76.0-94.3%. The overall relative standard deviations were in the range of 3.57-8.61%. The linearity is satisfactory with a correlation coefficient (r(2)) of 0.9913-0.9987 at both concentration ranges of 0.02-100 microg/kg and 200-5000 microg/kg. The method is capable of identifying closantel residues at > or =0.02 microg/kg levels and was applied in the determination of closantel residues in animal origin foods.

  15. A rapid ex vivo tissue model for optimising drug detection and ionisation in MALDI imaging studies.

    PubMed

    Huber, K; Aichler, M; Sun, N; Buck, A; Li, Z; Fernandez, I E; Hauck, S M; Zitzelsberger, H; Eickelberg, O; Janssen, K P; Keller, U; Walch, A

    2014-10-01

    The aim of this study was to establish an ex vivo model for a faster optimisation of sample preparation procedures, for example matrix choice, in matrix-assisted laser desorption/ionisation (MALDI) drug imaging studies. The ionisation properties of four drugs, afatinib, erlotinib, irinotecan and pirfenidone, were determined in an ex vivo tissue experiment by spotting decreasing dilution series onto liver sections. Hereby, the drug signals were distinctly detectable using different matrix compounds, which allowed the selection of the optimal matrix for each drug. The analysis of afatinib and erlotinib yielded high drug signals with α-cyano-4-hydroxycinnamic acid matrix, whereas 2,3-dihydroxybenzoic acid was identified as optimal matrix for irinotecan and pirfenidone detection. Our method was validated by a MALDI drug imaging approach of in vivo treated mouse tissue resulting in corresponding findings, indicating the spotting method as an appropriate approach to determine the matrix of choice. The present study shows the accordance between the detection of ex vivo spotted drugs and in vivo administered drugs by MALDI-TOF and MALDI-FT-ICR imaging, which has not been demonstrated so far. Our data suggest the ex vivo tissue spotting method as an easy and reliable model to optimise MALDI imaging measurements and to predict drug detection in tissue sections derived from treated mice prior to the recruitment of laboratory animals, which helps to save animals, time and costs.

  16. An experimental and theoretical study of core-valence double ionisation of acetaldehyde (ethanal).

    PubMed

    Zagorodskikh, S; Vapa, M; Vahtras, O; Zhaunerchyk, V; Mucke, M; Eland, J H D; Squibb, R J; Linusson, P; Jänkälä, K; Ågren, H; Feifel, R

    2016-01-28

    Core-valence double ionisation spectra of acetaldehyde (ethanal) are presented at photon energies above the carbon and oxygen 1s ionisation edges, measured by a versatile multi-electron coincidence spectroscopy technique. We use this molecule as a testbed for analyzing core-valence spectra by means of quantum chemical calculations of transition energies. These theoretical approaches range from two simple models, one based on orbital energies corrected by core valence interaction and one based on the equivalent core approximation, to a systematic series of quantum chemical electronic structure methods of increasing sophistication. The two simple models are found to provide a fast orbital interpretation of the spectra, in particular in the low energy parts, while the coverage of the full spectrum is best fulfilled by correlated models. CASPT2 is the most sophisticated model applied, but considering precision as well as computational costs, the single and double excitation configuration interaction model seems to provide the best option to analyze core-valence double hole spectra.

  17. Glioblastoma stem cells: radiobiological response to ionising radiations of different qualities.

    PubMed

    Pecchia, I; Dini, V; Ricci-Vitiani, L; Biffoni, M; Balduzzi, M; Fratini, E; Belli, M; Campa, A; Esposito, G; Cirrone, G; Romano, F; Stancampiano, C; Pelacchi, F; Pallini, R; Tabocchini, M A

    2015-09-01

    Glioblastoma multiforme (GBM) is the most common and malignant primary brain tumour, with very poor prognosis. The high recurrence rate and failure of conventional treatments are expected to be related to the presence of radio-resistant cancer stem cells (CSCs) inside the tumour mass. CSCs can both self-renew and differentiate into the heterogeneous lineages of cancer cells. Recent evidence showed a higher effectiveness of C-ions and protons in inactivating CSCs, suggesting a potential advantage of Hadrontherapy compared with conventional radiotherapy for GBM treatment. To investigate the mechanisms involved in the molecular and cellular responses of CSCs to ionising radiations, two GBM stem cell (GSC) lines, named lines 1 and 83, which were derived from patients with different clinical outcomes and having different metabolic profiles (as shown by NMR spectroscopy), were irradiated with (137)Cs photons and with protons or C-ions of 62 MeV u(-1) in the dose range of 5-40 Gy. The biological effects investigated were: cell death, cell cycle progression, and DNA damage induction and repair. Preliminary results show a different response to ionising radiation between the two GSC lines for the different end points investigated. Further experiments are in progress to consolidate the data and to get more insights on the influence of radiation quality.

  18. Gas chromatography with diode array detection in series with flame ionisation detection.

    PubMed

    Gras, Ronda; Luong, Jim; Shellie, Robert A

    2017-06-02

    We introduce a gas chromatography detection approach that uses diode array detection operated in series with flame ionisation detection and demonstrate the utility of the detection approach for determination of volatile organic compounds. Diode array detection brings ultraviolet - visible spectroscopy (over a range of 190-640nm) onto the capillary gas chromatography time-scale, where average peak widths of analytes are on the order of 3-5s. The non-destructive nature of the diode array detector affords serially-coupled flame ionisation detection. This arrangement delivers near-simultaneous selective and universal detection without incurring additional analytical time, and without recourse to column flow splitting. The hyphenated technique is shown to be effective for chromatographic applications spanning an equivalent volatility range from C1 to C7n-paraffin hydrocarbons. The approach introduced herein provides increased sensitivity and selectivity for classes of compounds amenable to electronic spectroscopy such as alkenes, dienes, sulfurs, and aromatic compounds. The approach is demonstrated for direct measurement of carbon disulfide in work place atmospheres with a detection limit of 93pg on column and for the direct measurement of 1,3-butadiene in hydrocarbon matrices and ambient air with a detection of 73pg on column, each in less than 5min. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Measuring technique for thermal ionisation mass spectrometry of human tracer kinetic study with stable cerium isotopes.

    PubMed

    Keiser, Teresa; Höllriegl, Vera; Giussani, Augusto; Oeh, Uwe

    2011-06-01

    Thermal ionisation mass spectrometry (TIMS) method has been developed for the simultaneous detection of different cerium isotopes in biological samples (i.e., blood and urine) at very low concentrations. The work has been done in the frame of a biokinetic study, where different stable cerium isotopes have been administered orally and intravenously as tracers to the human body. In order to develop an appropriate detection method for the tracers in the biological samples, an optimum sample preparation technique has been set and adapted to the specific requirements of the analysis technique used, i.e., TIMS. For sample evaporation and ionisation, the double tantalum filament technique showed the best results. The ions produced were simultaneously collected on a secondary electron multiplier so that the isotopic ratios of the cerium isotopes in the biological samples could be measured. The technique has been optimised for the determination of cerium down to 1 ng loaded on the evaporation filament corresponding to cerium concentrations of down to 1 ng ml(-1) in the blood or urine samples. It has been shown that the technique is reliable in application and enables studies on cerium metabolism and biokinetics in humans without employing radioactive tracers.

  20. The effect of non ionising electromagnetic radiation on RAAF personnel during World War II.

    PubMed

    Flaherty, J A

    1994-05-01

    Did exposure to non ionising electromagnetic radiation during World War II in the short term have a stimulating effect on the anterior pituitary gland, and in turn on the gonads of both sexes, since the figures obtained appeared to affect the sexes equally? Is it that the long-term effect of microwave radiation on personnel is to cause adenoma and carcinoma? Is this long-term effect similar to the long-term effect of X-rays on infants, children and adolescents? According to Harrison's Principles of Internal Medicine 1980 (page 1710): "X-rays to the head and neck in infancy, childhood or adolescence is associated with a high incidence of thyroid disease later in life. Nodular disease is found to be particularly common on 20% of patients at risk, and may not be apparent until 30 years or more after exposure. One-third of the nodular type are found to be carcinomatous." The effect of non ionising electromagnetic and microwave radiation on those who work in these fields certainly needs much more investigation. What will be the long-term effect of using micro-ovens on the rising generation?

  1. Adaptive response to ionising radiation induced by cadmium in zebrafish embryos.

    PubMed

    Choi, V W Y; Ng, C Y P; Kong, M K Y; Cheng, S H; Yu, K N

    2013-03-01

    An adaptive response is a biological response where the exposure of cells or animals to a low priming exposure induces mechanisms that protect the cells or animals against the detrimental effects of a subsequent larger challenging exposure. In realistic environmental situations, living organisms can be exposed to a mixture of stressors, and the resultant effects due to such exposures are referred to as multiple stressor effects. In the present work we demonstrated, via quantification of apoptosis in the embryos, that embryos of the zebrafish (Danio rerio) subjected to a priming exposure provided by one environmental stressor (cadmium in micromolar concentrations) could undergo an adaptive response against a subsequent challenging exposure provided by another environmental stressor (alpha particles). We concluded that zebrafish embryos treated with 1 to 10 μM Cd at 5 h postfertilisation (hpf) for both 1 and 5 h could undergo an adaptive response against subsequent ~4.4 mGy alpha-particle irradiation at 10 hpf, which could be interpreted as an antagonistic multiple stressor effect between Cd and ionising radiation. The zebrafish has become a popular vertebrate model for studying the in vivo response to ionising radiation. As such, our results suggested that multiple stressor effects should be carefully considered for human radiation risk assessment since the risk may be perturbed by another environmental stressor such as a heavy metal.

  2. Characterisation of PRESAGE: A new 3-D radiochromic solid polymer dosemeter for ionising radiation.

    PubMed

    Adamovics, J; Maryanski, M J

    2006-01-01

    For the past 50 years there has been interest in developing 3-D dosemeters for ionising radiation. Particular emphasis has been put on those dosemeters that change their optical properties in proportion to the absorbed dose. Many of the dosemeters that have been evaluated have had limitations such as lack of transparency, diffusion of the image of the dose distribution or poor stability of baseline optical density. Many of these performance limitations have been overcome by the development of PRESAGE, an optically clear polyurethane-based radiochromic 3-D dosemeter. The solid PRESAGE dosemeter is formulated with a free radical initiator and a leuco dye and it does not require a container to maintain its shape. The polyurethane matrix is tissue equivalent and prevents the diffusion of the dose distribution image. There is a linear dose-response, which is independent of both photon energy and dose rate. Simple precautions such as preventing long-term exposure to additional ionising radiation including ultraviolet and controlling storage temperatures prevent the bleaching of the radiochromic response field within the irradiated dosemeter.

  3. High-resolution laser spectroscopy with the Collinear Resonance Ionisation Spectroscopy (CRIS) experiment at CERN-ISOLDE

    NASA Astrophysics Data System (ADS)

    Cocolios, T. E.; de Groote, R. P.; Billowes, J.; Bissell, M. L.; Budinčević, I.; Day Goodacre, T.; Farooq-Smith, G. J.; Fedosseev, V. N.; Flanagan, K. T.; Franchoo, S.; Garcia Ruiz, R. F.; Gins, W.; Heylen, H.; Kron, T.; Li, R.; Lynch, K. M.; Marsh, B. A.; Neyens, G.; Rossel, R. E.; Rothe, S.; Smith, A. J.; Stroke, H. H.; Wendt, K. D. A.; Wilkins, S. G.; Yang, X.

    2016-06-01

    The Collinear Resonance Ionisation Spectroscopy (CRIS) experiment at CERN has achieved high-resolution resonance ionisation laser spectroscopy with a full width at half maximum linewidth of 20(1) MHz for 219,221 Fr, and has measured isotopes as short lived as 5 ms with 214 Fr. This development allows for greater precision in the study of hyperfine structures and isotope shifts, as well as a higher selectivity of single-isotope, even single-isomer, beams. These achievements are linked with the development of a new laser laboratory and new data-acquisition systems.

  4. Correlation of the ionisation response at selected points of IC sensitive regions with SEE sensitivity parameters under pulsed laser irradiation

    SciTech Connect

    Gordienko, A V; Mavritskii, O B; Egorov, A N; Pechenkin, A A; Savchenkov, D V

    2014-12-31

    The statistics of the ionisation response amplitude measured at selected points and their surroundings within sensitive regions of integrated circuits (ICs) under focused femtosecond laser irradiation is obtained for samples chosen from large batches of two types of ICs. A correlation between these data and the results of full-chip scanning is found for each type. The criteria for express validation of IC single-event effect (SEE) hardness based on ionisation response measurements at selected points are discussed. (laser applications and other topics in quantum electronics)

  5. Electrosprayed inulin microparticles for microbiota triggered targeting of colon.

    PubMed

    Jain, Arvind K; Sood, Vishesh; Bora, Meghali; Vasita, Rajesh; Katti, Dhirendra S

    2014-11-04

    Inulin, a naturally occurring polysaccharide, was acetylated to make it processable by electrospraying, a facile and single step method for microparticle fabrication. Electrospraying process parameters were optimized for fabrication of spherical and monodisperse indomethacin (IDM) loaded inulin acetate (INA) microparticles. The apparent entrapment efficiency of IDM was determined to be 100%, whereas working encapsulation efficiency was estimated to be 35.39 ± 1.63%. Differential scanning calorimetry and X-ray diffraction analysis confirmed molecular dispersion of IDM in an amorphous state within the INA matrix. Finally, the results from in vitro release study performed in simulated gastro-intestinal fluids demonstrated that IDM was released only in simulated colonic fluid that contained inulinase. Therefore, this study demonstrates that acetylation of inulin does not alter its susceptibility to inulinase and that microparticles fabricated from INA can be developed as a colon targeting drug delivery system.

  6. Hydration of Gas-Phase Ions Formed by Electrospray Ionization

    PubMed Central

    Rodriguez-Cruz, Sandra E.; Klassen, John S.; Williams, Evan R.

    2005-01-01

    The hydration of gas-phase ions produced by electrospray ionization was investigated. Evidence that the hydrated ions are formed by two mechanisms is presented. First, solvent condensation during the expansion inside the electrospray source clearly occurs. Second, some solvent evaporation from more extensively solvated ions or droplets is apparent. To the extent that these highly solvated ions have solution-phase structures, then the final isolated gas-phase structure of the ion will be determined by the solvent evaporation process. This process was investigated for hydrated gramicidin S in a Fourier-transform mass spectrometer. Unimolecular dissociation rate constants of isolated gramicidin S ions with between 2 and 14 associated water molecules were measured. These rate constants increased from 16 to 230 s−1 with increasing hydration, with smaller values corresponding to magic numbers. PMID:10497808

  7. Electrospray on superhydrophobic nozzles treated with argon and oxygen plasma

    NASA Astrophysics Data System (ADS)

    Byun, Doyoung; Lee, Youngjong; Tran, Si Bui Quang; Nugyen, Vu Dat; Kim, Sanghoon; Park, Baeho; Lee, Sukhan; Inamdar, Niraj; Bau, Haim H.

    2008-03-01

    We report on a simple process to fabricate electrohydrodynamic spraying devices with superhydrophobic nozzles. These devices are useful, among other things, in mass spectrometry and printing technology. The superhydrophobic nozzle is created by roughening the surface of the polyfluorotetraethylene (PTFE) by argon and oxygen plasma treatment. We have developed a polymer-based electrospray device with a flat, superhydrophobic nozzle capable of maintaining a high contact angle and stable jetting.

  8. Ultrahigh vacuum deposition of organic molecules by electrospray ionization

    SciTech Connect

    Hamann, Chr.; Woltmann, R.; Hong, I-Po; Hauptmann, N.; Karan, S.; Berndt, R.

    2011-03-15

    An electrospray apparatus for deposition of organic molecules on surfaces in ultrahigh vacuum is presented. The kinetic energy at the impact and mass to charge ratio of deposited ions can be controlled by an electrostatic quadrupole deflector and an in-line quadrupole mass spectrometer. With an ion funnel in the first two vacuum stages a high ion transmission is achieved. Experiments on porphyrin cations and deoxyribonucleic acid deposited on a Au(111) surface demonstrate the capabilities of the instrument.

  9. Liposomes self-assembled from electrosprayed composite microparticles

    NASA Astrophysics Data System (ADS)

    Yu, Deng-Guang; Yang, Jun-He; Wang, Xia; Tian, Feng

    2012-03-01

    Composite microparticles, consisting of polyvinylpyrrolidone (PVP), naproxen (NAP) and lecithin (PC), have been successfully prepared using an electrospraying process and exploited as templates to manipulate molecular self-assembly for the synthesis of liposomes in situ. Field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) observations demonstrate that the microparticles have an average diameter of 960 ± 140 nm and a homogeneous structure. X-ray diffraction (XRD) patterns, differential scanning calorimetry (DSC) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) results verify that the building blocks NAP and PC are scattered in the polymer matrix in a molecular way owing to the very fast drying of the electrospraying process and the favorable secondary interactions among the components. FESEM, scanning probe microscope (SPM) and TEM observations demonstrate that the liposomes can be achieved through molecular self-assembly in situ when the microparticles contact water thanks to ‘like prefers like’ and by means of the confinement effect of the microparticles. The liposomes have an encapsulation rate of 91.3%, and 80.7% of the drug in the liposomes can be freed into the dissolution medium in a sustained way and by a diffusion mechanism over a period of 24 h. The developed strategy not only provides a new, facile, and effective method to assemble and organize molecules of multiple components into liposomes with electrosprayed microparticles as templates, but also opens a new avenue for nanofabrication in a step-by-step and controllable way.

  10. Capillary isoelectric focusing-electrospray mass spectrometry for protein analysis

    SciTech Connect

    Tang, Q.; Harrata, A.K.; Lee, C.S.

    1995-10-01

    On-line combination of capillary isoelectric focusing (CIEF) with electrospray mass spectrometry (ESMS) as a two-dimensional separation system is demonstrated. Mixtures of model proteins including cytochrome c (horse heart), myoglobin (horse heart), and carbonic anhydrase II (bovine erythrocyte) are focused and cathodically mobilized in a polyacrylamide-coated capillary. At the end of CIEF capillary, the mobilized protein zones are analyzed by mass spectrometry coupled on-line to an electrospray interface with a coaxial sheath flow configuration. The effects of carrier ampholyte concentration on the CIEF separation and the protein electrospray ionization mass spectra are presented and discussed. In this study, the focusing effect of CIEF permits analysis of very dilute protein samples. A typical concentration factor of 50-100 times is observed. The concentration detection limit of myoglobin for a full-scan CIEF-ESMS analysis is in the range of 10{sup -7} M, 2 orders of magnitude over that possible with normal capillary zone electrophoresis ESMS. 35 refs., 5 figs., 2 tabs.

  11. Ultrasonically Aided Electrospray source for monodisperse, charged nanoparticles

    NASA Astrophysics Data System (ADS)

    Song, Weidong

    This dissertation presents a new method of producing nearly monodisperse electrospray using charged capillary standing waves. This method, based on the Ultrasonically Aided Electrospraying (UAE) technology concept invented by the author, includes the steps of dispensing a liquid on the top surface of a diaphragm so as to form a liquid film on the surface of the diaphragm, setting the diaphragm into vibration using piezoelectric transducers so as to induce capillary standing waves in the liquid film, applying electric charge to the capillary standing waves so that electrospray is extracted from the crests of the capillary standing waves. Theoretical analysis on the formation of charged particles from charged capillary standing waves at critically stable condition is performed. An experimental UAE system is designed, built, and tested and the performance of this new technology concept is assessed. Experimental results validate the capabilities of the UAE concept. The method has several applications including electric space propulsion, nano particulate technologies, nanoparticle spray coating and painting techniques, semiconductor fabrication and biomedical processes. Two example applications in electric space propulsion and nanoparticle spray coating are introduced.

  12. Looking into individual coffee beans during the roasting process: direct micro-probe sampling on-line photo-ionisation mass spectrometric analysis of coffee roasting gases.

    PubMed

    Hertz-Schünemann, Romy; Streibel, Thorsten; Ehlert, Sven; Zimmermann, Ralf

    2013-09-01

    A micro-probe (μ-probe) gas sampling device for on-line analysis of gases evolving in confined, small objects by single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) was developed. The technique is applied for the first time in a feasibility study to record the formation of volatile and flavour compounds during the roasting process within (inside) or in the direct vicinity (outside) of individual coffee beans. A real-time on-line analysis of evolving volatile and semi-volatile organic compounds (VOC and SVOC) as they are formed under the mild pyrolytic conditions of the roasting process was performed. The soft-ionisation mass spectra depict a molecular ion signature, which is well corresponding with the existing knowledge of coffee roasting and evolving compounds. Additionally, thereby it is possible to discriminate between Coffea arabica (Arabica) and Coffea canephora (Robusta). The recognized differences in the roasting gas profiles reflect the differences in the precursor composition of the coffee cultivars very well. Furthermore, a well-known set of marker compounds for Arabica and Robusta, namely the lipids kahweol and cafestol (detected in their dehydrated form at m/z 296 and m/z 298, respectively) were observed. If the variation in time of different compounds is observed, distinctly different evolution behaviours were detected. Here, phenol (m/z 94) and caffeine (m/z 194) are exemplary chosen, whereas phenol shows very sharp emission peaks, caffeine do not have this highly transient behaviour. Finally, the changes of the chemical signature as a function of the roasting time, the influence of sampling position (inside, outside) and cultivar (Arabica, Robusta) is investigated by multivariate statistics (PCA). In summary, this pilot study demonstrates the high potential of the measurement technique to enhance the fundamental knowledge of the formation processes of volatile and semi-volatile flavour compounds inside the individual coffee bean.

  13. SU-E-T-150: Brachytherapy QA Employing a High Resolution Liquid Filled Ionisation Chamber Array: Initial Experience and Limitations

    SciTech Connect

    Gainey, M; Kollefrath, M; Bruggmoser, G

    2015-06-15

    Purpose: Verifying a complex 3D brachytherapy dose distribution by measurement is non-trivial. Ideally a photon detector array should be independent of energy and angle, have high spatial resolution and be robust for routine clinical use. Methods: An iridium-192 source was used. A PMMA jig was constructed comprising an outer slab and a central insert with eight milled channels for 1.33mm (outer diameter) steel needles, see figure. All calculations were performed using an empty CT study reconstructing eight virtual needles (QA-CT), using the v2 source model (Elekta AG, Sweden). A high resolution liquid filled ionisation chamber array SRS1000, together with Verisoft software v6.0 (PTW Freiburg, Germany), was used to perform measurements of plans of increasing complexity to evaluate its suitability for device- and patient-specific QA. The dimension of backscatter material was investigated. The patient plan dwell time distribution was entered manually into the QA-CT and the dose distribution was calculated. Results: Our measurements indicate that the array is independent of energy and angle. The resulting measured dose values are linearly interpolated to 2025 values. Shifts of 1mm of the entire needle are readily detectable. Individual dwell position shifts (2.5mm) are also readily measurable. Moreover a dwell time increase of 1 second both in the edge and central region are detectable. Conclusion: The high resolution SRS1000 array is a powerful instrument for brachytherapy QA enabling 977 simultaneous measurements to be performed. Our measurements suggest 60mm of RW3 backscatter material upstream and downstream are sufficient. Local percentage difference analysis is useful for device based QA, normalized relative percentage difference is arguably better for patient specific QA. Automated transfer of patient plan dwell time distribution to the QA plan is required to enable a comprehensive patient QA study to be performed. Moreover the described measurement technique

  14. Expression of the progenitor marker NG2/CSPG4 predicts poor survival and resistance to ionising radiation in glioblastoma.

    PubMed

    Svendsen, Agnete; Verhoeff, Joost J C; Immervoll, Heike; Brøgger, Jan C; Kmiecik, Justyna; Poli, Aurelie; Netland, Inger A; Prestegarden, Lars; Planagumà, Jesús; Torsvik, Anja; Kjersem, Anneli Bohne; Sakariassen, Per Ø; Heggdal, Jan I; Van Furth, Wouter R; Bjerkvig, Rolf; Lund-Johansen, Morten; Enger, Per Ø; Felsberg, Joerg; Brons, Nicolaas H C; Tronstad, Karl J; Waha, Andreas; Chekenya, Martha

    2011-10-01

    Glioblastoma (GBM) is a highly aggressive brain tumour, where patients respond poorly to radiotherapy and exhibit dismal survival outcomes. The mechanisms of radioresistance are not completely understood. However, cancer cells with an immature stem-like phenotype are hypothesised to play a role in radioresistance. Since the progenitor marker neuron-glial-2 (NG2) has been shown to regulate several aspects of GBM progression in experimental systems, we hypothesised that its expression would influence the survival of GBM patients. Quantification of NG2 expression in 74 GBM biopsies from newly diagnosed and untreated patients revealed that 50% express high NG2 levels on tumour cells and associated vessels, being associated with significantly shorter survival. This effect was independent of age at diagnosis, treatment received and hypermethylation of the O(6)-methylguanine methyltransferase (MGMT) DNA repair gene promoter. NG2 was frequently co-expressed with nestin and vimentin but rarely with CD133 and the NG2 positive tumour cells harboured genetic aberrations typical for GBM. 2D proteomics of 11 randomly selected biopsies revealed upregulation of an antioxidant, peroxiredoxin-1 (PRDX-1), in the shortest surviving patients. Expression of PRDX-1 was associated with significantly reduced products of oxidative stress. Furthermore, NG2 expressing GBM cells showed resistance to ionising radiation (IR), rapidly recognised DNA damage and effectuated cell cycle checkpoint signalling. PRDX-1 knockdown transiently slowed tumour growth rates and sensitised them to IR in vivo. Our data establish NG2 as an important prognostic factor for GBM patient survival, by mediating resistance to radiotherapy through induction of ROS scavenging enzymes and preferential DNA damage signalling.

  15. Mechanism of Charging and Supercharging Molecules in Electrospray Ionization

    PubMed Central

    Iavarone, Anthony T.; Williams*, Evan R.

    2005-01-01

    The origin of the extent of charging and the mechanism by which multiply charged ions are formed in electrospray ionization have been hotly debated for over a decade. Many factors can affect the number of charges on an analyte ion. Here, we investigate the extent of charging of poly(propyleneimine) dendrimers (generations 3.0 and 5.0), cytochrome c, poly(ethylene glycol)s, and 1,n-diaminoalkanes formed from solutions of different composition. We demonstrate that in the absence of other factors, the surface tension of the electrospray droplet late in the desolvation process is a significant factor in determining the overall analyte charge. For poly(ethylene glycol)s, 1,n-diaminoalkanes, and poly(propyleneimine) dendrimers electrosprayed from single-component solutions, there is a clear relationship between the analyte charge and the solvent surface tension. Addition of m-nitrobenzyl alcohol (m-NBA) into electrospray solutions increases the charging when the original solution has a lower surface tension than m-NBA, but the degree of charging decreases when this compound is added to water, which has a higher surface tension. Similarly, the charging of cytochrome c ions formed from acidified denaturing solutions generally increases with increasing surface tension of the least volatile solvent. For the dendrimers investigated, there is a strong correlation between the average charge state of the dendrimer and the Rayleigh limiting charge calculated for a droplet of the same size as the analyte molecule and with the surface tension of the electrospray solvent. A bimodal charge distribution is observed for larger dendrimers formed from water/m-NBA solutions, suggesting the presence of more than one conformation in solution. A similar correlation is found between the extent of charging for 1,n-diaminoalkanes and the calculated Rayleigh limiting charge. These results provide strong evidence that multiply charged organic ions are formed by the charged residue mechanism. A

  16. A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

    PubMed

    Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

    2016-06-01

    In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples.

  17. Analysis of phospholipid species in human blood using normal-phase liquid chromatography coupled with electrospray ionization ion-trap tandem mass spectrometry.

    PubMed

    Uran, S; Larsen, A; Jacobsen, P B; Skotland, T

    2001-07-15

    A narrow-bore normal-phase high-performance liquid chromatography (HPLC) method was developed for separation of phospholipid classes in human blood. The separation was obtained using an HPLC diol column and a gradient of chloroform and methanol with 0.1% formic acid, titrated to pH 5.3 with ammonia and added 0.05% triethylamine. The HPLC system was coupled on-line with an electrospray ionisation ion-trap mass spectrometer. Chromatographic baseline separation was obtained between phosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, lyso-phosphatidylcholine, phosphatidylinositol and phosphatidylserine, eluting in that order. The total run time was 30 min. Plasmalogen phosphatidylethanolamine and sphingomyelin, which both are substances with structural similarities to the glycerophospholipids, had similar retention time as phosphatidylethanolamine, but were well separated from the other glycerophospholipid classes. The species from each class were identified using MS2 or MS3, which forms characteristic lyso-fragments. The combination of lyso-fragment mass, molecular ion and chromatographic retention time was used to identify each species, including 20 species of phosphatidylglycerol. The mass spectra obtained for the phospholipid classes are presented. Using this system 17 disaturated phospholipid species not earlier described to be present in blood were identified. The limit of detection varied between different phospholipid classes and was in the range 0.1-5 ng of injected substance.

  18. Quantification of levoglucosan and its isomers by High Performance Liquid Chromatography - Electrospray Ionization tandem Mass Spectrometry and its applications to atmospheric and soil samples

    NASA Astrophysics Data System (ADS)

    Piot, C.; Jaffrezo, J.-L.; Cozic, J.; Pissot, N.; El Haddad, I.; Marchand, N.; Besombes, J.-L.

    2011-07-01

    The determination of atmospheric concentrations of levoglucosan and its two isomers, unambiguous tracers of biomass burning emissions, became even more important with the development of wood as renewable energy for domestic heating. Many researches demonstrated the increase during recent years of atmospheric particulate matter load due to domestic biomass combustion in developed countries. Analysis of biomass burning tracers is traditionally performed with Gas Chromatography-Mass Spectrometry (GC-MS) technique after derivatization and requires an organic solvent extraction. A simpler and faster technique using Liquid Chromatography - Electrospray Ionisation - tandem Mass Spectrometry (LC-ESI-MS/MS) was optimized for the analysis of levoglucosan, mannosan and galactosan isomers after an aqueous extraction. This technique allows a good separation between the three compounds in a very reduced time (runtime ~5 min). LOD and LOQ of this method are 30 μg l-1 and 100 μg l-1 respectively, allowing the use of filters from low-volume sampler (as commonly used in routine campaigns). A comparison of simultaneous levoglucosan measurements by GC-MS and LC-ESI-MS/MS for about 50 samples coming from different types of sampling sites and seasons was realized and shows very good agreement between the two methods. Therefore LC-ESI-MS/MS method can be used as an alternative to GC-MS particularly for measurement campaigns in routine where analysis time is important and detection limit is reduced. This paper shows that this method is also applicable to other environmental sample types like soil.

  19. Quantification of levoglucosan and its isomers by High Performance Liquid Chromatography - Electrospray Ionization tandem Mass Spectrometry and its applications to atmospheric and soil samples

    NASA Astrophysics Data System (ADS)

    Piot, C.; Jaffrezo, J.-L.; Cozic, J.; Pissot, N.; El Haddad, I.; Marchand, N.; Besombes, J.-L.

    2012-01-01

    The determination of atmospheric concentrations of levoglucosan and its two isomers, unambiguous tracers of biomass burning emissions, became even more important with the development of wood as renewable energy for domestic heating. Many researches demonstrated the increase during recent years of atmospheric particulate matter load due to domestic biomass combustion in developed countries. Analysis of biomass burning tracers is traditionally performed with Gas Chromatography-Mass Spectrometry (GC-MS) technique after derivatization and requires an organic solvent extraction. A simpler and faster technique using Liquid Chromatography - Electrospray Ionisation - tandem Mass Spectrometry (LC-ESI-MS/MS) was optimized for the analysis of levoglucosan, mannosan and galactosan isomers after an aqueous extraction. This technique allows a good separation between the three compounds in a very reduced time (runtime ~5 min). LOD and LOQ of this method are 30 μg l-1 and 100 μg l-1 respectively, allowing the use of filters from low-volume sampler (as commonly used in routine campaigns). A comparison of simultaneous levoglucosan measurements by GC-MS and LC-ESI-MS/MS for about 50 samples coming from different types of sampling sites and seasons was realized and shows very good agreement between the two methods. Therefore LC-ESI-MS/MS method can be used as an alternative to GC-MS particularly for measurement campaigns in routine where analysis time is important and detection limit is reduced. This paper shows that this method is also applicable to other environmental sample types like soil.

  20. Low pressure electrospray ionization system and process for effective transmission of ions

    DOEpatents

    Tang, Keqi [Richland, WA; Page, Jason S [Kennewick, WA; Kelly, Ryan T [Wet Richland, WA; Smith, Richard D [Richland, WA

    2010-03-02

    A system and method are disclosed that provide up to complete transmission of ions between coupled stages with low effective ion losses. A novel "interfaceless" electrospray ionization system is further described that operates the electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer.

  1. Determination of equilibrium association constants of ligand-DNA complexes by electrospray mass spectrometry.

    PubMed

    Gabelica, Valérie

    2010-01-01

    Electrospray mass spectrometry can be used to detect ligand-DNA noncovalent complexes formed in solution. This chapter describes how to determine equilibrium association constants of the complexes. Particular attention is devoted to describing how to tune an electrospray mass spectrometer using a 12-mer oligodeoxynucleotides duplex in order to perform these experiments. This protocol can then be applied to any nucleic acid structure that can be ionized with electrospray mass spectrometry.

  2. Quantification of Fumaria officinalis isoquinoline alkaloids by nonaqueous capillary electrophoresis-electrospray ion trap mass spectrometry.

    PubMed

    Sturm, Sonja; Strasser, Eva-Maria; Stuppner, Hermann

    2006-04-21

    A capillary electrophoresis (CE) method using non-aqueous (NA) separation solutions combined with an ion trap mass spectrometer (MS and MS/MS) as detection device is presented for the separation, identification and quantification of isoquinoline alkaloids from Fumaria officinalis. The best results were obtained with a mixture of acetonitrile-methanol (9:1, v/v) containing 60mM ammonium acetate and 2.2M acetic acid as running electrolyte and an applied voltage of 30 kV. Electrospray MS measurements were performed in the positive ionization mode with isopropanol-water (1:1, v/v) as sheath liquid at a flow rate of 3 microl/min. Alkaloids were detected as [M+H](+)-ions and showed typical fragmentation patterns in MS/MS experiments. The developed assay was used for the quantification of seven isoquinoline alkaloids representing different structural subtypes in Fumariae herba extracts and F. herba containing phytopharmaceuticals.

  3. Liquid chromatography/electrospray ionization mass spectrometric characterization of Harpagophytum in equine urine and plasma.

    PubMed

    Colas, Cyril; Garcia, Patrice; Popot, Marie-Agnès; Bonnaire, Yves; Bouchonnet, Stéphane

    2006-01-01

    A method has been developed for the analysis and characterization in equine urine and plasma of iridoid glycosides: harpagide, harpagoside and 8-para-coumaroyl harpagide, which are the main active principles of Harpagophytum, a plant with antiinflammatory properties. The method involves liquid chromatography coupled with positive electrospray ionization mass spectrometry. The addition of sodium or lithium chloride instead of formic acid in the eluting solvent has been studied in order to enhance the signal and to modify the ion's internal energy. Fragmentation pathways and associated patterns are proposed for each analyte. A comparison of three types of mass spectrometer: a 3D ion trap, a triple quadrupole and a linear ion trap, has been conducted. The 3D ion trap was selected for drug screening analysis whereas the linear ion trap was retained for identification and quantitation analysis.

  4. Screening Anti-Cancer Drugs against Tubulin using Catch-and-Release Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rezaei Darestani, Reza; Winter, Philip; Kitova, Elena N.; Tuszynski, Jack A.; Klassen, John S.

    2016-05-01

    Tubulin, which is the building block of microtubules, plays an important role in cell division. This critical role makes tubulin an attractive target for the development of chemotherapeutic drugs to treat cancer. Currently, there is no general binding assay for tubulin-drug interactions. The present work describes the application of the catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS) assay to investigate the binding of colchicinoid drugs to αβ-tubulin dimers extracted from porcine brain. Proof-of-concept experiments using positive (ligands with known affinities) and negative (non-binders) controls were performed to establish the reliability of the assay. The assay was then used to screen a library of seven colchicinoid analogues to test their binding to tubulin and to rank their affinities.

  5. PFI-ZEKE photoelectron spectrum of CH2F2, ionisation potential and ionic fragmentation appearance potentials.

    PubMed

    Forysinski, Piotr W; Zielke, Philipp; Luckhaus, David; Signorell, Ruth

    2010-04-07

    The first vibrationally resolved pulsed-field-ionisation zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of difluoromethane from its adiabatic ionisation potential (formation of the C(2v) conformer of CH(2)F(2)(+)) to the onset of the first ionic fragmentation channel is presented. Precise values for the adiabatic ionisation potential (12.7252 +/- 0.0009 eV) and the appearance potentials of the H loss product (13.065 +/- 0.003 eV) and the F loss product (14.30 +/- 0.06 eV) of the cation are reported. Ab initio harmonic calculations were performed at the MP2 level with quadruple-zeta basis sets in an attempt to assign the newly observed vibrational structure which, in its previously published low resolution form, led to numerous speculations regarding its true origin. The adiabatic ionisation potential and the fragmentation appearance potentials for the three lowest dissociation channels are also predicted in the complete basis set limit of CCSD(T) theory.

  6. Dosimetric aspects of film/screen mammography: in-phantom dosimetry with thimble-type ionisation chambers.

    PubMed

    Zoetelief, J; de Wit, N J; Broerse, J J

    1989-09-01

    The characteristics of 0.6 cm3 thimble-type Baldwin-Farmer (BF 2571) ionisation chambers for absorbed dose determinations in-phantom at mammography installations are investigated. The most important aspects for in-phantom dosimetry in mammography concern the conversion from air kerma to absorbed dose in mammary gland tissue, the energy dependence of the sensitivity of the ionisation chamber and the displacement correction factor for measurements in-phantom. Due to the considerable uncertainties in the elemental composition of the mammary glands the conversion from air kerma to absorbed dose in the mammary gland tissue has an uncertainty of the order of +/- 20%. The air kerma calibration factor of the BF-ionisation chamber is about 10% larger at mammography radiation qualities than at 300 kV x-rays or 137Cs gamma rays. For depths in excess of about 15 mm a displacement correction factor of 0.69 +/- 0.06 is derived for measurements with the BF 2571 chamber inside polymethylmethacrylate (PMMA) phantoms irradiated with 30 kV x-rays (first HVL:0.29 mm Al). The previously reported discrepancy between dose measurements with TLD and ionisation chambers at the entrance surface of a phantom for mammography radiation qualities is resolved and could be attributed to attenuation in the TLD encapsulation material.

  7. Thin-Layer Chromatography/Desorption Electrospray Ionization Mass Spectrometry: Investigation of Goldenseal Alkaloids

    SciTech Connect

    Van Berkel, Gary J; Tomkins, Bruce A; Kertesz, Vilmos

    2007-01-01

    Desorption electrospray ionization mass spectrometry was investigated as a means to qualitatively identify and to quantify analytes directly from developed normal-phase thin layer chromatography plates. The atmospheric sampling capillary of a commercial ion trap mass spectrometer was extended to permit sampling and ionization of analytes in bands separated on intact TLC plates (up to 10 cm x 10 cm). A surface positioning software package and the appropriate hardware enabled computer-controlled surface scanning along the length of development lanes or at fixed RF value across the plates versus the stationary desorption electrospray emitter. Goldenseal (Hydrastis canadensis) and related alkaloids and commercial dietary supplements were used as standards and samples. Alkaloid standards and samples were spotted and separated on aluminum- or glass-backed plates using established literature methods. The mass spectral signal levels as a function of desorption spray solvent were investigated with acetonitrile proving superior to methanol. The detection levels (ca. 5 ng each or 14 -28 pmol) in mass spectral full scan mode were determined statistically from the calibration curves (2.5 - 100 pmol) for the standards berberine, palmatine and hydrastinine spotted as a mixture and separated on the plates. Qualitative screening of the major alkaloids present in six different over-the-counter "goldenseal" dietary supplements was accomplished by obtaining full scan mass spectra during surface scans along the development lane in the direction of increasing RF value. In one sample, alkaloids were detected that strongly suggested the presence of at least one additional herb undeclared on the product label. These same data indicated the misidentification of one of the alkaloids in the TLC literature. Quantities of the alkaloids present in two of the samples determined using the mass spectral data were in reasonable agreement with the label values indicating the quantitative ability of

  8. Comprehensive Biothreat Cluster Identification by PCR/Electrospray-Ionization Mass Spectrometry

    PubMed Central

    Sampath, Rangarajan; Mulholland, Niveen; Blyn, Lawrence B.; Massire, Christian; Whitehouse, Chris A.; Waybright, Nicole; Harter, Courtney; Bogan, Joseph; Miranda, Mary Sue; Smith, David; Baldwin, Carson; Wolcott, Mark; Norwood, David; Kreft, Rachael; Frinder, Mark; Lovari, Robert; Yasuda, Irene; Matthews, Heather; Toleno, Donna; Housley, Roberta; Duncan, David; Li, Feng; Warren, Robin; Eshoo, Mark W.; Hall, Thomas A.; Hofstadler, Steven A.; Ecker, David J.

    2012-01-01

    Technology for comprehensive identification of biothreats in environmental and clinical specimens is needed to protect citizens in the case of a biological attack. This is a challenge because there are dozens of bacterial and viral species that might be used in a biological attack and many have closely related near-neighbor organisms that are harmless. The biothreat agent, along with its near neighbors, can be thought of as a biothreat cluster or a biocluster for short. The ability to comprehensively detect the important biothreat clusters with resolution sufficient to distinguish the near neighbors with an extremely low false positive rate is required. A technological solution to this problem can be achieved by coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS). The biothreat assay described here detects ten bacterial and four viral biothreat clusters on the NIAID priority pathogen and HHS/USDA select agent lists. Detection of each of the biothreat clusters was validated by analysis of a broad collection of biothreat organisms and near neighbors prepared by spiking biothreat nucleic acids into nucleic acids extracted from filtered environmental air. Analytical experiments were carried out to determine breadth of coverage, limits of detection, linearity, sensitivity, and specificity. Further, the assay breadth was demonstrated by testing a diverse collection of organisms from each biothreat cluster. The biothreat assay as configured was able to detect all the target organism clusters and did not misidentify any of the near-neighbor organisms as threats. Coupling biothreat cluster-specific PCR to electrospray ionization mass spectrometry simultaneously provides the breadth of coverage, discrimination of near neighbors, and an extremely low false positive rate due to the requirement that an amplicon with a precise base composition of a biothreat agent be detected by mass spectrometry. PMID:22768032

  9. Comparison of Internal Energy Distributions of Ions Created by Electrospray Ionization and Laser Ablation-Liquid Vortex Capture-Electrospray Ionization

    SciTech Connect

    Cahill, John F.; Kertesz, Vilmos; Ovchinnikova, Olga S.; Van Berkel, Gary J.

    2015-06-27

    Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed non-contact liquid-vortex capture probe has been used to efficiently collect 355 nm UV laser ablated material in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appear to be classic electrospray ionization spectra; however, the softness of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. A series of benzlypyridinium salts, known as thermometer ions, were used to compare internal energy distributions between electrospray ionization and the UV laser ablation liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. This data indicates ions formed directly by UV laser ablation, if any, are likely an extremely small constituent of the total ion signal observed. Instead, neutral molecules, clusters or particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream then electrosprayed are the predominant source of ion signal observed. The electrospray ionization process used controls the softness of the technique.

  10. Comparison of Internal Energy Distributions of Ions Created by Electrospray Ionization and Laser Ablation-Liquid Vortex Capture-Electrospray Ionization

    DOE PAGES

    Cahill, John F.; Kertesz, Vilmos; Ovchinnikova, Olga S.; ...

    2015-06-27

    Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed non-contact liquid-vortex capture probe has been used to efficiently collect 355 nm UV laser ablated material in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appear to be classic electrospray ionization spectra; however, the softness of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. A series of benzlypyridinium salts, known as thermometer ions, were used to comparemore » internal energy distributions between electrospray ionization and the UV laser ablation liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. This data indicates ions formed directly by UV laser ablation, if any, are likely an extremely small constituent of the total ion signal observed. Instead, neutral molecules, clusters or particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream then electrosprayed are the predominant source of ion signal observed. The electrospray ionization process used controls the softness of the technique.« less

  11. Ionisation in turbulent magnetic molecular clouds. I. Effect on density and mass-to-flux ratio structures

    NASA Astrophysics Data System (ADS)

    Bailey, Nicole D.; Basu, Shantanu; Caselli, Paola

    2017-05-01

    Context. Previous studies show that the physical structures and kinematics of a region depend significantly on the ionisation fraction. These studies have only considered these effects in non-ideal magnetohydrodynamic simulations with microturbulence. The next logical step is to explore the effects of turbulence on ionised magnetic molecular clouds and then compare model predictions with observations to assess the importance of turbulence in the dynamical evolution of molecular clouds. Aims: In this paper, we extend our previous studies of the effect of ionisation fractions on star formation to clouds that include both non-ideal magnetohydrodynamics and turbulence. We aim to quantify the importance of a treatment of the ionisation fraction in turbulent magnetised media and investigate the effect of the turbulence on shaping the clouds and filaments before star formation sets in. In particular, here we investigate how the structure, mass and width of filamentary structures depend on the amount of turbulence in ionised media and the initial mass-to-flux ratio. Methods: To determine the effects of turbulence and mass-to-flux ratio on the evolution of non-ideal magnetised clouds with varying ionisation profiles, we have run two sets of simulations. The first set assumes different initial turbulent Mach values for a fixed initial mass-to-flux ratio. The second set assumes different initial mass-to-flux ratio values for a fixed initial turbulent Mach number. Both sets explore the effect of using one of two ionisation profiles: step-like (SL) or cosmic ray only (CR-only). We compare the resulting density and mass-to-flux ratio structures both qualitatively and quantitatively via filament and core masses and filament fitting techniques (Gaussian and Plummer profiles). Results: We find that even with almost no turbulence, filamentary structure still exists although at lower density contours. Comparison of simulations shows that for turbulent Mach numbers above 2, there is

  12. Electrospray tandem mass spectrometric investigations of morphinans.

    PubMed

    Raith, Klaus; Neubert, Reinhard; Poeaknapo, Chotima; Boettcher, Christian; Zenk, Meinhart H; Schmidt, Jürgen

    2003-11-01

    In this study positive ESI tandem mass spectra of the [M + H]+ ions of morphinan alkaloids obtained using an ion trap MS were compared with those from a triple quadrupole MS. This allows to assess the differences of the tandem-in-time versus the tandem-in-space principle, often hampering the development of ESI MS/MS libraries. Fragmentation pathways and possible fragment ion structures were discussed. In order to obtain elemental composition, accurate mass measurements were performed. According to the MS/MS fragmentation pathway, the investigated compounds can be grouped into 4 subsets: (1) morphine and codeine, (2) morphinone, codeinone, and neopinone, (3) thebaine and oripavine, (4) salutaridine and salutaridinol. Salutaridinol-7-O-acetate shows a different fragmentation behavior because of the favored loss of acetic acid. Although most fragment ions occur in both ion trap and triple quad tandem mass spectra, some are exclusively seen in either type. For triple quad, quadrupole time-of-flight and FT-ICR MS/MS, the base peak of morphine results from an ion at m/z 165 that contains neither nitrogen nor oxygen. This ion is not found in ion trap MS/MS, but in subsequential MS3 and MS4.

  13. Ionisation chamber containing boron as a neutron detector in medical accelerator fields.

    PubMed

    Zielczynski, M; Gryzinski, M A; Golnik, N; Tulik, P

    2007-01-01

    A combination of the recombination principle of H(10) measurements with the use of the ionisation chambers containing boron has been presented, in order to increase the relative sensitivity of the chamber to neutrons by a factor close to the radiation quality factor of photoneutrons. Three types of the chambers were investigated. Two of them were filled with BF(3) and the third one contained electrodes covered with B(4)C. All the chambers were placed in paraffin moderators. The response of the chambers was investigated, depending on gas pressure and polarising voltage. The results showed that it was possible to obtain nearly the same response of the chamber to H(10) for photons and neutrons in a restricted energy range; however, further investigations are needed to make an optimum design.

  14. Laser Ablation/Ionisation Mass Spectrometry: Sensitive and Quantitative Chemical Depth Profiling of Solid Materials.

    PubMed

    Riedo, Andreas; Grimaudo, Valentine; Moreno-García, Pavel; Neuland, Maike B; Tulej, Marek; Broekmann, Peter; Wurz, Peter

    2016-01-01

    Direct quantitative and sensitive chemical analysis of solid materials with high spatial resolution, both in lateral and vertical direction is of high importance in various fields of analytical research, ranging from in situ space research to the semiconductor industry. Accurate knowledge of the chemical composition of solid materials allows a better understanding of physical and chemical processes that formed/altered the material and allows e.g. to further improve these processes. So far, state-of-the-art techniques such as SIMS, LA-ICP-MS or GD-MS have been applied for chemical analyses in these fields of research. In this report we review the current measurement capability and the applicability of our Laser Ablation/Ionisation Mass Spectrometer (instrument name LMS) for the chemical analysis of solids with high spatial resolution. The most recent chemical analyses conducted on various solid materials, including e.g. alloys, fossils and meteorites are discussed.

  15. Correlation of spectroscopic and biochemical assays post-ionising radiation exposure in human skin cell analogues

    NASA Astrophysics Data System (ADS)

    Meade, A. D.; Byrne, H. J.; Lyng, F. M.

    2005-06-01

    Raman spectroscopy, as an evaluation of the products of ionising radiation exposure in biological systems, has been utilised mainly in the evaluation of the impact of exposure in tissue, cellular constituents and live animals. It has also been recently demonstrated that Raman spectroscopy can demonstrate key spectroscopic changes in the live cell associated with significant apoptotic and necrotic chemical damage. The present preliminary work utilises Raman spectroscopy at 514.5 nm to evaluate the results of exposure to γ-rays in HaCaT cells from a Co-60 therapy source, in tandem with other biological assays. The results demonstrate that Raman spectral changes may be correlated with changes in the cell also identified in parallel biochemical assays.

  16. Ionisation density effects following optical excitation in LiF:Mg, Ti (TLD-100).

    PubMed

    Weiss, D; Horowitz, Y; Oster, L

    2007-01-01

    The TL signal following 5 eV photon excitation of previously irradiated and readout material has been studied as a function of ionisation density and various experimental parameters: (i) maximum temperature of the first readout; (ii) photon fluence; (iii) photon energy and (iv) beta ray dose. Following alpha particle irradiation, the ratio of the second-readout to first-readout TL signal, epsilon(alpha,) has been found to be 10-20 times higher than that following beta irradiation, indicative of the possibility of using the double ratio epsilon(alpha)/epsilon(beta) as a mixed-field discriminator. The beginning of an attempt to explain this unusual effect is offered in the framework of the track structure theory and kinetic modelling of the beta ray dose-response of the first and second readouts.

  17. X-ray reflection from black-hole accretion discs with a radially stratified ionisation

    NASA Astrophysics Data System (ADS)

    Svoboda, J.; Domcek, V.; Dovčiak, M.; Guainazzi, M.; Marinucci, A.

    2015-07-01

    Recent X-ray observations have suggested a very high compactness of coronae in Active Galactic Nuclei as well as in X-ray Binaries. The compactness of the source implies that the black-hole accretion disc irradiation is a strong function of radius. We will show how the X-ray spectra are modified assuming the radially stratified ionisation according to the illumination by a point-like source on the black-hole rotational axis. We will discuss how this affects the measurements of the other model parameters, such as spin and radial emissivity. We will show the application of this model to the recent XMM-Newton/NUSTAR data of an active galaxy MCG-6-30-15.

  18. Non-ionising radiation human exposure assessment near telecommunication devices in Croatia.

    PubMed

    Simunić, Dina

    2006-03-01

    This paper gives an overview of the regulatory acts in non-ionising radiation in the world, with a special emphasis on basic guidelines issued by the International Commission on Non-Ionizing Radiation Protection (ICNIRP). ICNIRP Guidelines are implemented in many countries worldwide. Croatia has also implemented them indirectly through the European Recommendation 1999/519/EC. The Croatian regulatory acts include the Non-lonising Radiation Protection Act, Ordinance on Electromagnetic Fields (EMF) Protection, and the Ordinance on Basic Requirements for Devices which produce Optical Radiation and Measures for Optical Radiation Protection. Dosimetry and densitometry are compliant with relevant international and European standards. The paper presents an example of densitometric human exposure assessment in complex indoor exposure conditions. In spite of a high number of indoor and outdoor sources and the "worst-case exposure assessment", the results are within the limits defined by the Croatian EMF Ordinance.

  19. Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of bacteriochlorophylls from Chlorobiaceae: characteristic fragmentations.

    PubMed

    Airs, Ruth L; Keely, Brendan J

    2002-01-01

    Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry/mass spectrometry (APCI-LC/MS/MS) has been applied to the study of bacteriochlorophylls c, d, and e of phototrophic prokaryotes. Cultures of Chlorobiaceae containing bacteriochlorophyll c, d or e were examined using a high-resolution high-performance liquid chromatography (HPLC) method and APCI-LC/MS/MS employing post-column addition of formic acid. The results reveal complex distributions of bacteriochlorophyll homologues, with some closely eluting species giving isobaric protonated molecules. On-line LC/MS/MS studies reveal characteristic fragment ions for bacteriochlorophylls c, d, and e. Fragmentations involving loss of the extended alkyl substituents that are unique to bacteriochlorophylls c, d and e and their derivatives have been rationalised by studying the phaeophorbides and the results applied to the direct study of the bacteriochlorophylls.

  20. CF3(+) and CF2H(+): new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry.

    PubMed

    Blake, Robert S; Ouheda, Saleh A; Evans, Corey J; Monks, Paul S

    2016-11-28

    Alkanes provide a particular analytical challenge to commonly used chemical ionisation methods such as proton-transfer from water owing to their basicity. It is demonstrated that the fluorocarbon ions CF3(+) and CF2H(+), generated from CF4, as reagents provide an effective means of detecting light n-alkanes in the range C2-C6 using direct chemical ionisation mass spectrometry. The present work assesses the applicability of the reagents in Chemical Ionisation Mass Spectrometric (CI-TOF-MS) environments with factors such as high moisture content, operating pressures of 1-10 Torr, accelerating electric fields (E/N) and long-lived intermediate complex formation. Of the commonly used chemical ionisation reagents, H3O(+) and NO(+) only react with hexane and higher while O2(+) reacts with all the target samples, but creates significant fragmentation. By contrast, CF3(+) and CF2H(+) acting together were found to produce little or no fragmentation. In dry conditions with E/N = 100 Td or higher the relative intensity of CF2H(+) to CF3(+) was mostly less than 1% but always less than 3%, making CF3(+) the main reagent ion. Using O2(+) in a parallel series of experiments, a substantially greater degree of fragmentation was observed. The detection sensitivities of the alkanes with CF3(+) and CF2H(+), while relatively low, were found to be better than those observed with O2(+). Experiments using alkane mixtures in the ppm range have shown the ionisation technique based on CF3(+) and CF2H(+) to be particularly useful for measurements of alkane/air mixtures found in polluted environments. As a demonstration of the technique's effectiveness in complex mixtures, the detection of n-alkanes in a smoker's breath is demonstrated.

  1. Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

    NASA Astrophysics Data System (ADS)

    Bannan, T.; Booth, M.; Benyezzar, M.; Bacak, A.; Alfarra, M. R. R.; Topping, D. O.; Percival, C.

    2015-12-01

    Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

  2. Computer modeling and experimental work on the astrobiological implications of the martian subsurface ionising radiation environment

    NASA Astrophysics Data System (ADS)

    Dartnell, Lewis R.

    Any microbial life extant in the top meters of the martian subsurface is likely to be held dormant for long periods of time by the current permafrost conditions. In this potential habitable zone, a major environmental hazard is the ionising radiation field generated by the flux of exogenous energetic particles: solar energetic protons and galactic cosmic rays. The research reported here constitutes the first multidisciplinary approach to assessing the astrobiological impact of this radiation on Mars. A sophisticated computer model has been constructed de novo to characterise this complex subsurface ionising radiation field and explore the influence of variation in crucial parameters such as atmospheric density, surface composition, and primary radiation spectra. Microbiological work has been conducted to isolate novel cold-tolerant bacterial strains from the Dry Valleys environment of Antarctica, an analogue site to the martian surface, and determine their phylogenetic diversity and survival under high-dose gamma-ray exposure frozen at -79 °C, a temperature characteristic of the martian mid-latitude permafrost. Original results are presented pertinent to microbial survival time, persistence of organic biomarkers, and calibration of the optically stimulated luminescence dating technique, as a function of depth. The model predicts a population of radiation resistant cells to survive in martian permafrost soil for 450,000 years at 2 m depth, the proposed drill length of the ExoMars rover. The Antarctic culturing studies identified representatives of four bacterial genera. The novel isolate Brevundimonas sp. MV.7 is found to show 99% 16S sequence similarity to cells discovered in NASA spacecraft assembly clean rooms, with the experimental irradiation determining this strain to suffer 10-6 population inactivation after a radiation dose of 7.5 kGy in martian permafrost conditions. Integrating the modelling and experimental irradiation, this research finds a contaminant

  3. A photo-ionised canopy for the shock-excited Criss-Cross nebula

    NASA Astrophysics Data System (ADS)

    Temporin, S.; Weinberger, R.; Stecklum, B.

    2007-05-01

    Aims:We study a new broad, well-defined arc of optical nebulosity close to the cloud-shock interacting Criss-Cross nebula, derive the basic physical properties of the nebulosity, and revise those of the nebula, and compare both objects to simulations of cloud-shock interactions from the literature. Methods: Deep optical, partly wide-field images were used to reveal the intricate morphology and overall extent of the nebulosities. Optical spectroscopy enabled us to uncover their nature. Results: The two nebulosities are obviously physically linked, but are of different types; the Criss-Cross nebula is, as was also shown in an earlier paper, excited via a slow shock from the expanding Orion-Eridanus bubble, but the broad arc is definitely photo-ionised. The source for ionising photons appears to be hot gas in this bubble. Some results of simulations of interactions of SNRs with interstellar clouds available from the literature bear a striking resemblance to our nebulae, which appear to represent an example - unrivalled in closeness and clarity - of an early-to-medium stage in the destruction of an isolated cloud over-run by a highly evolved SNR. Thereby the Criss-Cross nebula is, when seen from the SNR, the rear disrupted part of the original, small cloud, whereas the arc is probably its still rather intact front part. Based on observations made with the Nordic Optical Telescope, operated on the island of La Palma jointly by Denmark, Finland, Iceland, Norway, and Sweden, at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias.

  4. Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

    NASA Astrophysics Data System (ADS)

    Bannan, Thomas; Booth, A. Murray; Alfarra, Rami; Bacak, Asan; Pericval, Carl

    2016-04-01

    Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

  5. Arsenous acid ionisation in aqueous solutions from 25 to 300 °C

    NASA Astrophysics Data System (ADS)

    Zakaznova-Herzog, V. P.; Seward, T. M.; Suleimenov, O. M.

    2006-04-01

    The ultraviolet spectra of dilute, aqueous arsenic (III)-containing solutions have been measured from 25 to 300 °C at the saturated vapour pressure. From these measurements, the equilibrium constant was obtained for the reaction H3AsO3⇄H++H2AsO3-; for which p K1 (arsenous acid) decreases from 9.25 to 7.11 over a temperature range from 25 to 300 °C. In addition, electrospray mass spectrometric measurements support the conclusion that the arsenous acid moeities in low density aqueous media are HAsO 2 and AsO 2-.

  6. Specification of the quality of ionising radiations for unified dosimetry in radiobiology and radiological protection

    NASA Astrophysics Data System (ADS)

    Alkharam, Ali Salem

    It is widely agreed in radiobiological and biophysical research that the DNA is the dominant target which can lead to terminal biological damage in the form of cancer or cell death. A main objective in radiation protection is to set the limits of the possible harmful effects to the general population exposed to ionising radiation at low level (environmental level). The initial slope of the dose-response curve is found to be an appropriate parameter to achieve this objective. Bench mark data sets of the initial effects of ionising radiation on cells in vitro were formed which include both physical characterisation of the radiation and the radiobiological parameters. These data-bases include the mammalian cell end-points: cellular inactivation, chromosome dicentrics, HPRT mutations and oncogenic transformations. On the molecular scale, the databases include single-strand and double strand breaks induced in the DNA of both mammalian and non-mammalian cells. Analysis of bio-effect mechanisms of damage to mammalian cells in terms of the quality parameter 'mean free path for linear primary ionisation' for ionising radiation, strongly suggest that there is a common mechanism for the biological endpoints of dicentrics, mutations, and oncogemc transformations. A unified response is obtained for all types of heavy ions and all cells which show: a common inflection point at inter-spacing distance equivalent to lambda0 = 1.4+/- 0.5 nm, a saturation region at lambda < lambda0 and almost constant slope for lambda < lambda0. The lethal lesions are identified as dsb's in the intracellular DNA. It follows that radiation risk factors can be determined on the basis of simple ratios to the inactivation cross sections. The size of these genes are found to be in close proximity to the optimised saturation levels. The probabilities of risk with respect to inactivation, for chromosome dicentrics, oncogenic transformations, and mutations of the HPRT gene are respectively 0.18, 1.6 x 10

  7. Detection of stanozolol and its metabolites in equine urine by liquid chromatography-electrospray ionization ion trap mass spectrometry.

    PubMed

    McKinney, Andrew R; Suann, Craig J; Dunstan, Anthony J; Mulley, Stephen L; Ridley, Damon D; Stenhouse, Allen M

    2004-11-05

    The equine phase I and phase II metabolism of the synthetic anabolic steroid stanozolol was investigated following its administration by intramuscular injection to a thoroughbred gelding. The major phase I biotransformations were hydroxylation at C16 and one other site, while phase II metabolism in the form of sulfate and beta-glucuronide conjugation was extensive. An analytical procedure was developed for the detection of stanozolol and its metabolites in equine urine using solid phase extraction, acid solvolysis of phase II conjugates and analysis by positive ion electrospray ionization ion trap LC-MS.

  8. Cone-jet electrospray in a dielectric liquid atmosphere

    NASA Astrophysics Data System (ADS)

    Barrero, Antonio; López-Herrera, José M.; Boucard, Arnaud; Loscertales, Ignacio G.; Márquez, Manuel

    2002-11-01

    Dispersion of liquids in a gas atmosphere or vacuum by applying an intense electric field is a well-known phenomenon. In fact, when the electric field on a liquid surface reaches a threshold value, the surface becomes unstable and forms a conical meniscus from whose vertex charge and mass are emitted. The conical meniscus attached to the end of a capillary needle and the emitted jet are steady for an appropriate range of values of both the applied electric field and the flow rate injected through the needle. Semi-conducting liquids can also be steadily dispersed into a dielectric liquid atmosphere in the cone jet mode. In this work, we report some experimental results of the electrospraying of water, ethylene-glycol, and glycerol in both heptane and hexane. The technique may be of interest for the production of fine emulsions, coating of particles containing drugs or any other substance, etc. The experimental setup for the spraying does not differ substantially from those used in standard electrosprays in gas atmosphere or vacuum. Measurements of the current emitted from the cone and the size of the particles as well as their standard deviation in size have been obtained as a function of the injected flow rate and the applied voltage. A Sympatec system has been used for measurements of the droplet size and the dispersion of the hydrosol. The influence of the liquids properties, such as electrical conductivity, permittivity ratio, and surface tension of the couple of liquids, on the scaling laws has been also investigated. Results agree well with the scaling laws for electrosprays in air.

  9. Numerical simulation of electrospray in the cone-jet mode.

    PubMed

    Herrada, M A; López-Herrera, J M; Gañán-Calvo, A M; Vega, E J; Montanero, J M; Popinet, S

    2012-08-01

    We present a robust and computationally efficient numerical scheme for simulating steady electrohydrodynamic atomization processes (electrospray). The main simplification assumed in this scheme is that all the free electrical charges are distributed over the interface. A comparison of the results with those calculated with a volume-of-fluid method showed that the numerical scheme presented here accurately describes the flow pattern within the entire liquid domain. Experiments were performed to partially validate the numerical predictions. The simulations reproduced accurately the experimental shape of the liquid cone jet, providing correct values of the emitted electric current even for configurations very close to the cone-jet stability limit.

  10. An integrated strategy for rapid and accurate determination of free and cell-bound microcystins and related peptides in natural blooms by liquid chromatography-electrospray-high resolution mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry using both positive and negative ionization modes.

    PubMed

    Flores, Cintia; Caixach, Josep

    2015-08-14

    An integrated high resolution mass spectrometry (HRMS) strategy has been developed for rapid and accurate determination of free and cell-bound microcystins (MCs) and related peptides in water blooms. The natural samples (water and algae) were filtered for independent analysis of aqueous and sestonic fractions. These fractions were analyzed by MALDI-TOF/TOF-MS and ESI-Orbitrap-HCD-MS. MALDI, ESI and the study of fragmentation sequences have been provided crucial structural information. The potential of combined positive and negative ionization modes, full scan and fragmentation acquisition modes (TOF/TOF and HCD) by HRMS and high resolution and accurate mass was investigated in order to allow unequivocal determination of MCs. Besides, a reliable quantitation has been possible by HRMS. This composition helped to decrease the probability of false positives and negatives, as alternative to commonly used LC-ESI-MS/MS methods. The analysis was non-target, therefore covered the possibility to analyze all MC analogs concurrently without any pre-selection of target MC. Furthermore, archived data was subjected to retrospective "post-targeted" analysis and a screening of other potential toxins and related peptides as anabaenopeptins in the samples was done. Finally, the MS protocol and identification tools suggested were applied to the analysis of characteristic water blooms from Spanish reservoirs.

  11. The use of particle beam mass spectrometry for the measurement of impurities in a nabumetone drug substance, not easily amenable to atmospheric pressure ionisation techniques.

    PubMed

    Wolff, J C; Hawtin, P N; Monté, S; Balogh, M; Jones, T

    2001-01-01

    Liquid chromatography/particle beam mass spectrometry (LC/PB-MS) was used for the structural elucidation of some impurities in nabumetone as this compound poorly ionises by atmospheric pressure ionisation (API) techniques. PB-MS was optimised for nabumetone and a sensitivity study was carried out. To obtain full scan electron ionisation spectra a minimum of 100 ng of compound on column was needed. By using 20 mg/mL solutions of nabumetone, impurities at levels of about 250 ppm mass fraction relative to nabumetone could be detected. Results were compared with LC/API-MS and previous GC/MS.

  12. Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Zarzana, Christopher A.; Groenewold, Gary S.; Benson, Michael T.; Delmore, James; Tsuda, Tetsuya; Hagiwara, Rika

    2015-09-01

    Metal fluoroanions are of significant interest for fundamental structure and reactivity studies and for making isotope ratio measurements that are free from isobaric overlap. Iron fluoroanions [FeF4]- and [FeF3]- were generated by electrospray ionization of solutions of Fe(III) and Fe(II) with the fluorinating ionic liquid 1-ethyl-3-methylimidazolium fluorohydrogenate [EMIm]+[F(HF)2.3]-. Solutions containing Fe(III) salts produce predominately uncomplexed [FeF4]- in the negative ion spectrum, as do solutions containing salts of Fe(II). This behavior contrasts with that of solutions of FeCl3 and FeCl2 (without [EMIm]+[F(HF)2.3]-) that preserve the solution-phase oxidation state by producing the gas-phase halide complexes [FeCl4]- and [FeCl3]-, respectively. Thus, the electrospray-[EMIm]+[F(HF)2.3]- process is oxidative with respect to Fe(II). The positive ion spectra of Fe with [EMIm]+[F(HF)2.3]- displays cluster ions having the general formula [EMIm]+ (n+1)[FeF4]- n, and DFT calculations predict stable complexes, both of which substantiate the conclusion that [FeF4]- is present in solution stabilized by the imidazolium cation. The negative ion ESI mass spectrum of the Fe-ionic liquid solution has a very low background in the region of the [FeF4]- complex, and isotope ratios measured for both [FeF4]- and adventitious [SiF5]- produced values in close agreement with theoretical values; this suggests that very wide isotope ratio measurements should be attainable with good accuracy and precision when the ion formation scheme is implemented on a dedicated isotope ratio mass spectrometer.

  13. β-Methylphenylethylamines: common fragmentation pathways with amphetamines in electrospray ionization collision-induced dissociation.

    PubMed

    Brown, David H; Hansson, Robert; Oosthuizen, Francois; Sumner, Nathan

    2016-01-01

    β-Methylphenylethylamines are positional isomers of amphetamines and have been discovered in sporting supplements. Although the fragmentation of the β-methylphenylethylamine and N-methyl-β-methylphenylethylamine in gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) systems is significantly different to their amphetamine and methylamphetamine isomers, under electrospray ionization commonly used in liquid chromatography-mass spectrometry (LC-MS) systems, the fragmentation of each of the isomeric pairs is almost identical. The similarities in fragmentation make it possible for the misidentification of the β-methylphenylethylamines as the illicit amphetamines. It is proposed that the similarities are due to a fragmentation pathway involving a common phenonium ion intermediate. By careful control of fragmentation energies in liquid chromatography-tandem mass spectrometry (LC-MS/MS) systems and/or close examination of the relative abundances of product ions formed by collision-induced dissociation (qualifier ratios), it is possible to distinguish the β-methylphenylethylamines from the amphetamines, even if significant retention time separation is not achieved. In liquid chromatography-electrospray ionization-quadrupole time of flight (LC-ESI-QTOF) systems the mass spectra of the β-methylphenylethylamines are identical to their amphetamine isomers. In such systems, retention time separation of the isomers is critical to avoid misidentification. During this study β-methylphenylethylamine and N-methyl-β-methylphenylethylamine have been identified in commercially available sporting supplements and oral fluid samples taken during the course of road-side drugs-in-drivers and workplace testing programmes. Copyright © 2015 John Wiley & Sons, Ltd.

  14. Characterization of Coordination Complexes by Desorption Electrospray Mass Spectrometry with a Capillary Target

    SciTech Connect

    Gary S. Groenewold; Anthony D. Appelhans; Michael E. McIlwain; Garold L. Gresham

    2011-03-01

    Metal coordination complexes were formed directly from liquid surfaces using desorption electrospray ionization (DESI) mass spectrometry. The approach is attractive because it separates complexities of ESI spray droplet formation from delivery of the analyte solution, and thereby gets around difficulty resulting from alteration of the spray process by changes in solution chemistry. Cs+, Ba2+, and La3+ coordination complexes were formed using 18-crown-6 (18c6) and triethylphosphate (TEP) as ligands (L), that had the general formula [Mn+(NO3-)n-1(L)m]+. Formation of singly charged cation complexes was preferred, with charge reduction at the metal site accomplished by attachment of nitrate. Using TEP as a model phosphoryl ligand, alkali metals coordinate with up to three ligands, with Cs+ preferring fewer than Na+. Ba2+ and La3+ are formed as ion pair complexes [Ba(NO3)]+ and [La(NO3)2]+, and both will coordinate with up to four TEP ligands. Using 18c6, Cs+ forms a bis-ligand complex. In contrast, [Ba(NO3)]+ prefers a single 18c6 ligand, while La forms mainly [La(NO3)2(18c6)]+, for which DFT calculations suggested a structure in which the nitrate ligands occupy pseudo-axial positions on opposing sides of the crown. Lower abundances of bis-18c6 complexes were also formed together with doubly charged [La(NO3)(18c6)n]2+ complexes (n = 2 – 4). The results suggest an alternative strategy for probing metal speciation in solution that is less perturbed by the droplet formation and ionization mechanisms operating in conventional electrospray ionization mass spectrometry.

  15. Desorption electrospray ionization mass spectrometry for trace analysis of agrochemicals in food.

    PubMed

    García-Reyes, Juan F; Jackson, Ayanna U; Molina-Díaz, Antonio; Cooks, R Graham

    2009-01-15

    Desorption electrospray ionization (DESI) is applied to the rapid, in situ, direct qualitative and quantitative (ultra)trace analysis of agrochemicals in foodstuffs. To evaluate the potential of DESI mass spectrometry (MS) in toxic residue testing in food, 16 representative multiclass agricultural chemicals (pesticides, insecticides, herbicides, and fungicides) were selected (namely, ametryn, amitraz, azoxystrobin, bitertanol, buprofezin, imazalil, imazalil metabolite, isofenphos-methyl, malathion, nitenpyram, prochloraz, spinosad, terbuthylazine, thiabendazole, and thiacloprid). The DESI-MS experiments were performed using 3 microL of solution spotted onto conventional smooth poly(tetrafluoroethylene) (PTFE) surfaces, with examination by MS and tandem mass spectrometry (MS/MS) using an ion trap mass spectrometer. Optimization of the spray solvent led to the use of acetonitrile/water (80:20) (v/v), with 1% formic acid. Most of the compounds tested showed remarkable sensitivity in the positive ion mode, approaching that attainable with conventional direct infusion electrospray mass spectrometry. To evaluate the potential of the proposed approach in real samples, different experiments were performed including the direct DESI-MS/MS analysis of fruit peels and also of fruit/vegetable extracts. The results proved that DESI allows the detection and confirmation of traces of agrochemicals in actual market-purchased samples. In addition, MS/MS confirmation of selected pesticides in spiked vegetable extracts was obtained at absolute levels as low as 1 pg for ametryn. Quantitation of imazalil residues was also undertaken using an isotopically labeled standard. The data obtained were in agreement with those from the liquid chromatography mass spectrometry (LC-MS) reference method, with relative standard deviation (RSD) values consistently below 15%. The results obtained demonstrate the sensitivity of DESI as they meet the stringent European Union pesticide regulation

  16. Structure-response relationship in electrospray ionization-mass spectrometry of sartans by artificial neural networks.

    PubMed

    Golubović, Jelena; Birkemeyer, Claudia; Protić, Ana; Otašević, Biljana; Zečević, Mira

    2016-03-18

    Quantitative structure-property relationship (QSPR) methods are based on the hypothesis that changes in the molecular structure are reflected in changes in the observed property of the molecule. Artificial neural network is a technique of data analysis, which sets out to emulate the human brain's way of working. For the first time a quantitative structure-response relationship in electrospray ionization-mass spectrometry (ESI-MS) by means of artificial neural networks (ANN) on the group of angiotensin II receptor antagonists--sartans has been established. The investigated descriptors correspond to different properties of the analytes: polarity (logP), ionizability (pKa), surface area (solvent excluded volume) and number of proton acceptors. The influence of the instrumental parameters: methanol content in mobile phase, mobile phase pH and flow rate was also examined. Best performance showed a multilayer perceptron network with the architecture 6-3-3-1, trained with backpropagation algorithm. It showed high prediction ability on the previously unseen (test) data set with a coefficient of determination of 0.994. High prediction ability of the model would enable prediction of ESI-MS responsiveness under different conditions. This is particularly important in the method development phase. Also, prediction of responsiveness can be important in case of gradient-elution LC-MS and LC-MS/MS methods in which instrumental conditions are varied during time. Polarity, chargeability and surface area all appeared to be crucial for electrospray ionization whereby signal intensity appeared to be the result of a simultaneous influence of the molecular descriptors and their interactions. Percentage of organic phase in the mobile phase showed a positive, while flow rate showed a negative impact on signal intensity.

  17. Direct electrospray tandem mass spectrometry of the unstable hydroperoxy bishemiacetal product derived from cholesterol ozonolysis.

    PubMed

    Pulfer, Melissa K; Harrison, Kathleen; Murphy, Robert C

    2004-02-01

    Cholesterol is the most abundant neutral lipid in the epithelial lining fluid of the lower airways of the lung also known as pulmonary surfactant and a potential target for reaction with ambient ozone when inspired into the human lung. The isolated double bond of cholesterol has been shown to be susceptible to attack by ozone, but the major reaction product from cholesterol ozonolysis had been remarkably difficult to structurally characterize. Recently, NMR and X-ray crystallography have been used to suggest the formation of a hydroperoxy, hydroxy hemiacetal product, using various derivatives and models of cholesterol to stabilize this chemically reactive product. Electrospray ionization mass spectrometry was used to study the somewhat unstable ozonolysis product of cholesterol which was found to display unique ionization and fragmentation properties when collisionally activated. The electron-deficient carbon atoms of this highly oxygenated product permitted covalent attachment of an acetate anion during negative ion electrospray ionization, leading to the formation of abundant adduct ions at m/z 511. Surprisingly, positive ions were not readily formed. Collision induced dissociation of the adduct anion yielded a major ion at m/z 477, corresponding to the loss of hydrogen peroxide. The most abundant fragment ion following collisional activation was observed at m/z 93, resulting from a complex rearrangement subsequent to the attack of the hydroperoxide anion on the carbon center of the acetate adduct. Based on the interpretation of the tandem mass spectral data, the major cholesterol ozonization product was characterized as a hydroperoxy, hydroxy hemiacetal derivative, which was consistent with the NMR and X-ray crystallographic studies which were carried out on the more stable methyl ether derivative.

  18. Selection of the Optimum Electrospray Voltage for Gradient Elution LC-MS Measurements

    PubMed Central

    Marginean, Ioan; Kelly, Ryan T.; Moore, Ronald J.; Prior, David C.; LaMarche, Brian L.; Tang, Keqi; Smith, Richard D.

    2009-01-01

    Changes in liquid composition during gradient elution liquid chromatography (LC) coupled to mass spectrometry (MS) analyses affect the electrospray operation. To establish methodologies for judicious selection of the electrospray voltage, we monitored in real-time the effect of the LC gradient on the spray current. The optimum range of the electrospray voltage decreased as the concentration of organic solvent in the eluent increased during reversed-phase LC analyses. These results provided the means to rationally select the voltage so as to ensure effective electrospray operation throughout gradient-elution LC separations. For analyses in which the electrospray was operated at constant voltage, a small run-to-run variation in the spray current was observed, indicating a changing electric field due to fouling or degradation of the emitter. Algorithms using feedback from spray current measurements to maintain the electrospray voltage within the optimum operating range throughout gradient elution LC-MS were evaluated. The electrospray operation with voltage regulation and at a constant, judiciously selected voltage during gradient elution LC-MS measurements produced data with similar reproducibility. SYNOPSIS Electrospray current measurements during gradient elution liquid chromatography analyses provide reliable feedback for monitoring, understanding, and improving performance. PMID:19196520

  19. 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

  20. Transferability of the Electrospray Ionization Efficiency Scale between Different Instruments

    NASA Astrophysics Data System (ADS)

    Liigand, Jaanus; Kruve, Anneli; Liigand, Piia; Laaniste, Asko; Girod, Marion; Antoine, Rodolphe; Leito, Ivo

    2015-11-01

    For the first time, quantitative electrospray (ESI) ionization efficiencies (IE), expressed as log IE values, obtained on different mass-spectrometric setups (four mass analyzers and four ESI sources) are compared for 15 compounds of diverse properties. The general trends of change of IE with molecular structure are the same with all experimental setups. The obtained IE scales could be applied on different setups: there were no statistically significant changes in the order of ionization efficiency and the root mean of squared differences of the log IE values of compounds between the scales compiled on different instruments were found to be between 0.21 and 0.55 log units. The results show that orthogonal ESI source geometry gives better differentiating power and additional pneumatic assistance improves it even more. It is also shown that the ionization efficiency values are transferable between different mass-spectrometric setups by three anchoring points and a linear model. The root mean square error of log IE prediction ranged from 0.24 to 0.72 depending on the instrument. This work demonstrates for the first time the inter-instrument transferability of quantitative electrospray ionization efficiency data.

  1. Electrosprayed Janus Particles for Combined Photo-Chemotherapy.

    PubMed

    Sanchez-Vazquez, Brenda; Amaral, Adérito J R; Yu, Deng-Guang; Pasparakis, George; Williams, Gareth R

    2017-07-01

    This work is a proof of concept study establishing the potential of electrosprayed Janus particles for combined photodynamic therapy-chemotherapy. Sub-micron-sized particles of polyvinylpyrrolidone containing either an anti-cancer drug (carmofur) or a photosensitiser (rose bengal; RB), and Janus particles containing both in separate compartments were prepared. The functional components were present in the amorphous form in all the particles, and infrared spectroscopy indicated that intermolecular interactions formed between the different species. In vitro drug release studies showed that both carmofur and RB were released at approximately the same rate, with dissolution complete after around 250 min. Cytotoxicity studies were undertaken on model human dermal fibroblasts (HDF) and lung cancer (A549) cells, and the influence of light on cell death explored. Formulations containing carmofur as the sole active ingredient were highly toxic to both cell lines, with or without a light treatment. The RB formulations were non-toxic to HDF when no light was applied, and with photo-treatment caused large amounts of cell death for both A549 and HDF cells. The Janus formulation containing both RB and carmofur was non-toxic to HDF without light, and only slightly toxic with the photo-treatment. In contrast, it was hugely toxic to A549 cells when light was applied. The Janus particles are thus highly selective for cancer cells, and it is hence proposed that such electrosprayed particles containing both a chemotherapeutic agent and photosensitiser have great potential in combined chemotherapy/photodynamic therapy.

  2. Unexpected Analyte Oxidation during Desorption Electrospray Ionization - Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a result of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.

  3. Targeting Sessile Droplets with Electrospray to Form Nanoparticle Deposits

    NASA Astrophysics Data System (ADS)

    Chiarot, Paul; Daeumer, Matthias; Maktabi, Sepehr; Yong, Xin

    2016-11-01

    The ability to print ordered deposits of nanoparticles has significant implications for electronics and photonics manufacturing. In this work, electrospray atomization was used to deliver dry nanoparticles to the surface of sacrificial sessile droplets. The particles were subsequently mapped to a glass substrate upon complete evaporation of the target droplet to create a deposit. The influence of the key electrospray operating parameters on the final deposit structure were explored, including: spray time, nanoparticle concentration, and initial sacrificial droplet volume. Once the nanoparticles were delivered to the interface, evaporatively-driven transport of the particles across the surface of the sessile droplet played a significant role in determining the structure of the deposit. When the contact line of the target sessile droplet was pinned during evaporation, the final deposit had greater particle density at the edge and center. The particles were distributed more uniformly across the deposit when the contact line of the target droplet moved during evaporation. The influence of thermal gradients on the final deposit structure was investigated by heating the substrate to increase the sessile droplet temperature. We also conducted computational simulations of evaporating particle-laden droplets and explored the influences of contact line behavior and nanoparticle surface chemistry on the deposit structure. This research supported by the National Science Foundation (Award 1538090).

  4. Flow Interface for Charge Reduced Electrospray of Nanoparticle Solutions

    PubMed Central

    Adou, Kouame; Johnston, Murray V.

    2009-01-01

    A charge reduction (CR) interface for electrospray ionization was characterized that permits simultaneous analysis of nanoparticle solutions by multiple detection methods. In the direct infusion configuration, a constant flow of analyte solution undergoes electrospray ionization (ESI). The charged aerosol is sampled directly into the atmospheric pressure inlet of a quadrupole time-of-flight mass spectrometer (QTOF) and to a CR device followed by a differential mobility analyzer (DMA) and condensation particle counter (CPC). In the plug injection configuration, analyte solution is injected into a liquid chromatograph. The effluent is split to an evaporative light scattering detector (ELSD) and the ESI interface. The charged aerosol is then sampled through the CR device directly into the CPC. Performance characteristics of the two configurations were studied with sucrose and protein solutions. When a liquid flow rate in the low µL/min range was used, the reconstructed droplet size distribution from the ESI interface had an average diameter of 184 nm with a geometric standard deviation of 1.4. For the first configuration, the linear working range was wider for ESI-MS than CR-DMA-CPC. For the second configuration, the detection efficiency, defined as the fraction of molecules flowing through the ESI interface that are ultimately detected by the CPC, was on the order of 10−6. Simultaneous measurements with ELSD and CPC were consistent with analyte molecular size and may provide a means of estimating the size of unknown particles. PMID:19924869

  5. Scaling up the power of an electrospray microthruster

    NASA Astrophysics Data System (ADS)

    Lenguito, G.; Fernandez de la Mora, J.; Gomez, A.

    2014-05-01

    We report on the development of an electrospray (ES) microthruster that, by emitting fast nanodroplets, covers a wide range of specific impulse and thrust at high (>50%) propulsion efficiency. To achieve a useful thrust, many ES microthrusters must operate in parallel (multiplexing). The multiplexed electrospray microthruster (MES) is packaged in an alumina case that can operate at voltages up to ΔV = 7.56 kV and a reservoir pressure up to 5 bar. We compared nozzle arrays with 7, 37 and 91 capillaries (ID/OD = 10/30 µm). To ensure uniform flow through the various emitters, the hydraulic resistance was increased by filling the capillaries with 2.01 µm beads. The MES devices sprayed the ionic liquid ethylammonium nitrate. The 37-MES device covered a 2.6-fold range of specific impulse reaching 1870 s, and a 4.2-fold range of thrust up to 31.1 µN. The 91-MES device reached higher thrust, but it covered a narrower range. All devices operated stably for hours with modest current fluctuations. The beam cleared the electrodes, with no signs of erosion. The developed microthruster has already reached performances suitable for fine attitude control of microsatellites. Further scaling up by one order of magnitude would enable orbit change and station keeping for small satellites.

  6. On the electrospraying of conducting liquids in dielectric liquid baths

    NASA Astrophysics Data System (ADS)

    Gómez-Marín, Álvaro; Loscertales, Ignacio G.; Márquez, Manuel; Barrero, Antonio

    2004-11-01

    Steady cone-jets of conducting liquids inside dielectris liquid baths are easily obtained. In particular water and glycerol have been electrosprayed in either heptane or vaseline oil. Experimental results show that the current emitted from the cone-jet depends on the flow rate and the liquid properties in the same way that it does in air. On the contrary, the effects of the bath inertia plays an important role to determine the size of droplets. Also the addition of small amounts of both water-soluble and lipid-soluble surfactants changes appreciably the spray characteristics. The influence of either lipid-soluble or water soluble surfactants at different concentrations on the droplet size of a water electrospray in oil or heptane has been experimentally obtained. In the case of glycerol, the high viscosity of the fluid gives rise to very long jets presenting kink instabilitiy far from the vertex cone. Much more stable jets are obtained by adding small amounts of lipid or water-soluble surfactants. In those cases, the electric field on the very long jet of glycerol is very small and a big droplet is formed at the end of the jet.

  7. Development and Characterization of electrosprayed Nanoparticles for encapsulation of Curcumin.

    PubMed

    Esmaili, Zahra; Bayrami, Samaneh; Abedin Dorkoosh, Farid; Akbari Javar, Hamid; Seyedjafari, Ehsan; Zargarian, Seyed Shahrooz; Haddadi-Asl, Vahid

    2017-09-11

    Curcumin has been proven to be an effective herbal derived anti-inflammatory and antioxidant biocompatible agent. In this research PLGA (as a biocompatible and GRAS polymer) nanoparticles containing Curcumin were electrospryed from different polymeric solutions with different concentrations for the first time. Morphology of these nanoparticles in the absence/presence of Curcumin was evaluated by SEM, TEM and XPS analyses. Perfectly shaped nanoparticles with an average size of 300 and 320 nanometers were observed for neat and Curcumin loaded PLGA, respectively. Curcumin-loaded electrosprayed nanoparticles showed a normal moderate initial burst and then a prolonged release period. Weibull, Peppas and modified Korsmeyer-Peppas models were applied to study the kinetic and mechanism of curcmin release from PLGA nanoparticles. Results showed high specific surface area and spherical geometry of the nanoparticles. Effectiveness of the electrospray method as a promising technique for preparing Curcumin-loaded nanoparticles was confirmed in this study. This article is protected by copyright. All rights reserved. © 2017 Wiley Periodicals, Inc.

  8. Electrospray Ionization Mass Spectrometry of hexanitrohexaazaisowurtzitane (CL-20)

    SciTech Connect

    Campbell, James A.; Szecsody, Jim E.; Devary, Brooks J.; Valenzuela, Blandina R.

    2007-09-03

    Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling’s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase

  9. Oxidative degradation of bis (2,4,4-trimethylpentyl) dithiophosphinic acid in nitric acid studied by electrospray ionization mass spectrometry

    SciTech Connect

    G. S. Groenewold; D. R. Peterman

    2012-10-01

    Samples of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301) were analyzed using direct infusion electrospray ionization mass spectrometry. Positive ion spectra of standard and stereo-pure acids displayed ions typical of the unmodified compound, cationized monomeric and dimeric cluster ion species. In addition, a significant ions 2 u less than the dimeric clusters were seen, that correspond to an oxidatively coupled species designated Cyx2 that is observed as H- or Na-cationized species in the electrospray analyses. Based on uncorrected ion intensities, Cyx2 is estimated to account for about 20% of the total in the standard materials. When samples that were contacted with 3 M HNO3 were analyzed, the positive ion spectrum consisted nearly entirely of ions derived from the oxidatively coupled product, indicating that the acid promotes coupling. The negative ion spectra of the standard acids consisted nearly entirely of the conjugate base that is formed by deprotonation of the acids, and cluster ions containing multiple acid molecules. The negative spectra of the HNO3-contacted samples also contained the conjugate base of the unmodified acid, but also two other species that correspond to the dioxo- and perthio- derivatives. It is concluded that HNO3 contact causes significant oxidation, forming at least three major products, Cyx2, the perthio-acid, and the dioxo-acid.

  10. Derivatization of Dextran for Multiply Charged Ion Formation and Electrospray Ionization Time-of-Flight Mass Spectrometric Analysis

    NASA Astrophysics Data System (ADS)

    Tapia, Jesus B.; Hibbard, Hailey A. J.; Reynolds, Melissa M.

    2017-06-01

    We present the use of a simple, one-pot derivatization to allow the polysaccharide dextran to carry multiple positive charges, shifting its molecular weight distribution to a lower m/z range. We performed this derivatization because molecular weight measurements of polysaccharides by mass spectrometry are challenging because of their lack of readily ionizable groups. The absence of ionizable groups limits proton abstraction and suppresses proton adduction during the ionization process, producing mass spectra with predominantly singly charged metal adduct ions, thereby limiting the detection of large polysaccharides. To address this challenge, we derivatized dextran T1 (approximately 1 kDa) by attaching ethylenediamine, giving dextran readily ionizable, terminal amine functional groups. The attached ethylenediamine groups facilitated proton adduction during the ionization process in positive ion mode. Using the low molecular weight dextran T1, we tracked the number of ethylenediamine attachments by measuring the mass shift from underivatized to derivatized dextran T1. Using electrospray ionization time-of-flight mass spectrometry, we observed derivatized dextran chains ranging from two to nine glucose residues with between one and four attachments/charges. Our success in shifting derivatized dextran T1 toward the low m/z range suggests potential for this derivatization as a viable route for analysis of high molecular weight polysaccharides using electrospray ionization time-of-flight mass spectrometry.

  11. An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system

    SciTech Connect

    Ford, Michael J; Van Berkel, Gary J

    2004-01-01

    A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed.

  12. An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system.

    PubMed

    Ford, Michael J; Van Berkel, Gary J

    2004-01-01

    A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed. Copyright 2004 John Wiley & Sons, Ltd.

  13. Derivatization of Dextran for Multiply Charged Ion Formation and Electrospray Ionization Time-of-Flight Mass Spectrometric Analysis

    NASA Astrophysics Data System (ADS)

    Tapia, Jesus B.; Hibbard, Hailey A. J.; Reynolds, Melissa M.

    2017-10-01

    We present the use of a simple, one-pot derivatization to allow the polysaccharide dextran to carry multiple positive charges, shifting its molecular weight distribution to a lower m/ z range. We performed this derivatization because molecular weight measurements of polysaccharides by mass spectrometry are challenging because of their lack of readily ionizable groups. The absence of ionizable groups limits proton abstraction and suppresses proton adduction during the ionization process, producing mass spectra with predominantly singly charged metal adduct ions, thereby limiting the detection of large polysaccharides. To address this challenge, we derivatized dextran T1 (approximately 1 kDa) by attaching ethylenediamine, giving dextran readily ionizable, terminal amine functional groups. The attached ethylenediamine groups facilitated proton adduction during the ionization process in positive ion mode. Using the low molecular weight dextran T1, we tracked the number of ethylenediamine attachments by measuring the mass shift from underivatized to derivatized dextran T1. Using electrospray ionization time-of-flight mass spectrometry, we observed derivatized dextran chains ranging from two to nine glucose residues with between one and four attachments/charges. Our success in shifting derivatized dextran T1 toward the low m/ z range suggests potential for this derivatization as a viable route for analysis of high molecular weight polysaccharides using electrospray ionization time-of-flight mass spectrometry. [Figure not available: see fulltext.

  14. Influence of ionisation zone motion in high power impulse magnetron sputtering on angular ion flux and NbO x film growth

    NASA Astrophysics Data System (ADS)

    Franz, Robert; Clavero, César; Kolbeck, Jonathan; Anders, André

    2016-02-01

    The ion energies and fluxes in the high power impulse magnetron sputtering plasma from a Nb target were analysed angularly resolved along the tangential direction of the racetrack. A reactive oxygen-containing atmosphere was used as such discharge conditions are typically employed for the synthesis of thin films. Asymmetries in the flux distribution of the recorded ions as well as their energies and charge states were noticed when varying the angle between mass-energy analyser and target surface. More positively charged ions with higher count rates in the medium energy range of their distributions were detected in +\\mathbf{E}× \\mathbf{B} than in -\\mathbf{E}× \\mathbf{B} direction, thus confirming the notion that ionisation zones (also known as spokes or plasma bunches) are associated with moving potential humps. The motion of the recorded negatively charged high-energy oxygen ions was unaffected. Nb{{\\text{O}}x} thin films at different angles and positions were synthesised and analysed as to their structure and properties in order to correlate the observed plasma properties to the film growth conditions. The chemical composition and the film thickness varied with changing deposition angle, where the latter, similar to the ion fluxes, was higher in +\\mathbf{E}× \\mathbf{B} than in -\\mathbf{E}× \\mathbf{B} direction.

  15. Influence of ionisation zone motion in high power impulse magnetron sputtering on angular ion flux and NbOx film growth

    DOE PAGES

    Franz, Robert; Clavero, César; Kolbeck, Jonathan; ...

    2016-01-21

    Here, the ion energies and fluxes in the high power impulse magnetron sputtering plasma from a Nb target were analysed angularly resolved along the tangential direction of the racetrack. A reactive oxygen-containing atmosphere was used as such discharge conditions are typically employed for the synthesis of thin films. Asymmetries in the flux distribution of the recorded ions as well as their energies and charge states were noticed when varying the angle between mass-energy analyser and target surface. More positively charged ions with higher count rates in the medium energy range of their distributions were detected in +E x B thanmore » in -E x B direction, thus confirming the notion that ionisation zones (also known as spokes or plasma bunches) are associated with moving potential humps. The motion of the recorded negatively charged high-energy oxygen ions was unaffected. NbOx thin films at different angles and positions were synthesised and analysed as to their structure and properties in order to correlate the observed plasma properties to the film growth conditions. The chemical composition and the film thickness varied with changing deposition angle, where the latter, similar to the ion fluxes, was higher in +E x B than in -E x B direction.« less

  16. Influence of ionisation zone motion in high power impulse magnetron sputtering on angular ion flux and NbOx film growth

    SciTech Connect

    Franz, Robert; Clavero, César; Kolbeck, Jonathan; Anders, André

    2016-01-21

    Here, the ion energies and fluxes in the high power impulse magnetron sputtering plasma from a Nb target were analysed angularly resolved along the tangential direction of the racetrack. A reactive oxygen-containing atmosphere was used as such discharge conditions are typically employed for the synthesis of thin films. Asymmetries in the flux distribution of the recorded ions as well as their energies and charge states were noticed when varying the angle between mass-energy analyser and target surface. More positively charged ions with higher count rates in the medium energy range of their distributions were detected in +E x B than in -E x B direction, thus confirming the notion that ionisation zones (also known as spokes or plasma bunches) are associated with moving potential humps. The motion of the recorded negatively charged high-energy oxygen ions was unaffected. NbOx thin films at different angles and positions were synthesised and analysed as to their structure and properties in order to correlate the observed plasma properties to the film growth conditions. The chemical composition and the film thickness varied with changing deposition angle, where the latter, similar to the ion fluxes, was higher in +E x B than in -E x B direction.

  17. Efficiency of generation of highly ionised atoms under resonance absorption of CO{sub 2}-laser radiation

    SciTech Connect

    Gus'kov, Sergei Yu; Demchenko, N N; Makarov, K N; Rozanov, Vladislav B; Satov, Yu A; Sharkov, Boris Yu

    2011-10-31

    We consider the generation of beams of highly ionised atoms in solid targets irradiated with CO{sub 2}-laser pulses. We present experimental results on generation of Mg and Pb ions from laser plasma at a radiation flux density q Almost-Equal-To 10{sup 14} W cm{sup -2}. We have developed a theoretical model describing the plasma heating by CO{sub 2}-laser radiation at a high pulse intensity on the target, taking into account the ponderomotive forces affecting the behaviour of the interaction of light with the plasma. It is shown that in the case of resonance absorption of laser radiation by the plasma, the efficiency of generation of highly ionised atoms of the target substance is higher than the efficiency of generation in the case of classical absorption. The results of the numerical calculation by the developed model are in good agreement with the experiment.

  18. Fast nucleotide identification through fingerprinting using gold nanoparticle-based surface-assisted laser desorption/ionisation.

    PubMed

    Larguinho, Miguel; Capelo, José L; Baptista, Pedro V

    2013-02-15

    We report a method centred on gold nanoparticle-based surface-assisted laser desorption/ionisation for analysis of deoxynucleotides and alkylated nucleobases. Gold nanoparticles allow for enhanced analysis capability by eliminating undesired signature peaks; thus more elegant mass spectra can be attained that allow identification by nucleotide mass fingerprint. The resulting fingerprinting patterns on the spectra are compared and associated with the presence of different nucleotides in the sample. This method can be easily extended to modified nucleotides implicated in genome lesions due to exposure to environment chemicals, such as DNA adducts (e.g. guanine adducts). The use of gold nanoparticles for surface-assisted laser desorption/ionisation can be an useful tool to resolve common issues of background noise when analysing nucleic acids samples.

  19. New example of proline-induced fragmentation in electrospray ionization mass spectrometry of peptides.

    PubMed

    Maux, Delphine; Enjalbal, Christine; Martinez, Jean; Aubagnac, Jean-Louis

    2002-01-01

    The positive ion electrospray ionization (ESI+) mass spectra of peptides usually display only protonated molecules provided that soft ionization conditions are applied (low cone voltage to prevent in-source dissociations). Such ions can be multiply charged depending on the molecular weight of the studied compounds. We have experienced an unexpected behavior during the ESI analysis of a modified peptide of relatively high mass (3079 Da). A specific fragmentation occurred even under soft energetic conditions, leading to a mass spectrum containing multiply charged molecular and fragment ions. The selective rupture involved the amide bond between the glutamic acid and proline residues (E-P sequence). The successive replacement of each amino acid by an alanine residue (positional scanning study) was undertaken to assess which part of the sequence induced such selective and abundant fragmentation on multiply charged species. The succession P-P was evidenced as the minimum unit giving rise to the first peptide bond rupture in the sequence X-P-P. Any acidic amino acid at the X position (X = D, E) favored the fragmentation by an intramolecular interaction. Such proline-induced fragmentation occurring readily in the source differed from the literature data on the specific behavior of proline-containing peptides where bond ruptures occur solely in dissociation conditions.

  20. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Evolution of tubular singular pulsed beams in a nonlinear dielectric medium upon ionisation

    NASA Astrophysics Data System (ADS)

    Vlasov, R. A.; Khasanov, O. Kh; Smirnova, T. V.

    2005-10-01

    The dynamics of a high-power femtosecond tubular pulsed beam in a dielectric medium is numerically analysed upon optically induced ionisation. It is found that the balance between nonlinearities of opposite sign and different magnitude in the case of multiphoton ionisation favours the establishment of a quasi-soliton regime of radiation propagation over a distance exceeding several diffraction lengths. The use of these beams enables attaining high-density light fields and generate high-density plasmas.

  1. Electrochemically induced pH changes resulting in protein unfolding in the ion source of an electrospray mass spectrometer.

    PubMed

    Konermann, L; Silva, E A; Sogbein, O F

    2001-10-15

    The operation of an electrospray ion source in the positive ion mode involves charge-balancing oxidation reactions at the liquid/metal interface of the sprayer capillary. One of these reactions is the electrolytic oxidation of water. The protons generated in this process acidify the analyte solution within the electrospray capillary. This work explores the effects of this acidification on the electrospray ionization (ESI) mass spectrum of the protein cytochrome c (cyt c). In aqueous solution containing 40% propanol, cyt c unfolds around pH 5.6. Mass spectra recorded under these conditions, using a simple ESI series circuit, display a bimodal charge-state distribution that reflects an equilibrium mixture of folded and unfolded protein in solution. These spectra are not strongly affected by electrochemical acidification. An "external loop" is added to the ESI circuit when the metal needle of the sample injection syringe is connected to ground. The resulting circuit represents two coupled electrolytic cells that share the ESI capillary as a common anode. Under these conditions, the rate of charge-balancing oxidation reactions is dramatically increased because the ion source has to supply electrons for both, the external circuit and the ESI circuit. The analytical implications of this effect are briefly discussed. Mass spectra of cyt c recorded with the syringe needle grounded are shifted to higher charge states, indicating that electrochemical acidification has caused the protein to unfold in the ion source. The acidification can be suppressed by increasing the flow rate and lowering the electrolyte concentration of the solution and by using an electrolyte that acts as redox buffer. The observed acidification is similar for sprayer capillaries made of platinum and stainless steel. Removal of the protective oxide layer on the stainless steel surface results in effective redox buffering for a few minutes.

  2. Ionisation response in semiconductor structures exposed to the X-ray radiation of a femtosecond laser-plasma source

    NASA Astrophysics Data System (ADS)

    Chumakov, A. I.; Belova, M. P.; Kessarinsky, L. N.; Borisov, A. Ya; Ivanov, K. A.; Tsymbalov, I. N.; Volkov, R. V.; Savel'ev, A. B.; Galanina, L. I.; Chirskaya, N. P.; Novikov, L. S.

    2017-06-01

    The possibilities of applying a femtosecond laser-plasma source of X-ray radiation for modelling the effect of single nuclear particles based on the principle of equivalent charge generation are analysed. The parameters of femtosecond X-ray radiation for the experimental modelling of individual radiation effects are validated. The experimental setup forming the X-ray radiation is described. The results of comparative ionisation response modelling in simple electronic devices using the FLUKA and FEANT codes are presented.

  3. Potential errors in relative dose measurements in kilovoltage photon beams due to polarity effects in plane-parallel ionisation chambers.

    PubMed

    Dowdell, S; Tyler, M; McNamara, J; Sloan, K; Ceylan, A; Rinks, A

    2016-11-15

    Plane-parallel ionisation chambers are regularly used to conduct relative dosimetry measurements for therapeutic kilovoltage beams during commissioning and routine quality assurance. This paper presents the first quantification of the polarity effect in kilovoltage photon beams for two types of commercially available plane-parallel ionisation chambers used for such measurements. Measurements were performed at various depths along the central axis in a solid water phantom and for different field sizes at 2 cm depth to determine the polarity effect for PTW Advanced Markus and Roos ionisation chambers (PTW-Freiburg, Germany). Data was acquired for kilovoltage beams between 100 kVp (half-value layer (HVL)  =  2.88 mm Al) and 250 kVp (HVL  =  2.12 mm Cu) and field sizes of 3-15 cm diameter for 30 cm focus-source distance (FSD) and 4  ×  4 cm(2)-20  ×  20 cm(2) for 50 cm FSD. Substantial polarity effects, up to 9.6%, were observed for the Advanced Markus chamber compared to a maximum 0.5% for the Roos chamber. The magnitude of the polarity effect was observed to increase with field size and beam energy but was consistent with depth. The polarity effect is directly influenced by chamber design, with potentially large polarity effects for some plane-parallel ionisation chambers. Depending on the specific chamber used, polarity corrections may be required for output factor measurements of kilovoltage photon beams. Failure to account for polarity effects could lead to an incorrect dose being delivered to the patient.

  4. Potential errors in relative dose measurements in kilovoltage photon beams due to polarity effects in plane-parallel ionisation chambers

    NASA Astrophysics Data System (ADS)

    Dowdell, S.; Tyler, M.; McNamara, J.; Sloan, K.; Ceylan, A.; Rinks, A.

    2016-12-01

    Plane-parallel ionisation chambers are regularly used to conduct relative dosimetry measurements for therapeutic kilovoltage beams during commissioning and routine quality assurance. This paper presents the first quantification of the polarity effect in kilovoltage photon beams for two types of commercially available plane-parallel ionisation chambers used for such measurements. Measurements were performed at various depths along the central axis in a solid water phantom and for different field sizes at 2 cm depth to determine the polarity effect for PTW Advanced Markus and Roos ionisation chambers (PTW-Freiburg, Germany). Data was acquired for kilovoltage beams between 100 kVp (half-value layer (HVL)  =  2.88 mm Al) and 250 kVp (HVL  =  2.12 mm Cu) and field sizes of 3-15 cm diameter for 30 cm focus-source distance (FSD) and 4  ×  4 cm2-20  ×  20 cm2 for 50 cm FSD. Substantial polarity effects, up to 9.6%, were observed for the Advanced Markus chamber compared to a maximum 0.5% for the Roos chamber. The magnitude of the polarity effect was observed to increase with field size and beam energy but was consistent with depth. The polarity effect is directly influenced by chamber design, with potentially large polarity effects for some plane-parallel ionisation chambers. Depending on the specific chamber used, polarity corrections may be required for output factor measurements of kilovoltage photon beams. Failure to account for polarity effects could lead to an incorrect dose being delivered to the patient.

  5. Formation of 2-propanol in condensed molecular films of acetaldehyde following electron impact ionisation-induced proton transfer*

    NASA Astrophysics Data System (ADS)

    Borrmann, Tobias; Swiderek, Petra

    2016-06-01

    Experimental studies on thin condensed layers of acetaldehyde have previously revealed that electron exposure at an energy above the ionisation threshold leads to formation of 2-propanol. However, the mechanism of this reaction remained unclear. Therefore, a computational approach is used to explore the electron-induced reactions of acetaldehyde yielding 2-propanol. Starting from hydrogen-bonded dimers of acetaldehyde we show that the initial ionisation event triggers proton transfer between the two acetaldehyde moieties resulting in a hydrogen-bonded complex of a [OCCH3] radical and a protonated acetaldehyde cation. Given an excess energy of up to 0.75 eV and a favourable arrangement, a methyl radical released upon dissociation of the CC bond within the [OCCH3] radical can migrate to the carbonyl carbon of the protonated acetaldehyde cation. This produces a 2-propanol radical cation and CO. Neutral 2-propanol is then obtained by recombination with a second electron. A mechanism involving ionisation-driven proton transfer is thus proposed as pathway to the formation of 2-propanol during electron exposure of condensed layers of acetaldehyde.

  6. Investigation of the ionisation density dependence of the glow curve characteristics of LIF:MG,TI (TLD-100)

    PubMed Central

    Horowitz, Y. S.; Horowitz, A.; Oster, L.; Marino, S.; Datz, H.; Margaliot, M.

    2008-01-01

    The dependence of the shape of the glow curve of LiF:Mg,Ti (TLD-100) on ionisation density was investigated using irradiation with 90Sr/90Y beta rays, 60 and 250 kVp X rays, various heavy-charged particles and 0.2 and 14 MeV neutrons. Special attention is focused on the properties of high-temperature thermoluminescence; specifically, the behaviour of the high-temperature ratio (HTR) of Peaks 7 and 8 as a function of batch and annealing protocol. The correlation of Peaks 7 and 8 with average linear-energy-transfer (LET) is also investigated. The HTR of Peak 7 is found to be independent of LET for values of LET approximately >30 keV µm−1. The behaviour of the HTR of Peak 8 with LET is observed to be erratic, which suggests that applications using the HTR should separate the contributions of Peaks 7 and 8 using computerised glow curve deconvolution. The behaviour of the HTR following neutron irradiation is complex and not fully understood. The shape of composite Peak 5 is observed to be broader following high ionisation alpha particle irradiation, suggesting that the combined use of the HTR and the shape of Peak 5 could lead to improved ionisation density discrimination for particles of high LET. PMID:18667402

  7. Spectrometre de masse a ionisation Penning selective: Elimination des corrections necessaires a la determination du rapport isotopique de l'hydrogene

    NASA Astrophysics Data System (ADS)

    Letarte, Sylvain

    Dans le but d'ameliorer la precision avec laquelle le rapport isotopique de l'hydrogene peut etre determine, un spectrometre de masse a ionisation Penning a ete construit pour provoquer l'ionisation selective de l'hydrogene moleculaire et de l'hydrure de deuterium a partir d'un melange gazeux. L'utilisation d'atomes dans des etats d'excitation metastable s'est averee une solution adequate pour reponde a cette attente. L'emploi de l'helium, a l'interieur d'une source d'atomes metastables construit specifiquement pour ce travail, ne permet pas d'obtenir un spectre de masse compose uniquement des deux molecules d'interet. L'ionisation de ces dernieres provient de deux processus distincts, soient l'ionisation Penning et l'ionisation par bombardement electronique. Contrairement a l'helium, il a ete demontre que le neon metastable est un candidat ideal pour produire l'ionisation selective de type Penning. Le nombre d'ions produits est directement proportionnel au courant de la decharge electrique et de la pression d'operation de la source d'atomes metastables. Ces resultats demontrent le potentiel d'un tel spectrometre de masse pour ameliorer la precision a laquelle le rapport isotopique peut etre determine comparativement aux autres techniques existantes.

  8. Highly informative multiclass profiling of lipids by ultra-high performance liquid chromatography - Low resolution (quadrupole) mass spectrometry by using electrospray ionization and atmospheric pressure chemical ionization interfaces.

    PubMed

    Beccaria, Marco; Inferrera, Veronica; Rigano, Francesca; Gorynski, Krzysztof; Purcaro, Giorgia; Pawliszyn, Janusz; Dugo, Paola; Mondello, Luigi

    2017-08-04

    A simple, fast, and versatile method, using an ultra-high performance liquid chromatography system coupled with a low resolution (single quadrupole) mass spectrometer was optimized to perform multiclass lipid profiling of human plasma. Particular attention was made to develop a method suitable for both electrospray ionization and atmospheric pressure chemical ionization interfaces (sequentially in positive- and negative-ion mode), without any modification of the chromatographic conditions (mobile phase, flow-rate, gradient, etc.). Emphasis was given to the extrapolation of the structural information based on the fragmentation pattern obtained using atmospheric pressure chemical ionization interface, under each different ionization condition, highlighting the complementary information obtained using the electrospray ionization interface, of support for related molecule ions identification. Furthermore, mass spectra of phosphatidylserine and phosphatidylinositol obtained using the atmospheric pressure chemical ionization interface are reported and discussed for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. [Simultaneous determination of ephedrine and N-methylephedrine in urine by solid phase extraction-ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry].

    PubMed

    Zhang, Lin; Zhang, Fucheng; Wang, Zhaohong; Jiang, Ye; Xu, Meng; Li, Hong

    2013-09-01

    A rapid and sensitive method has been developed for the simultaneous determination of ephedrine and N-methylephedrine in urine samples by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI MS/MS). The samples were extracted with Oasis MCX solid phase extraction cartridges and measured in the modes of electrospray positive ionization (ESI +) and multiple reaction monitoring (MRM). Good linearities were observed in the range of 0.025 0 - 2.50 microg/L with correlation coefficient over 0.999 0 for both analytes. The recoveries were above 80% with RSDs less than 5.0%. The limits of detection were 0.01 microg/L. The method proves to be rapid and sensitive for the trace determination of ephedrine and N-methylephedrine in urine samples.

  10. {sup 14}C-atrazine metaboite identification in field-grown sugarcane and sorghum by using radioactive detection and electrospray tandem mass spectrometry

    SciTech Connect

    Larson, J.D.; Ash, S.G.; Talaat, R.E

    1996-10-01

    The metabolism of [2,4,6-{sup 14}C]-atrazine in field-grown sugarcane and sorghum produced several dechlorinated, dealkylated, and/or glutathione metabolites. These metabolites were identified by gas chromatography-mass spectrometry and electrospray-tandem mass spectrometry. The subsequent metabolism of glutathione adducts of atrazine and N-dealkylated atrazine to novel metabolites were studied. Lanthionine, lanthionine sulfoxide, glucose-thiolactate and glutamine adducts of atrazine are examples of metabolites that we postulate arise from a common intermediate metabolite of atrazine, i.e., atrazine-glutathione adduct at position 2. The mass spectra as well as the postulated metabolic pathways will be discussed. The identification of such metabolites at trace levels in plant tissues were made possible by the coupling of the radioactive detector and electrospray interface on-line to the tandem mass spectrometer.

  11. Xpg limits the expansion of haematopoietic stem and progenitor cells after ionising radiation

    PubMed Central

    Avila, Alush I.; Illing, Anett; Becker, Friedrich; Maerz, Lars D.; Morita, Yohei; Philipp, Melanie; Burkhalter, Martin D.

    2016-01-01

    Reduced capacity of genome maintenance represents a problem for any organism, potentially causing premature death, carcinogenesis, or accelerated ageing. Strikingly though, loss of certain genome stability factors can be beneficial, especially for the maintenance of tissue stem cells of the intestine and the haematopoietic system. We therefore screened for genome stability factors negatively impacting maintenance of haematopoietic stem cells (HSC) in the context of ionising radiation (IR). We found that in vivo knock down of Xeroderma pigmentosum, complementation group G (Xpg) causes elevation of HSC numbers after IR treatment, while numbers of haematopoietic progenitors are elevated to a lesser extent. IR rapidly induces Xpg both on mRNA and on protein level. Prevention of this induction does not influence activation of the checkpoint cascade, yet attenuates late checkpoint steps such as induction of p21 and Noxa. This causes a leaky cell cycle arrest and lower levels of apoptosis, both contributing to increased colony formation and transformation rates. Xpg thus helps to adequately induce DNA damage responses after IR, thereby keeping the expansion of damaged cells under control. This represents a new function of Xpg in the response to IR, in addition to its well-characterized role in nucleotide excision repair. PMID:27137888

  12. Effect of penetrating ionising radiation on the mechanical properties of pericardium

    NASA Astrophysics Data System (ADS)

    Daar, Eman; Woods, E.; Keddie, J. L.; Nisbet, A.; Bradley, D. A.

    2010-07-01

    The pericardium is an anistropic composite material made up of collagen and elastin fibres embedded in an amorphous matrix mainly composed of proteoglycan and hyaluronan. The collagen fibres are arranged in layers, with different directions of alignment in each layer, giving rise to interesting mechanical properties of pericardium, including the ability to undergo large deformation during performance of regular physiological functions. The present study aims to investigate the effect of penetrating photon ionising radiation on bovine pericardium tissue, being part of a study of the effect of cardiac doses received in breast radiotherapy and the possibility that this can give rise to cardiovascular complications. Irradiation doses in the range 5-80 Gy were used. To characterise the various mechanical properties [elastic modulus, stress relaxation, ultimate tensile strength (UTS) and fracture] a uniaxial tensile test method was applied. The preliminary results reflect the wide inter-sample variations that are expected in dealing with tissues, with only a weak indication of increase in the UTS of the pericardium tissue with increase in radiation dose. Such an effect has also been observed by others, with reduction in UTS at doses of 80 Gy.

  13. 100 years of Cosmic Rays - from the ionisation of air to beyond the LHC

    NASA Astrophysics Data System (ADS)

    Watson, Alan

    2012-03-01

    The study of cosmic rays has impacted on many disciplines, including astrophysics, particle physics, carbon dating and radio astronomy: it has thus had scientific and societal impact. They were discovered in 1912 as a result of the efforts by some of the most distinguished scientists of that era, puzzled by their inability to explain the discharge of ionisation chambers. I will describe some of the early work that led, inter alia, to the discovery of the positron, the muon and the first strange particles and thus to the birth of particle physics. In 1938 it was found that showers of particles that arrive at the earth simultaneously are produced by primary cosmic rays of ˜10^15 eV, about 10^5 times more energetic than any particles that had been contemplated before. I will discuss how study of these showers has led to the discovery of cosmic rays of energies as great as 3 x 10^20 eV, challenging our understanding of where and how they are created. Data from the Pierre Auger Observatory, the largest cosmic-ray detector ever built, is now being used for astrophysical studies and to give glimpses of some hadronic physics at centre-of-mass energies more than 4 times greater than are accessible at the LHC.

  14. Variability in the H +3 emission of Saturn: Consequences for ionisation rates and temperature

    NASA Astrophysics Data System (ADS)

    Melin, Henrik; Miller, Steve; Stallard, Tom; Trafton, L. M.; Geballe, T. R.

    2007-01-01

    We present an analysis of observations of the auroral/polar regions of Saturn, carried out in 1999, 2004 and 2005, making use of the facility spectrometer, CGS4, on the United Kingdom Infrared Telescope (UKIRT), Mauna Kea, Hawaii. We obtain temperatures of 380(±70) K in 1999 and 420(±70) K in 2004. (The 2005 data has insufficient spectral resolution for a temperature determination to be made.) Our most probable interpretation is that the temperature of Saturn's auroral/polar H +3 layer should be taken as 400(±50) K. This is lower than the value obtained by Miller et al. [Miller, S., and 10 colleagues, 2000. Philos. Trans. R. Soc. 358, 2485-2502], which is shown to be in error. Our analysis reveals clearly that the line emission due to H +3 varies considerably, showing nearly an order of magnitude increase when one compares the data obtained in 1999 with those of 2004. Our conclusion is that this variability is (mainly) due to the changing H +3 column density. By analogy with modelling results obtained for Jupiter, we estimate that the particle (keV electron) precipitation experienced by Saturn must be ˜20 times greater in 2004 than in 1999, to produce this additional ionisation. The H +3 emission increases, but this is insufficient to offset most of the heating due to the extra particle precipitation, indicating that this ion does not act as a "thermostat" on Saturn, in the same way that it does on Jupiter.

  15. Resolving Ionisation and Metallicity on Parsec Scales Across Primordial Analogues with HST-WFC3

    NASA Astrophysics Data System (ADS)

    James, B. L.; Auger, M.; Calzetti, D.; Kewley, L.; Aloisi, A.; Pettini, M.; Trussler, J.

    2016-06-01

    Nearby Blue Compact Dwarf (BCD) galaxies are excellent laboratories for conducting detailed spatially resolved spectroscopic analyses of star-formation (SF), feedback, and chemical evolution in relatively pristine, low-metallicity environments analogous to those thought to exist in the early Universe. In this talk I will show a new, extensive dataset of narrow-band HST-WFC3 imaging where I essentially use HST as a high-spatial-resolution IFU to map six major emission lines in unprecedented detail, including HeII emission from WR stars. In this pioneering study, I spatially resolve diagnostic line ratios on sub-pc scales in two BCDs and deduce which ionisation mechanisms (e.g. shocks and/or photoionisation) are at work and assess their role in shaping the global galaxy properties. Moreover, I will present the first 'metallicity image' of a star-forming galaxy, revealing inhomogeneities on scales as small as <50~pc. This work not only demonstrates the benefits of high-resolution spatially-resolved observations in assessing the effects of feedback mechanisms and accurate chemical abundances, but also the limitations of emission line diagnostic tools which can break down on scales smaller than a H II region. Both aspects are especially relevant as we enter the era of extremely large telescopes, when observing structure on ˜~10~pc scales will no longer be limited to the local universe.

  16. Ionising radiation exposure in patients with circular frame treatment of distal tibial fractures.

    PubMed

    Bryant, H; Dearden, P M C; Harwood, P J; Wood, T J; Sharma, H K

    2015-08-01

    Total radiation exposure accumulated during circular frame treatment of distal tibial fractures was quantified in 47 patients treated by a single surgeon from February 2007 until Oct 2010. The radiation exposures for all relevant radiology procedures for the distal tibial injury were included to estimate the radiation risk to the patient. The median time of treatment in the frame was 169 days (range 105-368 days). Patients underwent a median of 13 sets of plain radiographs; at least one intra operative exposure and 16 patients underwent CT scanning. The median total effective dose per patient from time of injury to discharge was 0.025mSv (interquartile range 0.013-0.162 and minimum to maximum 0.01-0.53). The only variable shown to be an independent predictor of cumulative radiation dose on multivariate analysis was the use of CT scanning. This was associated with a 13-fold increase in overall exposure. Radiation exposure during treatment of distal tibial fractures with a circular frame in this group was well within accepted safe limits. The fact that use of CT was the only significant predictor of overall exposure serves as a reminder to individually assess the risk and utility of radiological investigations on an individual basis. This is consistent with the UK legal requirements for justification of all X-ray imaging, as set out in the Ionising Radiation (Medical Exposure) Regulations 2000 [1].

  17. On the divergences in assessment of environmental impacts from ionising radiation following the Fukushima accident.

    PubMed

    Strand, P; Sundell-Bergman, S; Brown, J E; Dowdall, M

    2017-04-01

    The accident at the Fukushima-Daiichi Nuclear Power Station on March 11, 2011, led to significant contamination of the surrounding terrestrial and marine environments. Whilst impacts on human health remain the primary concern in the aftermath of such an accident, recent years have seen a significant body of work conducted on the assessment of the accident's impacts on both the terrestrial and marine environment. Such assessments have been undertaken at various levels of biological organisation, for different species, using different methodologies and coming, in many cases, to divergent conclusions as to the effects of the accident on the environment. This article provides an overview of the work conducted in relation to the environmental impacts of the Fukushima accident, critically comparing and contrasting methodologies and results with a view towards finding reasons for discrepancies, should they indeed exist. Based on the outcomes of studies conducted to date, it would appear that in order to avoid the fractured and disparate conclusions drawn in the aftermath of previous accidents, radioactive contaminants and their effects can no longer simply be viewed in isolation with respect to the ecosystems these effects may impact. A combination of laboratory based and field studies with a focus on ecosystem functioning and effects could offer the best opportunities for coherence in the interpretation of the results of studies into the environmental impacts of ionising radiation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Differentiating Microbial Forensic qPCR Target and Control Products by Electrospray Ionization Mass Spectrometry

    PubMed Central

    Motley, S. Timothy; Redden, Cassie L.; Sannes-Lowery, Kristin A.; Eshoo, Mark W.; Hofstadler, Steven A.; Burans, James P.

    2013-01-01

    Molecular bioforensic research is dependent on rapid and sensitive methods such as real-time PCR (qPCR) for the identification of microorganisms. The use of synthetic positive control templates containing small modifications outside the primer and probe regions is essential to ensure all aspects of the assay are functioning properly, including the primers and probes. However, a typical qPCR or reverse transcriptase qPCR (qRT-PCR) assay is limited in differentiating products generated from positive controls and biological samples because the fluorescent probe signals generated from each type of amplicon are indistinguishable. Additional methods used to differentiate amplicons, including melt curves, secondary probes, and amplicon sequencing, require significant time to implement and validate and present technical challenges that limit their use for microbial forensic applications. To solve this problem, we have developed a novel application of electrospray ionization mass spectrometry (ESI-MS) to rapidly differentiate qPCR amplicons generated with positive biological samples from those generated with synthetic positive controls. The method has sensitivity equivalent to qPCR and supports the confident and timely determination of the presence of a biothreat agent that is crucial for policymakers and law enforcement. Additionally, it eliminates the need for time-consuming methods to confirm qPCR results, including development and validation of secondary probes or sequencing of small amplicons. In this study, we demonstrate the effectiveness of this approach with microbial forensic qPCR assays targeting multiple biodefense agents (bacterial, viral, and toxin) for the ability to rapidly discriminate between a positive control and a positive sample. PMID:23675878

  19. Differentiating microbial forensic qPCR target and control products by electrospray ionization mass spectrometry.

    PubMed

    Motley, S Timothy; Redden, Cassie L; Sannes-Lowery, Kristin A; Eshoo, Mark W; Hofstadler, Steven A; Burans, James P; Rosovitz, M J

    2013-06-01

    Molecular bioforensic research is dependent on rapid and sensitive methods such as real-time PCR (qPCR) for the identification of microorganisms. The use of synthetic positive control templates containing small modifications outside the primer and probe regions is essential to ensure all aspects of the assay are functioning properly, including the primers and probes. However, a typical qPCR or reverse transcriptase qPCR (qRT-PCR) assay is limited in differentiating products generated from positive controls and biological samples because the fluorescent probe signals generated from each type of amplicon are indistinguishable. Additional methods used to differentiate amplicons, including melt curves, secondary probes, and amplicon sequencing, require significant time to implement and validate and present technical challenges that limit their use for microbial forensic applications. To solve this problem, we have developed a novel application of electrospray ionization mass spectrometry (ESI-MS) to rapidly differentiate qPCR amplicons generated with positive biological samples from those generated with synthetic positive controls. The method has sensitivity equivalent to qPCR and supports the confident and timely determination of the presence of a biothreat agent that is crucial for policymakers and law enforcement. Additionally, it eliminates the need for time-consuming methods to confirm qPCR results, including development and validation of secondary probes or sequencing of small amplicons. In this study, we demonstrate the effectiveness of this approach with microbial forensic qPCR assays targeting multiple biodefense agents (bacterial, viral, and toxin) for the ability to rapidly discriminate between a positive control and a positive sample.

  20. Ionic liquid-assisted electrospray ionization of polysaccharides.

    PubMed

    Chang, Yu-Ling; Lee, Yuan-Chun; Yang, Wen-Bin; Chen, Chung-Hsuan

    2011-04-01

    In this work, we give the report of significant detection sensitivity improvement of electrospray ionization (ESI) mass spectra of polysaccharides by adding various ionic liquid compounds into samples. Mass spectra obtained were greatly simplified and appeared to be similar to spectra from matrix-assisted laser desorption/ionization due to the narrow charge number distribution. Mass spectra of polysaccharides with the attachment of either anion or cation of ionic liquid compounds were observed. No protonated or deprotonated polysaccharide ions were detected when ionic liquid compounds were added into samples. Little alkali-attached polysaccharide ions were observed. Ionic liquid-assisted ESI (ILA-ESI) mass spectrometry has significantly improved the detection sensitivity of large neutral polysaccharide compounds. Copyright © 2011 John Wiley & Sons, Ltd.

  1. Improved Imaging Resolution in Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    Imaging resolution of desorption electrospray ionization mass spectrometry (DESI-MS) was investigated using printed patterns on paper and thin-layer chromatography (TLC) plate surfaces. Resolution approaching 40 m was achieved with a typical DESI-MS setup, which is approximately 5 times better than the best resolution reported previously. This improvement was accomplished with careful control of operational parameters (particularly spray tip-to-surface distance, solvent flow rate, and spacing of lane scans). Also, an appropriately strong analyte/surface interaction and uniform surface texture on the size scale no larger that the desired imaging resolution were required to achieve this resolution. Overall, conditions providing the smallest possible effective desorption/ionization area in the DESI impact plume region and minimizing the analyte redistribution on the surface during analysis led to the improved DESI-MS imaging resolution.

  2. Microfabricated emitter array for an ionic liquid electrospray thruster

    NASA Astrophysics Data System (ADS)

    Nakagawa, Kaito; Tsuchiya, Toshiyuki; Takao, Yoshinori

    2017-06-01

    We have fabricated needle-shaped emitters on a Si wafer by a MEMS process, and measured the voltage-current characteristics and the frequency dependence of a bipolar pulse voltage for ionic liquid electrospray thrusters, which can be mounted on nanosatellites ( ≲ 10 kg). Although the extracted current did not increase with increasing number of emitters, probably owing to the lack of uniformity of the emitters fabricated, we have demonstrated that the emitted current depends on the gap distance between the emitter and the extractor grid electrode, and low frequencies of the bipolar pulse voltage are desirable for thruster operation. Moreover, the Bosch process is required for fabricating a reservoir of ionic liquid, which prevents undesirable electrical short circuits, and the minimum emitter pitch to prevent loss of ion beams to the extractor is estimated to be about 400 µm.

  3. Collisional cooling of large ions in electrospray mass spectrometry.

    PubMed

    Chernushevich, Igor V; Thomson, Bruce A

    2004-03-15

    Collisional cooling of ions in the rf-only multipole guides has become a method of choice for coupling electrospray sources to various mass analyzers. Normally parameters of such ion guides (length, pressure) provide enough thermalization and focusing for ions in a wide mass range. Noncovalent complexes, however, have more compact conformations than denatured biomolecules of similar mass and, therefore may not be transmitted efficiently through standard ion guides, as demonstrated by theoretical analysis, simulations, and experiments. Several methods of improving collisional cooling for large compact ions have been developed on a quadrupole time-of-flight instrument, which include operating the ion guides at higher pressure and trapping ions to increase the cooling time. Improved transmission of heavy ions obtained with those methods is studied in experiments with proteasome 20S, an oligomeric protein noncovalent complex with molecular weight around 692,000, and a few other compounds.

  4. Combined electrophoretic-separation and electrospray method and system

    DOEpatents

    Smith, Richard D.; Olivares, Jose A.

    1989-01-01

    A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary zone electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit.

  5. Electrohydrodynamic simulation of an electrospray in a colloid thruster

    NASA Astrophysics Data System (ADS)

    Jugroot, Manish; Forget, Martin; Malardier-Jugroot, Cecile

    2012-02-01

    A precise understanding of electrosprays is highly interesting as the complexity of micro-technology (such as nano-material processing, spacecraft propulsion and mass-spectrometers) systems increases. A multi-component CFD-based model coupling fluid dynamics, charged species dynamics and electric field is developed. The simulations describe the charged fluid interface with emphasis on the Taylor cone formation and cone-jet transition under the effect of a electric field. The goal is to recapture this transition from a rounded liquid interface into a Taylor cone from an initial uniform distribution, without making assumptions on the behaviour, geometry or charge distribution of the system. The time evolution of the interface highlights the close interaction among space charge, coulombic forces and the surface tension, which appear as governing and competing processes in the transition. The results from the coupled formalism provide valuable insights on the physical phenomena and will be applied to a colloid thruster for small spacecrafts.

  6. pH Effects on Electrospray Ionization Efficiency

    NASA Astrophysics Data System (ADS)

    Liigand, Jaanus; Laaniste, Asko; Kruve, Anneli

    2017-03-01

    Electrospray ionization efficiency is known to be affected by mobile phase composition. In this paper, a detailed study of analyte ionization efficiency dependence on mobile phase pH is presented. The pH effect was studied on 28 compounds with different chemical properties. Neither p K a nor solution phase ionization degree by itself was observed to be sufficient at describing how aqueous phase pH affects the ionization efficiency of the analyte. Therefore, the analyte behavior was related to various physicochemical properties via linear discriminant analyses. Distinction between pH-dependent and pH-independent compounds was achieved using two parameters: number of potential charge centers and hydrogen bonding acceptor capacity (in the case of 80% acetonitrile) or polarity of neutral form of analyte and p K a (in the case of 20% acetonitrile). It was also observed that decreasing pH may increase ionization efficiency of a compound by more than two orders of magnitude.

  7. Influence of boric acid on electrospray ionization efficiency.

    PubMed

    Rebane, Riin; Herodes, Koit

    2012-01-01

    Liquid chromatography electrospray ionization mass-spectrometry (LC-ESI-MS) was used to analyze 9-fluorenylmethylmethoxycarbonyl chloride (Fmoc-Cl) and diethyl ethoxymethylenemalonate (Deemm) derivatives of three amino acids and five other compounds. Influence of boric acid on their ionization was investigated and dramatic impact on the signal was observed. The strongest signal suppression (6% of signal remains) was observed for the Deemm derivative of beta-Alanine (with ammonium acetate in eluent). With only formic acid as the eluent pH modifier, signal enhancement was observed, being largest for Fmoc-Cl derivative of Phenylalanine, 267%. Investigation of the influence of boric acid shows that it is a possible signal enhancer for LC-ESI-MS analysis.

  8. Combined electrophoretic-separation and electrospray method and system

    DOEpatents

    Smith, R.D.; Olivares, J.A.

    1989-06-27

    A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary zone electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., [+-]2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit. 10 figs.

  9. Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry.

    PubMed

    Cai, Yi; Liu, Pengyuan; Held, Michael A; Dewald, Howard D; Chen, Hao

    2016-04-18

    A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room-temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI-MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI-MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI-MS, which could have an impact in electrochemistry and bioanalysis fields.

  10. Water-assisted femtosecond laser machining of electrospray nozzles on glass microfluidic devices.

    PubMed

    An, Ran; Hoffman, Michelle D; Donoghue, Margaret A; Hunt, Alan J; Jacobson, Stephen C

    2008-09-15

    Using water-assisted femtosecond laser machining, we fabricated electrospray nozzles on glass coverslips and on assembled microfluidic devices. Machining the nozzles after device assembly facilitated alignment of the nozzles over the microchannels. The basic nozzle design is a through-hole in the coverslip to pass liquids and a trough machined around the through-hole to confine the electrospray and prevent liquid from wicking across the glass surface. Electrospray from the nozzles was stable with and without pressure-driven flow applied and was evaluated using mass spectra of the peptide bradykinin.

  11. On-line capillary isoelectric focusing-electrospray mass spectrometry for protein characterization

    SciTech Connect

    Tang, Qing; Harrata, K.A.; Lee, C.S.

    1996-12-31

    The integration of capillary isoelectric focusing (CIEF) with electrospray mass spectrometry (ESMS) as a two-dimensional separation system for protein characterization will be presented. Mixtures of protein variants are focused and cathodically mobilized in a polyacrylamide coated capillary. At the end of CIEF capillary, the mobilized protein zones are analyzed by mass spectrometry coupled on-line to an electrospray interface with a coaxial sheath flow configuration. The effects of carrier ampholyte concentration on the CIEF separation and the protein electrospray mass spectra will be discussed. On-line CIEF-ESMS with superior resolving power, speed, and sensitivity will be demonstrated for the analysis of hemoglobin and glycoprotein variants.

  12. Electrospray neutralization process and apparatus for generation of nano-aerosol and nano-structured materials

    SciTech Connect

    Bailey, Charles L.; Morozov, Victor; Vsevolodov, Nikolai N.

    2010-08-17

    The claimed invention describes methods and apparatuses for manufacturing nano-aerosols and nano-structured materials based on the neutralization of charged electrosprayed products with oppositely charged electrosprayed products. Electrosprayed products include molecular ions, nano-clusters and nano-fibers. Nano-aerosols can be generated when neutralization occurs in the gas phase. Neutralization of electrospan nano-fibers with molecular ions and charged nano-clusters may result in the formation of fibrous aerosols or free nano-mats. Nano-mats can also be produced on a suitable substrate, forming efficient nano-filters.

  13. Studying the chemistry of cationized triacylglycerols using electrospray ionization mass spectrometry and density functional theory computations.

    PubMed

    Grossert, J Stuart; Cubero Herrera, Lisandra; Ramaley, Louis; Melanson, Jeremy E

    2014-08-01

    Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na(+)). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na(+), Li(+), K(+), Ag(+), NH4(+)). While most cations bind to oxygen, Ag(+) binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M](+) was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS(3)). These lactones can account for all the major product ions in the MS(3) spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

  14. Analysis of isoflavones in soy drink by capillary zone electrophoresis coupled with electrospray ionization mass spectrometry.

    PubMed

    Bustamante-Rangel, M; Delgado-Zamarreño, M M; Carabias-Martínez, R; Domínguez-Álvarez, J

    2012-01-04

    Capillary zone electrophoresis coupled with electrospray ionization mass spectrometry (CZE-ESI-MS) has been applied for the first time for the separation and quantification of isoflavones in soy products. The proposed method was successfully applied to the determination of seven isoflavones, including aglycones and glucosides, in soy drink. The target compounds were the glucosides daidzin and genistin, and the aglycones daidzein, genistein, formononetin, biochanin A and glycitein. During CE separation in positive mode, the analytes were present as anions, and MS detection was carried out in ESI positive-ion mode. To prevent the frequent drops in current and to improve the resolution in the separation of analytes in anionic form, a programmed nebulizing gas pressure (PNP) was applied along the analysis. Extraction of isoflavones from soy drinks was carried out by liquid-liquid extraction using ethanol. The proposed extraction procedure is simple, efficient, and affords reproducible results. Quantification of the isoflavones in soy drinks using the external standard method did not produce good results; therefore, both internal standard and standard addition quantification methods were used, obtaining significantly similar results. The detection limits found were lower than 3.2 μg L(-1). Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations

    NASA Astrophysics Data System (ADS)

    Grossert, J. Stuart; Herrera, Lisandra Cubero; Ramaley, Louis; Melanson, Jeremy E.

    2014-08-01

    Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

  16. Multifunctional ZnO/Nylon 6 nanofiber mats by an electrospinning-electrospraying hybrid process for use in protective applications

    NASA Astrophysics Data System (ADS)

    Vitchuli, Narendiran; Shi, Quan; Nowak, Joshua; Kay, Kathryn; Caldwell, Jane M.; Breidt, Frederick; Bourham, Mohamed; McCord, Marian; Zhang, Xiangwu

    2011-10-01

    ZnO/Nylon 6 nanofiber mats were prepared by an electrospinning-electrospraying hybrid process in which ZnO nanoparticles were dispersed on the surface of Nylon 6 nanofibers without becoming completely embedded. The prepared ZnO/Nylon 6 nanofiber mats were evaluated for their abilities to kill bacteria or inhibit their growth and to catalytically detoxify chemicals. Results showed that these ZnO/Nylon 6 nanofiber mats had excellent antibacterial efficiency (99.99%) against both the Gram-negative Escherichia coli and Gram-positive Bacillus cereus bacteria. In addition, they exhibited good detoxifying efficiency (95%) against paraoxon, a simulant of highly toxic chemicals. ZnO/Nylon 6 nanofiber mats were also deposited onto nylon/cotton woven fabrics and the nanofiber mats did not significantly affect the moisture vapor transmission rates and air permeability values of the fabrics. Therefore, ZnO/Nylon 6 nanofiber mats prepared by the electrospinning-electrospraying hybrid process are promising material candidates for protective applications.

  17. Chemical Characterization of Crude Petroleum Using Nanospray Desorption Electrospray Ionization Coupled with High-Resolution Mass Spectrometry

    SciTech Connect

    Eckert, Peter A.; Roach, Patrick J.; Laskin, Alexander; Laskin, Julia

    2012-02-07

    Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of liquid petroleum crude oil samples. The analysis was performed in both positive and negative ionization modes using three solvents one of which (acetonitrile/toluene mixture) is commonly used in petroleomics studies while two other polar solvents (acetonitrile/water and methanol/water mixtures) are generally not compatible with petroleum characterization using mass spectrometry. The results demonstrate that nano-DESI analysis efficiently ionizes petroleum constituents soluble in a particular solvent. When acetonitrile/toluene is used as a solvent, nano-DESI generates electrospray-like spectra. In contrast, strikingly different spectra were obtained using acetonitrile/water and methanol/water. Comparison with the literature data indicates that these solvents selectively extract water-soluble constituents of the crude oil. Water-soluble compounds are predominantly observed as sodium adducts in nano-DESI spectra indicating that addition of sodium to the solvent may be a viable approach for efficient ionization of water-soluble crude oil constituents. Nano-DESI enables rapid screening of different classes of compounds in crude oil samples using solvents that are rarely used for petroleum characterization.

  18. Desorption electrospray ionization mass spectrometry for high-throughput analysis of pharmaceutical samples in the ambient environment.

    PubMed

    Chen, Huanwen; Talaty, Nari N; Takáts, Zoltán; Cooks, R Graham

    2005-11-01

    Desorption electrospray ionization (DESI) allows mass spectrometry to be used for on-line high-throughput monitoring of pharmaceutical samples in the ambient environment, without prior sample preparation. Positive and negative ion DESI are used to characterize the active ingredients in pharmaceutical samples formulated as tablets, ointments, and liquids. Compounds of a wide variety of chemical types are detected in these complex matrices. The effects on analytical performance of operating parameters, including the electrospray high voltage, heated capillary temperature, solvent infusion rate, and solvent composition, are evaluated and optimized. In addition to experiments in which a simple solvent is sprayed onto the solid analyte samples, reactive desorption is performed by adding reagents to the solvent spray to generate particularly stable or characteristic ions with the analytes of interest. A variable-speed moving belt was built for high-throughput sampling and used to provide rapid qualitative and semiquantitative information on drug constituents in tablets. Sampling rates as high as 3 samples/s are achieved in the ambient environment. Relative standard deviations of the relative ion abundances for major components in the mass spectra are in the range of 2-8%. Impurities and components present at levels as low as approximately 0.1% are identified and carryover effects are minimized in high-throughput on-line analysis of pharmaceutical samples.

  19. A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

    2011-01-01

    A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same