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Sample records for positive electrospray ionisation

  1. Electrospray ionisation mass spectrometry: principles and clinical applications.

    PubMed

    Ho, C S; Lam, C W K; Chan, M H M; Cheung, R C K; Law, L K; Lit, L C W; Ng, K F; Suen, M W M; Tai, H L

    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.

  2. The effect of electrospray solvent composition on desorption electrospray ionisation (DESI) efficiency and spatial resolution.

    PubMed

    Green, F M; Salter, T L; Gilmore, I S; Stokes, P; O'Connor, G

    2010-04-01

    In desorption electrospray ionisation (DESI) the interaction between the electrospray and the surface is key to two important analytical parameters, the spatial resolution and the sensitivity. We evaluate the effect of the electrospray solvent type, organic solvent fraction with water, analyte solubility and substrate wettability on DESI erosion diameter and material transferral into useful ion signal. To do this five amino acids, glycine, alanine, valine, leucine and phenylalanine are prepared as thin films on three substrates, UV/ozone treated glass, glass and polytetrafluoroethylene (PTFE). Four different solvents, acetonitrile (ACN), methanol (MeOH), ethanol (EtOH) and propan-2-ol (IPA), are used with organic solvent fractions with water varying from 0.1 to 1. These model systems allow the solubility or wettability to be kept constant as other parameters are varied. Additionally, comparison with electrospray ionisation (ESI) allows effects of ionisation efficiency to be determined. It is shown that the DESI efficiency is linearly dependent on the solubility (for these materials at least) and for analytes with solubilities below 1.5 g kg(-1), additional strategies may be required for DESI to be effective. We show that the DESI erosion diameter improves linearly with organic solvent fraction, with an organic solvent fraction of 0.9 instead of 0.5 leading to a 2 fold improvement. Furthermore, this leads to a 35 fold increase in DESI efficiency, defined as the molecular ion yield per unit area. It is shown that these improvements correlate with smaller droplet sizes rather than surface wetting or ionisation. PMID:20349538

  3. Simultaneous determination of amiloride and hydrochlorothiazide in human plasma by liquid chromatography/tandem mass spectrometry with positive/negative ion-switching electrospray ionisation.

    PubMed

    Song, Min; Hang, Taijun; Zhao, Hua; Wang, Li; Ge, Ping; Ma, Pengcheng

    2007-01-01

    A new method for simultaneous determination of amiloride and hydrochlorothiazide by liquid chromatography/electrospray tandem mass spectrometry (LC/MS/MS) operated in positive and negative ionization switching mode was developed and validated. Protein precipitation with acetonitrile was selected for sample preparation. The analytes were separated on a Phenomenex Curosil-PFP (250x4.6 mm, 5 microm) column by a gradient elution with a mobile phase consisting of 0.15% formic acid solution containing 0.23% ammonium acetate and methanol pumped at a flow rate of 1.0 mL.min(-1). Rizatriptan was used as the internal standard (IS) for quantification. The determination was carried out on a Waters Quattro-micro triple-quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode using the following transitions monitored simultaneously: positive m/z 230-->171 for amiloride, m/z 270-->158 for rizatriptan, and negative m/z 296-->205 for hydrochlorothiazide. The lower limits of quantification (LLOQs) were 0.1 and 1.0 ng.mL(-1) for amiloride and hydrochlorothiazide, respectively, which were lower than other published methods by using ultraviolet (UV), fluorimetric or mass spectrometric detection. The intra- and inter-day precision and accuracy were studied at three different concentration levels and were always better than 15% (n=5). This simple and robust LC/MS/MS method was successfully applied to the pharmacokinetic study of compound amiloride and hydrochlorothiazide tablets in healthy male Chinese volunteers. PMID:17902196

  4. 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.

  5. 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.

  6. A novel arsenical in clam kidney identified by liquid chromatography/electrospray ionisation mass spectrometry.

    PubMed

    Francesconi, K A; Edmonds, J S

    2001-01-01

    Kidneys of clams of the genus Tridacna accumulate metabolic products from symbiotic unicellular algae that grow in the mantles of the clams. These metabolites include organoarsenic compounds that are biosynthesised by algae from arsenate in seawater. The arsenic compounds in aqueous extracts of the kidney of the giant clam T. derasa were investigated by liquid chromatography/electrospray ionisation mass spectrometry. About 50% of the water-soluble arsenic was present as dimethylarsinoylribosides and dimethylarsinate which are common algal metabolites. The major compound in the kidney (50% of water-soluble arsenic) was identified as a 5-dimethylarsinoyl-2,3,4-trihydroxycarboxylic acid, a new natural product.

  7. Analysis of triacetone triperoxide complexes with alkali metal ions by electrospray and extractive electrospray ionisation combined with ion mobility spectrometry and mass spectrometry.

    PubMed

    Hill, Alex R; Edgar, Mark; Chatzigeorgiou, Maria; Reynolds, James C; Kelly, Paul F; Creaser, Colin S

    2015-01-01

    The complexation of triacetone triperoxide (TATP) with a range of alkali metals has been studied by electrospray ionisation-mass spectrometry yield [M+Cat](+) ions for all of the alkali metals. The formation of [2TATP+Li+LiX](+) (X = Br, Cl) sandwich complexes was also observed. Collision cross- sections for the lithium-containing complexes of TATP were measured by travelling wave ion mobility spectrometry mass spectrometry, and compared well with computationally determined structures. Extractive electrospray ionisation (EESI) using a lithium doped electrospray is demonstrated for the detection of TATP vapours desorbed from a metal surface. The limit of detection for EESI was shown to be 20 ng using the [TATP+Li](+) ion. PMID:26307706

  8. 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. PMID:26988473

  9. 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.

  10. High throughput volatile fatty acid skin metabolite profiling by thermal desorption secondary electrospray ionisation mass spectrometry.

    PubMed

    Martin, Helen J; Reynolds, James C; Riazanskaia, Svetlana; Thomas, C L Paul

    2014-09-01

    The non-invasive nature of volatile organic compound (VOC) sampling from skin makes this a priority in the development of new screening and diagnostic assays. Evaluation of recent literature highlights the tension between the analytical utility of ambient ionisation approaches for skin profiling and the practicality of undertaking larger campaigns (higher statistical power), or undertaking research in remote locations. This study describes how VOC may be sampled from skin and recovered from a polydimethylsilicone sampling coupon and analysed by thermal desorption (TD) interfaced to secondary electrospray ionisation (SESI) time-of-flight mass spectrometry (MS) for the high throughput screening of volatile fatty acids (VFAs) from human skin. Analysis times were reduced by 79% compared to gas chromatography-mass spectrometry methods (GC-MS) and limits of detection in the range 300 to 900 pg cm(-2) for VFA skin concentrations were obtained. Using body odour as a surrogate model for clinical testing 10 Filipino participants, 5 high and 5 low odour, were sampled in Manilla and the samples returned to the UK and screened by TD-SESI-MS and TD-GC-MS for malodour precursors with greater than >95% agreement between the two analytical techniques. Eight additional VFAs were also identified by both techniques with chains 4 to 15 carbons long being observed. TD-SESI-MS appears to have significant potential for the high throughput targeted screening of volatile biomarkers in human skin.

  11. Quantitative analysis of clenbuterol in meat products using liquid chromatography-electrospray ionisation tandem mass spectrometry.

    PubMed

    Guy, P A; Savoy, M C; Stadler, R H

    1999-12-24

    A method is presented that allows quantitation of clenbuterol in meat and liver products at the ng/kg level by liquid chromatography-electrospray ionisation tandem mass spectrometry (LC-ESIMS-MS) using a stable isotopically labeled internal standard. The practical procedure involves acid extraction followed by two solid-phase clean-up steps with C18 and strong cation-exchange (SCX) resins. The typical recovery of the analyte spiked at 0.4 microg/kg in meat and liver samples was at 63+/-7%. Mass spectral acquisition was done in multiple reaction monitoring (MRM) to provide a high degree of sensitivity, achieving a limit of detection and quantitation at 10 and 15 ng/kg, respectively. Two precursor ions at m/z 277 and 279, corresponding to the characteristic isotopic cluster of the two chlorine atoms of clenbuterol, were monitored by LC-ESIMS-MS to provide unambiguous identity of the analyte. Samples of meat and liver of various origins with either incurred residues or spiked with known amounts of clenbuterol were used to validate the method.

  12. Artificially-aged cachaça samples characterised by direct infusion electrospray ionisation mass spectrometry.

    PubMed

    de Souza, Patterson P; Resende, Ana M M; Augusti, Daniella V; Badotti, Fernanda; Gomes, Fátima de Cássia O; Catharino, Rodrigo R; Eberlin, Marcos N; Augusti, Rodinei

    2014-01-15

    Direct infusion electrospray ionisation mass spectrometry in the negative ion mode [ESI(-)-MS] was employed to evaluate the authenticity of aged cachaças, a traditional and valuable Brazilian alcoholic beverage prepared from the distillation of brewed sugarcane juice and aged in barrels made of common woods. Counterfeit samples were prepared by adding dyes, sawdust or essences to a freshly-distiled, much less valuable sample (white cachaça) to simulate the 1-2years long natural ageing in wooden barrels. A simple visual inspection revealed remarkable differences between the ESI(-)-MS of the authentic samples (aged in oak or amburana casks) and the artificially-aged counterfeit samples. A set of diagnostic ions were detectable in the ESI(-)-MS of the authentic samples aged in oak (m/z 197, 241, 301 and 307) and amburana (m/z 271 and 377/379). This fast and direct methodology seems useful as a routine procedure to monitor this highly profitable and common counterfeit practice. PMID:24054215

  13. Artificially-aged cachaça samples characterised by direct infusion electrospray ionisation mass spectrometry.

    PubMed

    de Souza, Patterson P; Resende, Ana M M; Augusti, Daniella V; Badotti, Fernanda; Gomes, Fátima de Cássia O; Catharino, Rodrigo R; Eberlin, Marcos N; Augusti, Rodinei

    2014-01-15

    Direct infusion electrospray ionisation mass spectrometry in the negative ion mode [ESI(-)-MS] was employed to evaluate the authenticity of aged cachaças, a traditional and valuable Brazilian alcoholic beverage prepared from the distillation of brewed sugarcane juice and aged in barrels made of common woods. Counterfeit samples were prepared by adding dyes, sawdust or essences to a freshly-distiled, much less valuable sample (white cachaça) to simulate the 1-2years long natural ageing in wooden barrels. A simple visual inspection revealed remarkable differences between the ESI(-)-MS of the authentic samples (aged in oak or amburana casks) and the artificially-aged counterfeit samples. A set of diagnostic ions were detectable in the ESI(-)-MS of the authentic samples aged in oak (m/z 197, 241, 301 and 307) and amburana (m/z 271 and 377/379). This fast and direct methodology seems useful as a routine procedure to monitor this highly profitable and common counterfeit practice.

  14. 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.

  15. 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. PMID:19592003

  16. On the determination of underivatised fatty alcohol ethoxylates by electrospray ionisation-mass spectrometry.

    PubMed

    Bernabé-Zafón, Virginia; Simó-Alfonso, Ernesto F; Ramis-Ramos, Guillermo

    2006-06-23

    The oligomers of fatty alcohol ethoxylates (FAEs) exhibit large sensitivity differences in mass spectrometry with electrospray ionisation (ESI-MS) and atmospheric pressure chemical ionization (APCI). Standards of the oligomers from m=1 to 7 ethylene oxide units (EOs) and linear alkyl chains from n=10 to 18 carbon atoms were infused to examine the relative sensitivities or response factors in several media. The response factors of the [M+H]+ and [M+Na]+ peaks in 9:1 acetonitrile/water and methanol/water media containing acid buffers increased following irregular patterns when n and m increased. In methanol/water the response factors depended on the parity of m, being larger than the average trend for the oligomers with an even value of m with respect to those having an odd value. This was attributed to the presence of an uncompensated C-O-C or C-O-H dipole in the former oligomers. The advantages of using ESI over APCI and of measuring the [M+H]+ peaks in an acid methanol/water medium containing 0.1 M HCl are discussed. The advantages and limitations of using models of the response factors to evaluate oligomer concentrations with a reduced set of selected standards are examined. The determination of underivatised FAEs using acid media was made compatible with previous HPLC separation by implementing either a triconcentric nebulizer fed with an acid liquid sheath, or a capillary T-union inserted between the column outlet and the biconcentric nebulizer, and fed with an acid stream provided by a syringe pump.

  17. 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.

  18. Letter: characterisation and identification of spermine and spermidine derivatives in Microdesmis keayana and Microdesmis puberula roots by electrospray ionisation tandem mass spectrometry and high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Roumy, Vincent; Hennebelle, Thierry; Zamblé, Alexis; Zamblé Yao, Jacques; Sahpaz, Sevser; Bailleul, François

    2008-01-01

    Three new N(1),N(5),N(14)-tris(4- hydroxycinnamoyl)spermines were identified in hydromethanolic root extracts of Microdesmis keayana J. Léonard and Microdesmis puberula Hook f. The electrospray ionisation tandem mass spectrometry (ESI-MS/MS) technique with specific nuclear magnetic resonance analysis of hydrolysed products made it possible to identify N(1),N(5),N(14)-tris(p-coumaroyl)spermine, N(1)-feruloyl,N(5),N(14)-di(p-coumaroyl)spermine and N(1),N(5),N(14)-tris(feruloyl)spermine, named keayanines B, C and D, respectively. ESI-MS/MS analysis most effectively provided structural data although high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry was also used to characterise four other compounds from Microdesmis puberula-keayanidines A, B, C and keayanine A-which had already been identified in M. keayana. This chemical data is the first to be published for M. puberula which is a commonly used plant in Central African traditional medicine. PMID:18493101

  19. Method development for the determination of selected pesticides on tobacco by high-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry.

    PubMed

    Mayer-Helm, Bernhard; Hofbauer, Ludwig; Müller, Jutta

    2008-02-15

    A method was developed for the quantitative determination of alachlor, benalaxyl, clomazone, diflubenzuron, dimethomorph, diphenamid, ethofumesate, metalaxyl, methoprene, metobromuron and piperonyl butoxide on tobacco. The pesticides were extracted with water and methanol from five different types of tobacco. The extracts were purified by partition on an extraction cartridge containing diatomaceous earth. The purified extracts were analysed by reversed-phase high-performance liquid chromatography connected to an atmospheric pressure ionisation-electrospray-triple quadrupole mass spectrometer operating in the positive ion mode. Two different transitions and their relative intensities were monitored for unambiguous identification. All pesticides presented overall recovery rates between 35% and 110%. The trueness is near 100% and the interday precision is below 15%. The limits of quantifications are equal or below the guidance residue levels proposed by the Agrochemical Advisory Committee of CORESTA, an association of organisations having scientific research relative to tobacco.

  20. Determination of alkyl benzyl and dialkyl dimethyl quaternary ammonium biocides in occupational hygiene and environmental media by liquid chromatography with electrospray ionisation mass spectrometry and tandem mass spectrometry.

    PubMed

    Ford, Michael J; Tetler, Lee W; White, John; Rimmer, Duncan

    2002-04-01

    A new method for the simultaneous qualitative and quantitative determination of alkyl benzyl and dialkyl quaternary ammonium compounds (QACs) has been developed. Analysis is by reversed-phase high-performance liquid chromatography coupled with electrospray ionisation mass spectrometry. QACs are extremely amenable to the electrospray ionisation technique (limit of detection of BAC C12 homologue 3 ng ml(-1)). The selectivity of mass spectrometric detection allows simultaneous determination of benzyl and dialkyl dimethyl ammonium compounds. The method was successfully applied to the analysis of real samples (occupational hygiene sampling devices, products and swimming pool water). Structural information was obtained by MS-MS and cone voltage ion dissociation techniques. Ion dissociation enabled the structural elucidation of an unknown quaternary ammonium compound present in a commercial formulation.

  1. 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.

  2. Characterisation of legumes by enzymatic hydrolysis, microdialysis sampling, and micro-high-performance anion-exchange chromatography with electrospray ionisation mass spectrometry.

    PubMed

    Okatch, Harriet; Torto, Nelson; Armateifio, Joan

    2003-04-11

    An assay based on enzymatic hydrolysisand microdialysis sampling, micro-high-performance anion-exchange chromatography (micro-HPAEC) with electrospray ionisation mass spectrometry (ESI-MS) for the characterisation of legumes is presented. Characterisation of two bean varieties; Phaseolus mungo and P. acutifilous was based upon enzymatic hydrolysis using an endo-beta-mannanase from Aspergillus niger with subsequent analysis of the hydrolysates with HPAEC-MS. The hydrolysates were detected in the positive ionisation mode after desalting the chromatographic effluent, employing a cation-exchange membrane desalting device with water as the regenerating liquid. Mass chromatograms, acquiredafter hydrolysis of both bean samples for 12 h, showed two different profiles of hydrolysates. The P. mungo bean hydrolysate showed the presence of saccharides with a degree of polymerisation (DP) in the range of 2-6, whereas that of P. acutifilous showed only DPs of 2-5. Both bean samples had one type of DP 2, but showed different types of DPs 3, 4 and 5. Only the P. mungo sample showed the presence of DP 6. The most abundant fraction for P. mungo was DP 4, whereas that for P. acutifilous was DP 5. Tandem MS of the hydrolysates showed that the DP 2 hydrolysates observed for the samples were of the same type, having a 1,6 linkage. Also tandem MS data for DPs 3, 4, and 5 showed that similar hydrolysates were present within the same sample as well as among the two samples. The data also showed the existence of 1,6 linkages for DP 3, 4, and 5 hydrolysates. The single enzymatic hydrolysis in combination with microdialysis and HPAEC with ESI-MS proved to be sufficient and reproducible for profiling and showing the difference between the two bean samples. PMID:12735463

  3. 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.

  4. Neutral and acidic products derived from hydroxyl radical-induced oxidation of arabinotriose assessed by electrospray ionisation mass spectrometry.

    PubMed

    Moreira, Ana S P; da Costa, Elisabete V; Evtuguin, Dmitry V; Coimbra, Manuel A; Nunes, Fernando M; Domingues, M Rosário M

    2014-04-01

    The oxidation of α-(1 → 5)-L-arabinotriose (Ara3), an oligosaccharide structurally related to side chains of coffee arabinogalactans, was studied in reaction with hydroxyl radicals generated under conditions of Fenton reaction (Fe(2+)/H2O2). The acidic and neutral oxidation products were separated by ligand exchange/size-exclusion chromatography, subsequently identified by electrospray ionisation mass spectrometry (ESI-MS) and structurally characterised by tandem MS (ESI-MS/MS). In acidic fraction were identified several oxidation products containing an acidic residue at the corresponding reducing end of Ara3, namely arabinonic acid, and erythronic, glyceric and glycolic acids formed by oxidative scission of the furanose ring. In neutral fractions were identified derivatives containing keto, hydroxy and hydroperoxy moieties, as well as derivatives resulting from the ring scission at the reducing end of Ara3. In both acidic and neutral fractions, beyond the trisaccharide derivatives, the corresponding di- and monosaccharide derivatives were identified indicating the occurrence of oxidative depolymerisation. The structural characterisation of these oxidation products by ESI-MS/MS allowed the differentiation of isobaric and isomeric species of acidic and neutral character. The species identified in this study may help in detection of roasting products associated with the free radical-mediated oxidation of coffee arabinogalactans.

  5. Single-stage accelerator mass spectrometer radiocarbon-interference identification and positive-ionisation characterisation

    NASA Astrophysics Data System (ADS)

    Wilcken, K. M.; Freeman, S. P. H. T.; Xu, S.; Dougans, A.

    2013-01-01

    A single-stage accelerator mass spectrometer (SSAMS) is a good alternative to conventional spectrometers based on tandem electrostatic acceleration for radiocarbon measurement and permits experimentation with both negative and positive carbon ions. However, such 14C AMS of either polarity ions is limited by an interference. In the case of anion acceleration we have newly determined this to be summed 13C and 16O by improvising an additional Wien filter on our SSAMS deck. Also, 14C AMS might be improved by removing its dependency on negative-ionisation in a sputter ion source. This requires negative-ionisation of sample atoms elsewhere to suppress the 14N interference, which we accomplish by transmitting initially positive ions through a thin membrane. The ionisation dependence on ion-energy is found to be consistent with previous experimentation with vapours and thicker foils.

  6. Simultaneous determination of volatile and non-volatile nitrosamines in processed meat products by liquid chromatography tandem mass spectrometry using atmospheric pressure chemical ionisation and electrospray ionisation.

    PubMed

    Herrmann, S S; Duedahl-Olesen, L; Granby, K

    2014-02-21

    A sensitive, selective and generic method has been developed for the simultaneous determination of the contents (μgkg(-1) range) of both volatile nitrosamines (VNA) and non-volatile nitrosamines (NVNA) in processed meat products. The extraction procedure only requires basic laboratory equipment and a small volume of organic solvent. Separation and quantification were performed by the developed LC-(APCI/ESI)MS/MS method. The method was validated using spiked samples of three different processed meat products. Satisfactory recoveries (50-130%) and precisions (2-23%) were obtained for eight VNA and six NVNAs with LODs generally between 0.2 and 1μgkg(-1), though for a few analyte/matrix combinations higher LODs were obtained (3 to 18μgkg(-1)). The validation results show that results obtained for one meat product is not always valid for other meat products. We were not able to obtain satisfactory results for N-nitrosohydroxyproline (NHPRO), N-nitrosodibenzylamine (NDBzA) and N-nitrosodiphenylamine (NDPhA). Application of the APCI interface improved the sensitivity of the method, because of less matrix interference, and gave the method a wider scope, as some NAs were ionisable only by APCI. However, it was only possible to ionize N-nitroso-thiazolidine-4-carboxylic acid (NTCA) and N-nitroso-2-methyl-thiazolidine-4-carboxylic acid (NMTCA) by ESI. The validated method was applied for the analysis of processed meat products and contents of N-nitrosodimethylamine (NDMA), N-nitrosopyrrolidine (NPYR), N-nitrosomethylaniline (NMA), N-nitrosoproline (NPRO), NTCA, and NMTCA were found in one or several nitrite cured meat products, whereas none were detected in non-nitrite cured bacon.

  7. 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.

  8. The simultaneous determination of selected flavonol glycosides and aglycones in Ginkgo biloba oral dosage forms by high-performance liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Dubber, M-J; Sewram, V; Mshicileli, N; Shephard, G S; Kanfer, I

    2005-04-01

    An accurate, precise and sensitive liquid chromatography-tandem mass spectrometric (LC-MS-MS) method was developed for the determination of two flavonol glycosides, rutin and quercitrin, together with the algycone markers, quercetin, kaempferol and isorhamnetin in several Ginkgo biloba solid oral dosage forms. In addition, a novel quercetin glycoside, not yet reported in Ginkgo extracts, was identified. Liquid chromatography was performed using a minibore high-performance liquid chromatography (HPLC) column (150 mm x 2.0mm i.d.) and a one step gradient of acetonitrile-formic acid (0.3%) at a flow rate of 0.5 ml/min. Baseline separation of the five selected flavonol marker compounds was achieved within 20 min at 45 degrees C. Tandem mass spectrometry was performed using electrospray ionisation (ESI) in the negative ion mode. The marker compounds exhibited linearity over the range of 3-26 microg/ml and intra- and inter-day standard deviations were better than 7% and 16%, respectively. All Ginkgo products investigated were found to contain varying amounts of target analytes.

  9. Fractionation and analysis of lipopolysaccharide-derived oligosaccharides by zwitterionic-type hydrophilic interaction liquid chromatography coupled with electrospray ionisation mass spectrometry.

    PubMed

    Man-Kupisinska, Aleksandra; Bobko, Ewelina; Gozdziewicz, Tomasz K; Maciejewska, Anna; Jachymek, Wojciech; Lugowski, Czeslaw; Lukasiewicz, Jolanta

    2016-06-01

    Lipopolysaccharide (LPS, endotoxin) is a main surface antigen and virulence factor of Gram-negative bacteria. Regardless of the source of LPS, this molecule, isolated from the smooth forms of bacteria, is characterised by a general structural layout encompassing three regions: (i) an O-specific polysaccharide (O-PS) - a polymer of repeating oligosaccharide units, (ii) core oligosaccharide (OS), and (iii) the lipid A anchoring LPS in the outer membrane of the cell envelope of Gram-negative bacteria. Structural analysis usually requires degradation of LPS and further efficient separation of various poly- and oligosaccharide glycoforms. The hydrophilic interaction liquid chromatography (HILIC) was shown as an efficient technique for separation of labelled or native neutral and acidic glycans, glycopeptides, sialylated glycans, glycosylated and nonglycosylated peptides. Herein we adopted ZIC(®) (zwitterionic stationary phase covalently attached to porous silica)-HILIC technology in combination with electrospray ionisation mass spectrometry to separate different LPS-derived oligosaccharides. As a result three effective procedures have been developed: (i) to separate different core oligosaccharides of Escherichia coli R1 LOS, (ii) to separate RU-[Hep]-Kdo oligosaccharides from core OS glycoforms of Hafnia alvei PCM 1200 LPS, and (iii) to separate Hep and Kdo-containing mono, di-, tri- and tetrasaccharides of H. alvei PCM 1200 LPS. Moreover, some of developed analytical procedures were scaled to semi-preparative protocols and used to obtain highly-purified fractions of the interest in larger quantities required for future evaluation, analysis, and biological applications. PMID:27085741

  10. Simultaneous determination of tanshinone IIA and cryptotanshinone in rat plasma by liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Li, Jing; Wang, Guangji; Li, Peng; Hao, Haiping

    2005-11-01

    Tanshinone IIA (TS) and cryptotanshinone (CT) are the major active constituents contained in Radix salvia miltiorrhiza. This paper described a rapid, sensitive and specific assay for the simultaneous quantitative determination of TS and CT in rat plasma. After a single step of liquid-liquid extraction, plasma samples were analyzed by high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) using a reversed-phase C18 column (150 mmx2.0 mm, 5 microm, Shim-pack VP-ODS column). The assay was linear in the concentration range of 2-200 ng/ml. The lower limits of quantification of TS and CT were 1 and 0.2 ng/ml, respectively. Recoveries of TS and CT were greater than 80%. The precisions and accuracies determined from 5 days were all within 12%. The assay was applied to a pharmacokinetic study in rats after an oral administration of total tanshinones with a dose of 150 mg/kg (containing 12% of TS and CT). Results showed that this simple and rapid method was sensitive enough to follow the plasma levels of TS and CT in rats, even though the concentration maximums of both were below 20 ng/ml after an oral administration of total tanshinones. PMID:16140046

  11. Histidine-containing host-defence skin peptides of anurans bind Cu2+. An electrospray ionisation mass spectrometry and computational modelling study.

    PubMed

    Wang, Tianfang; Andreazza, Hayley J; Pukala, Tara L; Sherman, Patrick J; Calabrese, Antonio N; Bowie, John H

    2011-05-15

    Anuran peptides which contain His, including caerin 1.8 (GLFKVLGSVAKHLLPHVVPVIAEKL-NH(2)), caerin 1.2 (GLLGVLGSVAKHVLPHVVPVIAEHL-NH(2)), Ala(15) maculatin 1.1 (GLFGVLAKVAAHVVAIEHF-NH(2)), fallaxidin 4.1 (GLLSFLPKVIGHLIHPPS-OH), riparin 5.1 (IVSYPDDAGEHAHKMG-NH(2)) and signiferin 2.1 (IIGHLIKTALGMLGL-NH(2)), all form MMet(2+) and (M + Met(2+)-2H(+))(2+) cluster ions (where Met is Cu, Mg and Zn) following electrospray ionisation (ESI) in a Waters QTOF 2 mass spectrometer. Peaks due to Cu(II) complexes are always the most abundant relative to other metal complexes. Information concerning metal(2+) connectivity in a complex has been obtained (at least in part) using b and y fragmentation data from ESI collision-induced dissociation tandem mass spectrometry (CID MS/MS). Theoretical calculations, using AMBER version 10, show that MCu(2+) complexes with the membrane active caerin 1.8, Ala(15) maculatin 1.1 and fallaxidin 4.1 are four-coordinate and approximating square planar, with ligands including His and Lys, together with the carbonyl oxygens of particular backbone amide groups. When binding can occur through two His, or one His and one Lys, the His/Lys ligand structure is the more stable for the studied systems. The three-dimensional (3D) structures of the complexes are always different from the previously determined structures of the uncomplexed model peptides (using 2D nuclear magnetic resonance (NMR) spectroscopy in membrane-mimicking solvents like trifluoroethanol/water). PMID:21488120

  12. 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.

  13. 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

    2014-09-01

    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

  14. Some critical aspects in the determination of binding constants by electrospray ionisation mass spectrometry at the example of arsenic bindings to sulphur-containing biomolecules.

    PubMed

    Schmidt, Anne-Christine; Steier, Sandra

    2010-08-01

    The influences of reactant concentrations, solvent type, acid strength, pH conditions and ionic strength on the determination of apparent gas-phase equilibrium constants K using electrospray ionisation mass spectrometry (ESI-MS) were elucidated. As example serves the interaction of the tripeptide glutathione (GSH) with phenylarsine oxide (PAO). It was shown that rising initial concentrations of both reactants were not adequately compensated by increasing signal intensities of the reaction products in the mass spectra. The equilibrium constant for the formation of the phenylarsenic-substituted peptide species decreased from 1.42 x 10(5) +/- 1.81 x 10(4) l micromol(-1) to 1.54 x 10(4) +/- 1.5 x 10(3) l micromol(-1) with rising initial GSH concentrations from 1 to 10 microM at fixed PAO molarity of 50 microM. K values resulting from a series with a fixed GSH molarity of 5 microM and a PAO molarity varied from 10 to 100 microM remained in a narrower range between 4.59 x 10(4) +/- 2.15 x 10(4) l micromol(-1) and 1.07 x 10(4) +/- 4.0 x 10(3) l micromol(-1). In contrast, consumption numbers calculated from the ion intensity ratios of reaction products to the unreacted peptide were not influenced by the initial reactant concentrations. In a water-acetonitrile-acetic acid mixture (48:50:2, v:v), the consumption of 5 micro M GSH increased from 8.3 +/- 1.4% to 39.6 +/- 1.6% with increased molar excess of PAO from 2 to 20, respectively. The GSH consumption was considerably enhanced in a changed solvent system consisting of 25% acetonitrile and 75% 10 mM ammonium formate, pH 5.0 (v:v) up to 80% of the original peptide amount at an only threefold molar arsenic excess.

  15. 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.

  16. Profile of phenolic compounds of Brazilian virgin olive oils by rapid resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry (RRLC-ESI-TOF-MS).

    PubMed

    Ballus, Cristiano Augusto; Quirantes-Piné, Rosa; Bakhouche, Abdelhakim; da Silva, Luiz Fernando de Oliveira; de Oliveira, Adelson Francisco; Coutinho, Enilton Fick; da Croce, Dorli Mario; Segura-Carretero, Antonio; Godoy, Helena Teixeira

    2015-03-01

    In recent years, agronomical researchers began to cultivate several olive varieties in different regions of Brazil to produce virgin olive oil (VOO). Because there has been no reported data regarding the phenolic profile of the first Brazilian VOO, the aim of this work was to determine phenolic contents of these samples using rapid-resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry. 25 VOO samples from Arbequina, Koroneiki, Arbosana, Grappolo, Manzanilla, Coratina, Frantoio and MGS Mariense varieties from three different Brazilian states and two crops were analysed. It was possible to quantify 19 phenolic compounds belonging to different classes. The results indicated that Brazilian VOOs have high total phenolic content because the values were comparable with those from high-quality VOOs produced in other countries. VOOs from Coratina, Arbosana and Grappolo presented the highest total phenolic content. These data will be useful in the development and improvement of Brazilian VOO. PMID:25306359

  17. 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.

  18. Rapid characterisation and comparison of saponin profiles in the seeds of Korean Leguminous species using ultra performance liquid chromatography with photodiode array detector and electrospray ionisation/mass spectrometry (UPLC-PDA-ESI/MS) analysis.

    PubMed

    Ha, Tae Joung; Lee, Byong Won; Park, Ki Hun; Jeong, Seong Hun; Kim, Hyun-Tae; Ko, Jong-Min; Baek, In-Youl; Lee, Jin Hwan

    2014-03-01

    The present work was reported on investigation of saponin profiles in nine different legume seeds, including soybean, adzuki bean, cowpea, common bean, scarlet runner bean, lentil, chick pea, hyacinth bean, and broad bean using ultra performance liquid chromatography with photodiode array detector and electrospray ionisation/mass spectrometry (UPLC-PDA-ESI/MS) technique. A total of twenty saponins were characterised under rapid and simple conditions within 15min by the 80% methanol extracts of all species. Their chemical structures were elucidated as soyasaponin Ab (1), soyasaponin Ba (2), soyasaponin Bb (3), soyasaponin Bc (4), soyasaponin Bd (5), soyasaponin αg (6), soyasaponin βg (7), soyasaponin βa (8), soyasaponin γg (9), soyasaponin γa (10), azukisaponin VI (11), azukisaponin IV (12), azukisaponin II (13), AzII (14), AzIV (15), lablaboside E (16), lablaboside F (17), lablaboside D (18), chikusetusaponin IVa (19), and lablab saponin I (20). The individual and total saponin compositions exhibited remarkable differences in all legume seeds. In particular, soyasaponin βa (8) was detected the predominant composition in soybean, cowpea, and lentil with various concentrations. Interestingly, soybean, adzuki bean, common bean, and scarlet runner bean had high saponin contents, while chick pea and broad bean showed low contents. PMID:24176342

  19. Simultaneous determination of nineteen hallucinogenic tryptamines/beta-calbolines and phenethylamines using gas chromatography-mass spectrometry and liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Kikura-Hanajiri, R; Hayashi, M; Saisho, K; Goda, Y

    2005-10-15

    To investigate the trend of non-controlled drugs of abuse, simultaneous analytical methods were developed using GC-MS and LC-ESI-MS for 8 tryptamines/beta-carbolines, 6 phenethylamines of typically non-controlled substances in Japan, and, additionally, five legally controlled tryptamines and phenethylamines originally found in fungi or plants. Moreover, the proposed methods were applied to analyses of these drugs in 99 kinds of products (a total number of 123 products purchased at adult shops or via the Internet over the past 2 years in Japan), which potentially advertised psychotropic/psychoactive effects. The samples were extracted with methanol under ultrasonication. After centrifugation, the extracts were filtered prior to injections. GC-MS analysis was performed using a DB-5MS capillary column. Regarding the LC-ESI-MS analysis; the separation of the target drugs was optimized on an ODS column in acetonitrile/MeOH (7:3)-10 mM ammonium formate buffer (pH 3.5)/acetonitrile (95:5) by a linear gradient program and a quantitative analysis was carried out by the monitoring of each [M+H]+ in the positive ion mode of ESI-MS. As a result of the analyses using GC-MS and LC-ESI-MS, 5-MeO-DIPT (the synthetic substance known by the street name "Foxy") was found in 8 out of the 99 kinds of products. Additionally, AMT (from brown powder), DMT (from dried plant), harmine and harmaline (from dried plant) were also found in some of the 99 products. These analytical methods could be useful for the investigation of the distribution of the non-controlled psychotropic tryptamines/beta-carbolines and phenethylamines in the market.

  20. 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.

  1. 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.

  2. Structural characterization and identification of ecdysteroids from Sida rhombifolia L. in positive electrospray ionization by tandem mass spectrometry.

    PubMed

    Wang, Yan-Hong; Avula, Bharathi; Jadhav, Atul N; Smillie, Troy J; Khan, Ikhlas A

    2008-08-01

    Seven ecdysteroids isolated from Sida rhombifolia L. were studied by electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) in the positive ion mode using an ion trap analyzer and high-performance liquid chromatography coupled with a diode-array detector (HPLC/DAD). The HPLC experiments were performed by means of a reversed-phase C(18) column and a binary mobile phase system consisting of water (containing 0.05% formic acid) and acetonitrile (containing 0.05% formic acid) under gradient elution conditions. According to mass spectral features and the substitution at C-2, C-20, C-24 and C-25, ecdysteroids in S. rhombifolia were classified into three sub-groups. Structural identification of these three sub-groups of ecdysteroids was established by LC/multi-stage ion trap mass spectrometry on-line or off-line. The fragmentation patterns of ecdysteroids yielded ions of successive loss of 1-4 water molecules. Furthermore, ions corresponding to the complete loss of the side chain at C-17 will help to identify the sub-groups of ecdysteroids in addition to containing a hydroxyl moiety at one of the above-mentioned positions. Based on the HPLC retention behavior, the diagnostic UV spectra and the molecular structural information provided by ESI-MS(n) spectra, a total of nine naturally occurring ecdysteroids were identified, of these two are identified for the first time in S. rhombifolia.

  3. Quantitative analysis of positional isomers of triacylglycerols via electrospray ionization tandem mass spectrometry of sodiated adducts.

    PubMed

    Herrera, Lisandra Cubero; Potvin, Michael A; Melanson, Jeremy E

    2010-09-01

    Herein we report a reversed-phase high-performance liquid chromatography tandem mass spectrometry (RP-HPLC/MS/MS) method for the analysis of positional isomers of triacylglycerols (TAGs) in vegetable oils. The fragmentation behavior of [M + X](+) ions (X = NH(4), Li, Na or Ag) was studied on a quadrupole-time-of-flight (Q-TOF) mass spectrometer under low-energy collision-induced dissociation (CID) conditions. Mass spectra that were dependent on the X(+) ion and the nature and position of the acyl substituents were observed for four pairs of 'AAB/ABA'-type TAGs, namely PPO/POP, OOP/OPO, LLO/LOL and OOL/OLO (where P is 16:0, palmitic acid; O is 18:1, oleic acid; and L is 18:2, linoleic acid). For the majority of [M + X](+) adducts, the loss of the fatty acid in the outer positions (sn-1 or sn-3) was favored over the loss in the central position (sn-2), which enabled the determination of the fractional abundance of the isomers. Ratios of the intensity of fragment ions at various AAB/ABA compositions produced linear calibration curves with positive slopes, comparable to those obtained traditionally by ESI-MS/MS of [M + NH(4)](+) adducts. The only exceptions were the [M + Ag](+) adducts of the PPO/POP system, which produced calibration curves with negative slopes. Sodium adducts provided the most consistent level of isomeric discrimination for the TAGs studied and also offered the most convenience in that they required no additive to the mobile phase. Therefore, calibration curve data derived from [M + Na](+) adducts were applied to the quantification of TAG regioisomers in sunflower and olive oils. The regiospecific analysis showed that palmitic acid was typically located at positions sn-1 or sn-3, whereas unsaturated fatty acids, oleic and linoleic acids were mostly found at the sn-2 position. PMID:20814981

  4. Sensitive monitoring of monoterpene metabolites in human urine using two-step derivatisation and positive chemical ionisation-tandem mass spectrometry.

    PubMed

    Schmidt, Lukas; Belov, Vladimir N; Göen, Thomas

    2013-09-01

    A gas chromatographic-positive chemical ionisation-tandem mass spectrometric (GC-PCI-MS/MS) method for the simultaneous determination of 10 oxidative metabolites of the monoterpenoid hydrocarbons α-pinene, (R)-limonene, and Δ(3)-carene ((+)-3-carene) in human urine was developed and tested for the monoterpene biomonitoring of the general population (n=36). The method involves enzymatic cleavage of the glucuronides followed by solid-supported liquid-liquid extraction and derivatisation using a two-step reaction with N,O-bis(trimethylsilyl)-trifluoroacetamide and N-(trimethylsilyl)imidazole. The method proved to be both sensitive and reliable with detection limits ranging from 0.1 to 0.3 μg L(-1). In contrast to the frequent and distinct quantities of (1S,2S,4R)-limonene-1,2-diol, the (1R,2R,4R)-stereoisomer could not be detected. The expected metabolite of (+)-3-carene, 3-caren-10-ol was not detected in any of the samples. All other metabolites were detected in almost all urine samples. The procedure enables for the first time the analysis of trace levels of a broad spectrum of mono- and bicyclic monoterpenoid metabolites (alcohols, diols, and carboxylic acids) in human urine. This analytical procedure is a powerful tool for population studies as well as for the discovery of human metabolism and toxicokinetics of monoterpenes. PMID:23953203

  5. Positron impact ionisation phenomena

    NASA Astrophysics Data System (ADS)

    Moxom, J.

    A magnetically guided beam of nearly-monoenergetic slow positrons has been used to study positron impact ionisation phenomena in gases. A novel hemispherical scattering cell incorporating an efficient ion extraction and detection system has been developed and has been utilised throughout this work. The energy spectra for the electrons ejected around 0° relative to the incident beam, following positron impact ionisation of Ar, have been measured by a time-of-flight method and a retarding electric field analyzer. The angular acceptance of the electron detection system has been estimated and used to compare the measured spectra with the double differential cross-sections calculated by Mandal et al (1986), Sil et al (1991) and Schultz and Reinhold (1990). The importance of the electron-capture-to-the-continuum process is discussed in this context and found to be minor at small forward angles, in contrast to the case of heavy positively charged projectiles. The apparatus was modified to produce a pulsed beam of slow positrons and utilised to measure in detail the total ionisation cross-section (Qt+) for a variety of atomic and molecular targets. For Ar, He and H2, Qt+ which includes contributions from Ps formation, has been subtracted from corresponding total cross-sections, in order to deduce the behaviour of the elastic scattering cross-section (Qel) in the vicinity of the Ps formation threshold (Eps). Here a small change in the gradient of Qel, has been found. The energy dependencies of the Qt+ for He, Ne and Ar, close to Eps have been interpreted in terms of threshold theory. In the case of Ar the outgoing Ps appears to be predominantly s-wave in character. For He and Ne the analysis suggests that the Ps contains significant contributions from a number of partial waves. In the case of O 2, structure in Qt+ has been found, which is attributed to coupling between two inelastic channels, namely Ps formation and excitation to the Schuman-Runge continuum.

  6. Detection and identification of alkylphosphonic acids by positive electrospray ionization tandem mass spectrometry using a tricationic reagent.

    PubMed

    Tak, Vijay; Pardasani, Deepak; Purohit, Ajay; Dubey, D K

    2011-11-30

    The retrospective detection and identification of degradation products of chemical warfare agents are of immense importance in order to prove their spillage and use. A highly sensitive liquid chromatography/electrospray ionization tandem mass spectrometric (LC/ESI-MS/MS) method--using an imidazolium-based tricationic reagent--was developed for the detection and identification of the anionic degradation products of nerve agents. A commercially available solution of 1,3-imidazolium-bis-(1-hexylbenzylimidazolium) trifluoride (IBHBI) formed adducts with alkylphosphonic acids (APAs), allowing detection of the APAs by positive mode ESI-MS. Tandem mass spectrometry was used for the unambiguous identification of the APAs. Parameters influencing the formation and stability of these adduct during mass spectrometric analysis, such as solvent composition, concentration of IBHBI, effect of pH and interferences by salts, were optimized. The absolute limits of detection (0.1 ng) for achieved for the APAs were better than those previously reported, and linear dynamic ranges of 10-2000 ng mL(-1) were achieved. The method was repeatable with a relative standard deviation ≤7.3%. APAs present in aqueous samples provided by the Organization for the Prohibition of Chemical Weapons during the 22(nd) and 24(th) Official Proficiency tests were detected and identified as IBHBI adducts. The added advantage of this method is that low-mass analytes are detected at higher mass, thus obviating the problem with background noise at low mass. PMID:22002694

  7. Highly efficient, selective and sensitive molecular screening of acetylcholinesterase inhibitors of natural origin by solid-phase extraction-liquid chromatography/electrospray ionisation-octopole-orthogonal acceleration time-of-flight-mass spectrometry and novel thin-layer chromatography-based bioautography.

    PubMed

    Mroczek, Tomasz

    2009-03-20

    Highly efficient, selective and sensitive molecular screening of natural acetylcholinesterase (AChE) inhibitors was developed and comprised optimized pressurized liquid extraction (PLE) of plant materials followed by highly selective solid-phase extraction (SPE) using Oasis HLB cartridges. Pure alkaloidal fractions were analyzed by a newly developed high-performance liquid-chromatography (HPLC) on a 3 microm Atlantis HILIC silica stationary phase combined with recently introduced electrospray ionisation (ESI) octopole-orthogonal acceleration time-of-flight (oa TOF)-mass spectrometry (MS) with high mass accuracy (about 2 ppm) and high sensitivity (absolute limit of detection (LOD) for galanthamine was about 43 fg at signal-to-noise 13:1). Moreover, a newly developed and validated TLC-bioautography permit galanthamine sensitivities at pg levels. In this way, more potent than galanthamine AChE inhibitor namely 1,2-dihydrogalanthamine in Narcissus jonquilla 'Pipit' extract could be found (with IC(50) value 0.19 microM lower of about 42% than that of galanthamine).

  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. Synchronized Polarization Induced Electrospray: Comprehensively Profiling Biomolecules in Single Cells by Combining both Positive-Ion and Negative-Ion Mass Spectra.

    PubMed

    Hu, Jun; Jiang, Xiao-Xiao; Wang, Jiang; Guan, Qi-Yuan; Zhang, Pan-Ke; Xu, Jing-Juan; Chen, Hong-Yuan

    2016-07-19

    In this work, a synchronized polarization induced electrospray ionization (SPI-ESI) method is developed and applied for the analysis of single-cell samples. In SPI-ESI, periodic alternating current square wave voltage (AC-SWV) is applied to induce the bipolar spray and both positive-ion and negative-ion mass spectra are obtained through one measurement by synchronizing the mode of mass analyzer with the bipolar spray process. Compared with conventional nanoelectrospray ionization (nESI, flow rate < 1000 nL/min), ultralow spray flow rate (pico-electrospray ionization, pESI, flow rate < 1000 pL/min) is achieved in SPI-ESI without loss of its sensitivity. The decrease of flow rate prolongs the MS signal duration from single-cell samples to acquire ms(2) data for components determination. To our knowledge, this is the first time to successfully achieve comprehensive analysis of single-cell samples by combining both positive-ion and negative-ion mass spectra. Ultimately, 86 components are profiled from single Allium cepa cells and 94 components are profiled from single PC-12 cells. PMID:27297455

  10. 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

  11. Characterization of cis- and trans-octadecenoic acid positional isomers in edible fat and oil using gas chromatography-flame ionisation detector equipped with highly polar ionic liquid capillary column.

    PubMed

    Yoshinaga, Kazuaki; Asanuma, Masaharu; Mizobe, Hoyo; Kojima, Koichi; Nagai, Toshiharu; Beppu, Fumiaki; Gotoh, Naohiro

    2014-10-01

    In this study, the characterisation of all cis- and trans-octadecenoic acid (C18:1) positional isomers in partially hydrogenated vegetable oil (PHVO) and milk fat, which contain several cis- and trans-C18:1 positional isomers, was achieved by gas chromatography-flame ionisation detector equipped with a highly polar ionic liquid capillary column (SLB-IL111). Prior to analysis, the cis- and trans-C18:1 fractions in PHVO and milk fat were separated using a silver-ion cartridge. The resolution of all cis-C18:1 positional isomers was successfully accomplished at the optimal isothermal column temperature of 120 °C. Similarly, the positional isomers of trans-C18:1, except for trans-6-C18:1 and trans-7-C18:1, were separated at 120 °C. The resolution of trans-6-C18:1 and trans-7-C18:1 isomers was made possible by increasing the column temperature to 160 °C. This analytical method is suitable for determining the cis- and trans-C18:1 positional isomers in edible fats and oils.

  12. 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. PMID

  13. Characterization of aluminum species with nitrate, perchlorate and sulfate ions in the positive and negative ion mode by electrospray ionization mass spectrometry.

    PubMed

    Urabe, Tatsuya; Tsugoshi, Takahisa; Tanaka, Miho

    2009-02-01

    The application of electrospray ionization mass spectrometry (ESI-MS) for aluminum speciation in the positive and negative ion modes was discussed. Aluminum nitrate, perchlorate and sulfate solutions were measured by ESI-MS. In the positive ion mode, aluminum species containing anions (Al-L; L=NO3, ClO4 and SO4) were identified, while [Al(OH)2(H2O)n]+ (n=2-4) were the main species. The affinity of the anions with Al3+ estimated by ESI-MS was consistent with the hardness of the anions (hard and soft acids and bases principle) and the results from 27Al nuclear magnetic resonance studies. This indicates that the results observed from the positive ion mode preserved the chemical state of aluminum in the solution. In the negative ion mode, [Al(OH)4-nLn]- (n=0-2, L=NO3, ClO4) were the main species, which were considered to be converted from positive aluminum species, [Al(OH)(H2O)n]+ (n=2-4), by the successive addition of anions. Anions did not only attach to one aluminum ion but also bridged two aluminum ions. In Al2(SO4)3 solution, the behavior of SO4(2-) in the negative ion mode differed from that of NO3- and ClO4-. This may reflect the affinity of SO4(2-) with Al3+ in the solution or in the mass spectrometer or in both. Finally, detection mechanisms for the aluminum species in the solution are proposed for both the positive and negative ion modes. It is shown that ESI-MS can be used to observe the interaction between Al3+ and anions. We show the importance of the interpretation of the results by ESI-MS for obtaining new information of the metal species in the solution. PMID:18946873

  14. Charge inversion of phospholipids by dimetal complexes for positive ion-mode electrospray ionization mass spectrometry analysis.

    PubMed

    Svane, Simon; Gorshkov, Vladimir; Kjeldsen, Frank

    2015-09-01

    Phospholipids are vital constituents of living cells, as they are involved in signaling and membrane formation. Mass spectrometry analysis of many phospholipids is preferentially performed in the negative ion-mode because of their acidic nature. Here we have studied the potential of a digallium and dizinc complex to charge-invert a range of different types of phospholipids and measured their ion yield and fragmentation behavior in positive ion-mode tandem mass spectrometry. The dimetal complexes bind specifically the phosphate groups of phospholipids and add an excess of up to three positive charges per phosphate group. Three different phosphoinositide phosphates (mono-, di-, and triphosphorylated inositides), a phosphatidic acid, a phosphatidylcholine, a phosphatidylethanolamine, and a phosphatidylglycerol were investigated. The intensities obtained in positive ion-mode of phosphoinositide phosphates and phosphatidic acid bound to {LGa2}(5+) were between 2.5- and 116-fold higher than that of the unmodified lipids in the negative ion-mode. Native phosphoinositide ions yielded upon CID in the negative ion-mode predominantly product ions due to losses of H3PO4, PO3(-) and H2O. In comparison, CID spectra of {LGa2}(5+)-bound phosphoinositides generally resulted in fragment ions corresponding to loss of the full diglyceride chain as well as the remaining headgroup bound to {LGa2}(5+) as the most abundant peaks. A number of signature fragment ions of moderate abundance were observed that allowed for distinction between the three regioisomers of 1,2-di(9Z-octadecenoyl)-sn-glycero-3-[phosphoinositol-x,y-bisphosphate] (PI(3,4)P2, PI(3,5)P2, PI(4,5)P2).

  15. Differentiation of Boc-protected alpha,delta-/delta,alpha- and beta,delta-/delta,beta-hybrid peptide positional isomers by electrospray ionization tandem mass spectrometry.

    PubMed

    Raju, G; Ramesh, V; Srinivas, R; Sharma, G V M; Shoban Babu, B

    2010-06-01

    Two new series of Boc-N-alpha,delta-/delta,alpha- and beta,delta-/delta,beta-hybrid peptides containing repeats of L-Ala-delta(5)-Caa/delta(5)-Caa-L-Ala and beta(3)-Caa-delta(5)-Caa/delta(5)-Caa-beta(3)-Caa (L-Ala = L-alanine, Caa = C-linked carbo amino acid derived from D-xylose) have been differentiated by both positive and negative ion electrospray ionization (ESI) ion trap tandem mass spectrometry (MS/MS). MS(n) spectra of protonated isomeric peptides produce characteristic fragmentation involving the peptide backbone, the Boc-group, and the side chain. The dipeptide positional isomers are differentiated by the collision-induced dissociation (CID) of the protonated peptides. The loss of 2-methylprop-1-ene is more pronounced for Boc-NH-L-Ala-delta-Caa-OCH(3) (1), whereas it is totally absent for its positional isomer Boc-NH-delta-Caa-L-Ala-OCH(3) (7), instead it shows significant loss of t-butanol. On the other hand, second isomeric pair shows significant loss of t-butanol and loss of acetone for Boc-NH-delta-Caa-beta-Caa-OCH(3) (18), whereas these are insignificant for its positional isomer Boc-NH-beta-Caa-delta-Caa-OCH(3) (13). The tetra- and hexapeptide positional isomers also show significant differences in MS(2) and MS(3) CID spectra. It is observed that 'b' ions are abundant when oxazolone structures are formed through five-membered cyclic transition state and cyclization process for larger 'b' ions led to its insignificant abundance. However, b(1)(+) ion is formed in case of delta,alpha-dipeptide that may have a six-membered substituted piperidone ion structure. Furthermore, ESI negative ion MS/MS has also been found to be useful for differentiating these isomeric peptide acids. Thus, the results of MS/MS of pairs of di-, tetra-, and hexapeptide positional isomers provide peptide sequencing information and distinguish the positional isomers.

  16. Differentiation of vanA-positive Enterococcus faecium from vanA-negative E. faecium by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Nakano, Satoshi; Matsumura, Yasufumi; Kato, Karin; Yunoki, Tomoyuki; Hotta, Go; Noguchi, Taro; Yamamoto, Masaki; Nagao, Miki; Ito, Yutaka; Takakura, Shunji; Ichiyama, Satoshi

    2014-09-01

    Vancomycin-resistant enterococci are important nosocomial pathogens that require rapid and accurate detection for infection control. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF/MS) has begun to be used in many clinical laboratories because it is a rapid, simple and inexpensive method for identifying micro-organisms. In this study, the performance of MALDI-TOF/MS to differentiate vanA-positive Enterococcus faecium (VPEF) from vanA-negative E. faecium (VNEF) was evaluated. A total of 61 VPEF isolates collected during regional surveillance in Kyoto (Japan) and 71 VNEF isolates collected from bacteraemia patients were analysed using MALDI-TOF/MS with three ClinProTools models. All of the isolates were correctly identified as E. faecium using the MALDI Biotyper system. To discriminate between VPEF and VNEF, all three ClinProTools models yielded >90% recognition capability (basic sensitivity) and cross-validation (reliability of the models); the genetic algorithm model exhibited the highest performance (99.18% and 92.40%, respectively). The high detection performance of MALDI-TOF/MS for VPEF offers the potential for routine laboratory use. PMID:25104134

  17. Differentiation of vanA-positive Enterococcus faecium from vanA-negative E. faecium by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Nakano, Satoshi; Matsumura, Yasufumi; Kato, Karin; Yunoki, Tomoyuki; Hotta, Go; Noguchi, Taro; Yamamoto, Masaki; Nagao, Miki; Ito, Yutaka; Takakura, Shunji; Ichiyama, Satoshi

    2014-09-01

    Vancomycin-resistant enterococci are important nosocomial pathogens that require rapid and accurate detection for infection control. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF/MS) has begun to be used in many clinical laboratories because it is a rapid, simple and inexpensive method for identifying micro-organisms. In this study, the performance of MALDI-TOF/MS to differentiate vanA-positive Enterococcus faecium (VPEF) from vanA-negative E. faecium (VNEF) was evaluated. A total of 61 VPEF isolates collected during regional surveillance in Kyoto (Japan) and 71 VNEF isolates collected from bacteraemia patients were analysed using MALDI-TOF/MS with three ClinProTools models. All of the isolates were correctly identified as E. faecium using the MALDI Biotyper system. To discriminate between VPEF and VNEF, all three ClinProTools models yielded >90% recognition capability (basic sensitivity) and cross-validation (reliability of the models); the genetic algorithm model exhibited the highest performance (99.18% and 92.40%, respectively). The high detection performance of MALDI-TOF/MS for VPEF offers the potential for routine laboratory use.

  18. Differentiation of Positional Isomers of Hybrid Peptides Containing Repeats of β-Nucleoside Derived Amino Acid (β-Nda-) and L-Amino Acids by Positive and Negative Ion Electrospray Ionization Tandem Mass Spectrometry (ESI-MS n )

    NASA Astrophysics Data System (ADS)

    Raju, B.; Ramesh, M.; Srinivas, R.; Chandrasekhar, S.; Kiranmai, N.; Sarma, V. U. M.

    2011-04-01

    A new class of positional isomeric pairs of -Boc protected oligopeptides comprised of alternating nucleoside derived β-amino acid (β-Nda-) and L-amino acid residues (alanine, valine, and phenylalanine) have been differentiated by both positive and negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-MS n ). The protonated dipeptide positional isomers with β-Nda- at the N-terminus lose CH3OH, NH3, and C2H4O2, whereas these processes are absent for the peptides with L-amino acids at the N-terminus. Instead, the presence of L-amino acids at the N-terminus results in characteristic retro-Mannich reaction involving elimination of imine. A good correlation has been observed between the conformational structure of the peptides and the abundance of y{n/+} and b{n/+} ions in MS n spectra. In the case of tetrapeptide isomers that are reported to form helical structures in solution phase, no y{n/+} and b{n/+} ions are observed when the corresponding amide -NH- participates in the helical structures. In contrast, significant y{n/+} and b{n/+} ions are formed when the amide -NH- is not involved in the H-bonding. In the case of tetra- and hexapeptides, it is observed that abundant b{n/+} ions are formed, presumably with stable oxazolone structures when the C-terminus of the b{n/+} ions possessed L-amino acid and the β-Nda- at the C-terminus appears to prevent the cyclization process leading to the absence of corresponding b{n/+} ions.

  19. High-performance liquid chromatography analysis of anti-inflammatory pharmaceuticals with ultraviolet and electrospray-mass spectrometry detection in suspected counterfeit homeopathic medicinal products.

    PubMed

    Panusa, Alessia; Multari, Giuseppina; Incarnato, Giampaolo; Gagliardi, Luigi

    2007-03-12

    A simple high-performance liquid chromatography (HPLC) method with both ultraviolet (UV) and electrospray ionisation mass spectrometry (ESI-MS) detection has been developed for the determination of seven pharmaceuticals in counterfeit homeopathic preparations. Naproxen, Ketoprofen, Ibuprofen, Diclofenac, Piroxicam, Nimesulide and Paracetamol were separated by reversed phase chromatography with acetonitrile-water (0.1% acetic acid) mobile phase, and detected by UV at 245 nm and by ESI-MS in negative ionisation mode with the exception of Paracetamol which was detected in positive ionisation mode. Benzoic acid was used as internal standard (IS). This method was successfully applied to the analysis of homeopathic preparations like mother tinctures, solutions, tablets, granules, creams, and suppositories. Linearity was studied with UV detection in the 50-400 microg mL(-1) range and with ESI-MS in the 0.1-50 microg mL(-1) range. Good correlation coefficients were found in both UV and ESI-MS. Detection limits ranged from 0.18 to 41.5 ng in UV and from 0.035 to 1.00 ng in ESI-MS.

  20. The effectiveness of photocatalytic ionisation disinfection of filter materials.

    PubMed

    Pietrzak, Katarzyna; Gutarowska, Beata

    2013-01-01

    The purpose of this study was to determine the effectiveness of photocatalytic ionisation as a disinfection method for filter materials contaminated by microorganisms, and to assess how air relative humidity (RH), time and microbe type influence the effectiveness of this disinfection. In the quantitative analysis of a used car air filter, bacterial contamination equalled 1.2 x 10(5) cfu/cm2, fungal contamination was 3.8 x 10(6) cfu/cm2, and the isolated microorganisms were Aspergillus niger, Bacillus megaterium, Cladosporium herbarum, Cryptococcus laurenti, Micrococcus sp., Rhodotorula glutinis and Staphylococcus cohnii. In the model experiment, three isolates (C. herbarum, R. glutinis, S. cohnii) and 3 ATCC species (A. niger, E. coli, S. aureus) were used for photocatalytic ionisation disinfection. The conditions of effective photocatalytic ionisation disinfection (R > or = 99.9%) were established as 2-3 h at RH = 77% (bacteria) and 6-24 h at RH = 53% (fungi). RH has an influence on the effectiveness of the photocatalytic disinfection process; the highest effectiveness was obtained for bacteria at RH = 77%, with results 5% higher than for RH = 49%. The studies show that the sensitivity of microorganisms to photocatalytic ionisation disinfection is ordered as follows: Gram-positive bacteria (S. cohnii, S. aureus), Gram-negative bacteria (E. coli), yeasts (R. glutinis), and moulds (C. herbarum, A. niger). Of all the mathematical models used for the description of death dynamics after photocatalytic ionisation disinfection, the Chick-Watson model is the most useful, but for more resistant microorganisms, the delayed Chick-Watson model is highly recommended. It therefore seems, that the presented disinfection method of photocatalytic ionisation can be successfully used to clean filtration materials.

  1. Use of high-performance liquid chromatography with diode array detection coupled to electrospray-Qq-time-of-flight mass spectrometry for the direct characterization of the phenolic fraction in organic commercial juices.

    PubMed

    Rodríguez-Medina, I C; Segura-Carretero, A; Fernández-Gutiérrez, A

    2009-06-01

    We have developed a direct method for the qualitative analysis of polyphenols in commercial organic fruit juices. The juices were diluted with water (50/50), filtered and directly injected. The analysis of phenolic compounds was carried out by reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to photodiode array detection (DAD) and electrospray ionisation-Qq-time-of-flight mass spectrometry (ESI-Qq-TOF-MS). A unique gradient program has been optimized for the separation of several phenolic classes and the analysis time was only 5 min. The fruit juice samples were successfully analysed in positive and negative ionisation modes. In positive mode the anthocyanins were identified whereas the vast majority of polyphenols were identified using the negative ionisation mode. The sensitivity, together with mass accuracy and true isotopic pattern of the Qq-TOF-MS, allowed the identification of the phenolic compounds. Moreover, the advantage of the proposed method is the combined search of MS and MS/MS spectra, which improves the identification of compounds considerably, reducing ambiguities and false positive hits. Therefore the total fragmentation of the compound ion leading to the aglycone ion or other fragments was corroborated by MS-MS. The method was successfully employed to characterize diverse phenolic families in commercially available organic juices from four different fruits and consequently could be used in the future for the quantification purposes to compare different content of polyphenols in juices.

  2. Bacterial spores survive electrospray charging and desolvation.

    PubMed

    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.

  3. 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

  4. Vertical profile measurements of lower troposphere ionisation

    NASA Astrophysics Data System (ADS)

    Harrison, R. G.; Nicoll, K. A.; Aplin, K. L.

    2014-11-01

    Vertical soundings of the atmospheric ion production rate have been obtained from Geiger counters integrated with conventional meteorological radiosondes. In launches made from Reading (UK) during 2013-2014, the Regener-Pfotzer ionisation maximum was at an altitude equivalent to a pressure of (63.1±2.4) hPa, or, expressed in terms of the local air density, (0.101±0.005) kg m-3. The measured ionisation profiles have been evaluated against the Usoskin-Kovaltsov model and, separately, surface neutron monitor data from Oulu. Model ionisation rates agree well with the observed cosmic ray ionisation below 20 km altitude. Above 10 km, the measured ionisation rates also correlate well with simultaneous neutron monitor data, although, consistently with previous work, measured variability at the ionisation maximum is greater than that found by the neutron monitor. However, in the lower atmosphere (below 5 km altitude), agreement between the measurements and simultaneous neutron monitor data is poor. For studies of transient lower atmosphere phenomena associated with cosmic ray ionisation, this indicates the need for in situ ionisation measurements and improved lower atmosphere parameterisations.

  5. Dicationic ion-pairing of phosphoric acid diesters post-liquid chromatography and subsequent determination by electrospray positive ionization-tandem mass spectrometry.

    PubMed

    Chu, Shaogang; Chen, Da; Letcher, Robert J

    2011-11-01

    Several organophosphate triesters are widely used as flame retardants and can be metabolized to dibutyl (DBP), diphenyl (DPhP), di(2-ethylhexyl) (DEHP) and di(1,3-dichloro-2-propyl) (or bis(1,3-dichloro-2-propyl); DDCPP) phosphoric acid, respectively. A highly sensitive liquid chromatography-electrospray ionization(+)-triple quadrupole mass spectrometry (LC-ESI(+)-QQQ-MS/MS) based analysis method was presently developed. In this method the target compounds were separated with a C(18)-based reversed phase LC column, and decamethonium hydroxide (dicatonic reagent) was introduced post-LC to form ion-pairs, which were subsequently detected by ESI(+). For the phosphate acid diester ion-pairs, the mass spectra showed the most abundant ion to be [(CH(3))(2)N(CH(2))(10)N(CH(3))(3)](+), with lesser abundances of [[M-H](-)[(CH(3))(3)N(CH(2))(9)CH(2)](2+)](+) and [CH(2)CH(CH(2))(8)N(CH(3))(3)](+). For DDCPP, the fragment ions of [[Cl](-)[(CH(3))(3)N(CH(2))(10)N(CH(3))(3)](2+)](+) and [[Cl](-)[(CH(3))(3)N(CH(2))(9)CH(2)](2+)](+) could also be observed. The limits of quantitation (LOQs) by LC-ESI(+)-MS/MS (based on multiple reaction monitoring) were 0.14, 0.03, 0.14 and 0.02 ng/mL for DPhP, DBP, DDCPP and DEHP, respectively. The response was highly linearly correlated (r>0.995) with concentration over the range of the LOD to 1000 ng/mL. The matrix effect on ESI+ was negligible for the samples in experiment of in vitro metabolism using rat liver microsomes. PMID:21945623

  6. Adsorption of ionisable pesticides in soils.

    PubMed

    Kah, M; Brown, C D

    2006-01-01

    Understanding the fate of a pesticide in soil is fundamental to the accurate assessment of its environmental behaviour and vital in ensuring the safe use of new and existing products. Ionisable pesticides comprise a significant proportion of both existing and new active substances registered for use in agriculture worldwide. This group of pesticides includes chemicals that are frequently found in groundwater and surface waters in many different countries. Despite this, approaches to predict the influence of soil properties on the behaviour of ionisable pesticides in soils are poorly developed. Current regulatory assessments frequently default to methods developed for nonionic chemicals, although it is evident that ionisable compounds do not often react like neutral molecules. This review presents the state of knowledge on the adsorption of ionisable pesticides in soils. It first introduces the issues concerning adsorption and the characteristics of this particular kind of chemical. The mechanisms postulated for the adsorption of ionisable pesticides are then described: these are hydrophobic partitioning, ionic exchange, charge transfer, ligand exchange, cation or water bridging, and the formation of bound residues. Relatively little experimental evidence is available, and we are still unable to determine the quantitative contribution of each process in a particular situation. Knowledge is still lacking concerning phenomena occurring at the surfaces of soil particles. Measurements do not allow determination of the operative pH at the surface of soil particles or in microenvironments, and the influence of ionic strength or competition effects is difficult to assess. Subsequently, the review focuses on the influence of soil properties on adsorption and on potential to predict the behaviour of ionisable pesticides in soils. Unlike hydrophobic compounds, adsorption of ionisable pesticides is highly sensitive to variation in pH. This relationship mainly derives from the

  7. 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.

  8. 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. PMID:25531669

  9. 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.

  10. New aspects in fragmentation of peptide nucleic acids: comparison of positive and negative ions by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Ziehe, Matthias; Grossmann, Tom N; Seitz, Oliver; Linscheid, Michael W

    2009-04-01

    The use of peptide nucleic acids (PNAs) is steadily increasing in biochemistry and diagnostics. So far, PNAs have mostly been investigated using cationic conditions in mass spectrometry. Furthermore, the use of fragmentation techniques developed for peptides and proteins like infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD) has barely been examined. However, especially the fragmentation behavior of PNA oligomers in negative ion mode is of high importance, due to the ability to interact with nucleic acids which are almost exclusively analyzed in the negatively charged state. In the current study PNA fragmentations under cationic and anionic conditions were investigated and different fragmentation techniques like collision-induced dissociation (CID), IRMPD and ECD were applied. Especially when using CID and IRMPD, amide bonds were broken, whereas ECD resulted in the elimination of nucleobases. Differences were also observed between positive and negative ionization, while the sequence coverage for the negative ions was superior to positive ions. The fragmentation behavior using IRMPD led to almost complete sequence coverage. Additionally, in anions the interesting effect of multiple eliminations of HNCO was found. PMID:19280610

  11. 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.

  12. 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. PMID:25668796

  13. Identification of molecular species of simple lipids by normal phase liquid chromatography-positive electrospray tandem mass spectrometry, and application of developed methods in comprehensive analysis of low erucic acid rapeseed oil lipids

    NASA Astrophysics Data System (ADS)

    Kalo, P. J.; Ollilainen, V.; Rocha, J. M.; Malcata, F. X.

    2006-07-01

    Mono-, di- and triacylglycerol (MAG, DAG, TAG), sterol ester (SE), free sterol (S) and free fatty acid (FFA) standards were analyzed in the presence of ammonium ions and ammonia by flow injection MS2 and MS3, and by normal phase-liquid chromatography (NP-LC) MS2 positive electrospray ionization (ESI) mass spectrometry (MS). The MS data recorded for ammonium adducts ([M + NH4]+) of TAGs, DAGs, and MAGs were consistent with stepwise fragmentation mechanisms. In the first step, ammonium ion in [M + NH4]+ donates proton to acylglycerol and ammonia is released. In the second step, FFA is cleaved from protonated TAG, water from protonated 1,3-DAG and MAG, both FFA and water from protonated 1,2-DAG, hence leading to formation of [DAG]+ ion from TAG and 1,3-DAG, [DAG]+ and [MAG]+ ions from 1,2-DAG, and [MAG]+ ion from MAG. In the third step, [DAG]+ ion of TAG is fragmented to yield [Acyl]+, [Acyl + 74]+, [DAG - 74]+ ions, [DAG] ion of 1,3-DAG to [Acyl]+ ions, and [MAG]+ ion of MAG to protonated FAs, which are decomposed to water and [Acyl]+ ions in the fourth step. A stepwise mechanism for fragmentation of FFA was also evident from MS2 and MS3 data. Molecular species of low erucic acid rapeseed oil simple lipids were identified from characteristic ions produced in the NP-LC-ESI-MS2 of [M + NH4]+ ions. The percentage composition of the molecular species of each lipid class was calculated from integrated extracted ion chromatograms of [(M + NH4)]+ ions of SE, TAG, MAG, and FFA, of the sum of [(M + NH4)]+ and [(M + NH4) - NH3 - H2O]+ ions of both regioisomers of DAGs, and of sterol fragment ions of S.

  14. Identification and fragmentation pathways of caffeine metabolites in urine samples via liquid chromatography with positive electrospray ionization coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometry and tandem mass spectrometry.

    PubMed

    Bianco, Giuliana; Abate, Salvatore; Labella, Cristiana; Cataldi, Tommaso R I

    2009-04-01

    Liquid chromatography (LC) with positive ion electrospray ionization (ESI+) coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) was employed for the simultaneous determination of caffeine and its metabolites in human urine within a single chromatographic run. LC/ESI-FTICRMS led to the unambiguous determination of the molecular masses of the studied compounds without interference from other biomolecules. A systematic and comprehensive study of the mass spectral behaviour of caffeine and its fourteen metabolites by tandem mass spectrometry (MS/MS) was performed, through in-source ion trap collision-induced dissociation (CID) of the protonated molecules, [M+H](+). A retro-Diels-Alder (RDA) process along with ring-contraction reactions were the major fragmentation pathways observed during CID. The base peak of xanthine precursors originates from the loss of methyl isocyanate (CH(3)NCO, 57 Da) or isocyanic acid (HNCO, 43 Da), which in turn lose a CO unit. Also uric acid derivatives shared a RDA rearrangement as a common fragmentation process and a successive loss of CO(2) or CO. The uracil derivatives showed a loss of a ketene unit (CH(2)CO, 42 Da) from the protonated molecule along with the loss of H(2)O or CO. To assess the potential of the present method three established metabolite ratios to measure P450 CYP1A2, N-acetyltransferase and xanthine oxidase activities were evaluated by a number of identified metabolites from healthy human urine samples after caffeine intake. PMID:19260028

  15. Cosmic ray induced ionisation of a molecular cloud shocked by the W28 supernova remnant

    NASA Astrophysics Data System (ADS)

    Vaupré, S.; Hily-Blant, P.; Ceccarelli, C.; Dubus, G.; Gabici, S.; Montmerle, T.

    2014-08-01

    Cosmic rays are an essential ingredient in the evolution of the interstellar medium, as they dominate the ionisation of the dense molecular gas, where stars and planets form. However, since they are efficiently scattered by the galactic magnetic fields, many questions remain open, such as where exactly they are accelerated, what is their original energy spectrum, and how they propagate into molecular clouds. In this work we present new observations and discuss in detail a method that allows us to measure the cosmic ray ionisation rate towards the molecular clouds close to the W28 supernova remnant. To perform these measurements, we use CO, HCO+, and DCO+ millimetre line observations and compare them with the predictions of radiative transfer and chemical models away from thermodynamical equilibrium. The CO observations allow us to constrain the density, temperature, and column density towards each observed position, while the DCO+/HCO+ abundance ratios provide us with constraints on the electron fraction and, consequently, on the cosmic ray ionisation rate. Towards positions located close to the supernova remnant, we find cosmic ray ionisation rates much larger (≳100) than those in standard galactic clouds. Conversely, towards one position situated at a larger distance, we derive a standard cosmic ray ionisation rate. Overall, these observations support the hypothesis that the γ rays observed in the region have a hadronic origin. In addition, based on CR diffusion estimates, we find that the ionisation of the gas is likely due to 0.1-1 GeV cosmic rays. Finally, these observations are also in agreement with the global picture of cosmic ray diffusion, in which the low-energy tail of the cosmic ray population diffuses at smaller distances than the high-energy counterpart.

  16. 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. PMID:26126928

  17. 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.

  18. Oxidation of amylose and amylopectin by hydroxyl radicals assessed by electrospray ionisation mass spectrometry.

    PubMed

    Simões, Joana; Moreira, Ana S P; da Costa, Elisabete; Evtyugin, Dmitry; Domingues, Pedro; Nunes, Fernando M; Coimbra, Manuel A; Domingues, M Rosário M

    2016-09-01

    The hydroxyl radicals (HO) are one of the most reactive oxygen species (ROS) involved in the oxidative damage of biological molecules, including carbohydrates. During the industrial processing of food, ROS can be formed. In order to identify the structural changes induced in starch by oxidation, amylose, amylopectin, and maltotriose, an oligosaccharide structurally related to these polysaccharides, were subjected to oxidation with HO generated under Fenton reaction conditions (Fe(2+)/H2O2). The oxidised polysaccharides were hydrolysed by α-amylase and the obtained oligosaccharides were fractionated by ligand-exchange/size-exclusion chromatography. Both acidic and neutral α-amylase resistant oligosaccharides were characterized by mass spectrometry. In oxidised neutral products, new keto, hydroxyl, and hydroperoxy moieties, and oxidative ring scission were observed at the reducing end of the oligosaccharides. The acid sugar residues occurred at the reducing end and included gluconic and glucuronic acid derivatives, and acids formed by oxidative ring scission, namely, arabinonic, erythronic, glyceric and glycolic acids.

  19. Cosmic-ray ionisation in collapsing clouds

    NASA Astrophysics Data System (ADS)

    Padovani, M.; Hennebelle, P.; Galli, D.

    2013-12-01

    Context. Cosmic rays play an important role in dense molecular cores, affecting their thermal and dynamical evolution and initiating the chemistry. Several studies have shown that the formation of protostellar discs in collapsing clouds is severely hampered by the braking torque exerted by the entrained magnetic field on the infalling gas, as long as the field remains frozen to the gas. Aims: In this paper we examine the possibility that the concentration and twisting of the field lines in the inner region of collapse can produce a significant reduction of the ionisation fraction. Methods: To check whether the cosmic-ray ionisation rate can fall below the critical value required to maintain good coupling, we first study the propagation of cosmic rays in a model of a static magnetised cloud varying the relative strength of the toroidal/poloidal components and the mass-to-flux ratio. We then follow the path of cosmic rays using realistic magnetic field configurations generated by numerical simulations of a rotating collapsing core with different initial conditions. Results: We find that an increment of the toroidal component of the magnetic field, or, in general, a more twisted configuration of the field lines, results in a decrease in the cosmic-ray flux. This is mainly due to the magnetic mirroring effect that is stronger where larger variations in the field direction are present. In particular, we find a decrease of the cosmic-ray ionisation rate below 10-18 s-1 in the central 300-400 AU, where density is higher than about 109 cm-3. This very low value of the ionisation rate is attained in the cases of intermediate and low magnetisation (mass-to-flux ratio λ = 5 and 17, respectively) and for toroidal fields larger than about 40% of the total field. Conclusions: Magnetic field effects can significantly reduce the ionisation fraction in collapsing clouds. We provide a handy fitting formula to compute approximately the attenuation of the cosmic-ray ionisation rate

  20. High-performance liquid chromatography-diode array and electrospray-mass spectrometry analysis of non-allowed substances in cosmetic products for preventing hair loss and other hormone-dependent skin diseases.

    PubMed

    De Orsi, Daniela; Pellegrini, Manuela; Pichini, Simona; Mattioli, Donatella; Marchei, Emilia; Gagliardi, Luigi

    2008-11-01

    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 minoxidil, progesterone, estrone, spironolactone, canrenone, hydrocortisone and triamcinolone acetonide in cosmetic products. The presence of these substances in commercial cosmetic samples is prohibited. The compounds were separated by reversed phase chromatography with water (0.1% trifluoroacetic acid) and acetonitrile gradient elution and detected by UV-DAD at 230, 254 and 280 nm and by ESI-MS positive ionisation mode. Benzoic acid was used as internal standard. Linearity was studied with UV-DAD detection from 1.50 to 1,000 microg/ml or mug/g range, depending on the different compounds and type of cosmetic preparation and with ESI-MS in the 50-1,000 ng/ml or ng/g range. Good determination coefficients (r(2)>or=0.99) were found in both UV and ESI-MS. 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. This method was successfully applied to the analysis of substances under investigations illegally added in cosmetic cream and lotions, sold on internet web sites to prevent hair loss and other hormone-dependent skin diseases, like acne and hirsutism. PMID:18656319

  1. 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. PMID:27088481

  2. Desorption electrospray ionization mass spectrometry of intact bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  3. 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.

  4. The fate of electrospray drops

    NASA Astrophysics Data System (ADS)

    Basaran, Osman; Collins, Robert; Sambath, Krishnaraj; Harris, Michael

    2015-11-01

    Drops subjected to strong electric fields emit thin fluid jets from conical structures (Taylor cones) that form at their surfaces. Such behavior has practical, e.g. electrospray mass spectrometry, and fundamental, e.g. raindrops in thunderclouds, implications. Theoretical analysis of the temporal development of such EHD tip-streaming phenomena is challenging given the large disparity in length scales between the macroscopic drops and the microscopic jets. Furthermore, there exist conflicting theories and measurements on the size and charge of these small electrospray droplets. We use theory and simulation to show that conductivity can be tuned to yield three scaling regimes for droplet radius and charge, a finding missed by previous studies. The amount of charge Q that electrospray droplets carry determines whether they are coulombically stable and charged below the Rayleigh limit of stability R or are unstable and hence prone to further explosions once formed. Previous experiments reported droplet charge values ranging from 1/10th to in excess of R. Simulations unequivocally show that electrospray droplets are coulombically stable at the instant they are created and that there exists a universal scaling law for droplet charge, Q=0.44 R.

  5. 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.

  6. Non-equilibrium calcium ionisation in the solar atmosphere

    NASA Astrophysics Data System (ADS)

    Wedemeyer-Böhm, S.; Carlsson, M.

    2011-04-01

    Context. The chromosphere of the Sun is a temporally and spatially very varying medium for which the assumption of ionisation equilibrium is questionable. Aims: Our aim is to determine the dominant processes and timescales for the ionisation equilibrium of calcium under solar chromospheric conditions. Methods: The study is based on numerical simulations with the RADYN code, which combines hydrodynamics with a detailed solution of the radiative transfer equation. The calculations include a detailed non-equilibrium treatment of hydrogen, calcium, and helium. Next to an hour long simulation sequence, additional simulations are produced, for which the stratification is slightly perturbed so that a ionisation relaxation timescale can be determined. The simulations are characterised by upwards propagating shock waves, which cause strong temperature fluctuations and variations of the (non-equilibrium) ionisation degree of calcium. Results: The passage of a hot shock front leads to a strong net ionisation of Ca II, rapidly followed by net recombination. The relaxation timescale of the calcium ionisation state is found to be of the order of a few seconds at the top of the photosphere and 10 to 30 s in the upper chromosphere. At heights around 1 Mm, we find typical values around 60 s and in extreme cases up to ~150 s. Generally, the timescales are significantly reduced in the wakes of ubiquitous hot shock fronts. The timescales can be reliably determined from a simple analysis of the eigenvalues of the transition rate matrix. The timescales are dominated by the radiative recombination from Ca III into the metastable Ca II energy levels of the 4d 2D term. These transitions depend strongly on the density of free electrons and therefore on the (non-equilibrium) ionisation degree of hydrogen, which is the main electron donor. Conclusions: The ionisation/recombination timescales derived here are too long for the assumption of an instantaneous ionisation equilibrium to be valid

  7. 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.

  8. 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...

  9. Effect of pressure on electrospray characteristics

    PubMed Central

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

    2009-01-01

    An experimental study of pulsating electrosprays operated at subambient pressure 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 pressure. The observed scaling amends the relationship currently used to calculate the electric field at the tip of the meniscus of an electrified liquid. PMID:19997584

  10. Electrospray and Taylor-Cone theory, Dole's beam of macromolecules at last?

    NASA Astrophysics Data System (ADS)

    Wilm, Matthias S.; Mann, Matthias

    1994-09-01

    A theoretical description of the electrostatic dispersion in electrospray is presented. The theory predicts the size of the zone at the tip of the Taylor Cone from which the liquid is ejected. To minimize this emission zone a modified electrospray ion source, the micro electrospray, has been constructed. With this ion source the size of the droplets is in the 200 nm range or below. The spray is very stable so that aqueous solutions can be dispersed in negative or positive mode without any assistance. The micro electrospray ion source is very efficient in the use of the applied amount of sample. Its flow rate of less than 25 nl/min makes MS-MS investigations on 0.5 [mu]l of sample possible. An overall transmission coefficient of 8 x 10-4 for a peptide from the solution state to the detector has been measured.

  11. 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

  12. 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.

  13. Molecular structure of fulvic acids by electrospray with quadrupole time-of-flight mass spectrometry.

    PubMed

    Plancque, G; Amekraz, B; Moulin, V; Toulhoat, P; Moulin, C

    2001-01-01

    Characterisation of the molecular structure of aquatic fulvic acids (FA) has been performed using a quadrupole time-of-flight (Q-TOF) mass spectrometer equipped with an electrospray ionisation interface. Molecular masses centred around 450 Da and sinusoidal spectral distributions have been obtained for all fulvic acids. Tandem mass spectrometry (MS/MS) experiments showed losses of 18 Da (H(2)O) and 44 Da (CO(2)), and possible molecular structures were determined for the first time to our knowledge. A methodology is reported for evaluating the average elemental composition of FA from high-resolution mass spectra by processing post-acquisition data calculations using molecular size distributions and atomic compositions of ions. The results are found to be consistent with elemental analysis data.

  14. 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

  15. Ionised Iron Lines in X-ray Reflection Spectra

    NASA Astrophysics Data System (ADS)

    Ballantyne, D. R.; Ross, R. R.; Fabian, A. C.

    2000-10-01

    We present results from new calculations of the reflected X-ray spectrum from ionised accretion disks in Active Galactic Nuclei (AGN). These calculations improve on our previous models by including the condition of hydrostatic balance in the vertical direction, following the work of Nayakshin, Kazanas & Kallman (2000). Our results show that, for gas pressure dominated accretion discs, ionised iron features are found in the reflection spectrum over a range of conditions. We also explore extending our results into radiation pressure dominated discs, and discuss the limitations of the current models.

  16. Laser-modified electron scattering from a slowly ionising atom

    NASA Technical Reports Server (NTRS)

    Fiordilino, E.; Mittleman, M. H.

    1983-01-01

    When an electron scatters from an atom in the presence of a laser field which is resonant with an atomic transition, off-shell effects enter into the cross section. These only become significant at higher laser intensities where the atom may also be ionised by the laser. Cross-sections are obtained for electron-atom scattering in which these off-shell effects appear and in which the slow ionisation of the atom by the laser is included. Experiments are suggested in which simplifications can occur and which still retain these 'exotic' effects.

  17. The influence of electrospray ion source design on matrix effects.

    PubMed

    Stahnke, Helen; Kittlaus, Stefan; Kempe, Günther; Hemmerling, Christlieb; Alder, Lutz

    2012-07-01

    This study investigates to which extent the design of electrospray ion sources influences the susceptibility to matrix effects (MEs) in liquid chromatography-tandem mass spectrometry (LC-MS/MS). For this purpose, MEs were measured under comparable conditions (identical sample extracts, identical LC column, same chromatographic method and always positive ion mode) on four LC-MS/MS instrument platforms. The instruments were combined with five electrospray ion sources, viz. Turbo Ion Spray, Turbo V(TM) Source, Standard ESI, Jet Stream ESI and Standard Z-Spray Source. The comparison of MEs could be made at all retention times because the method of permanent postcolumn infusion was applied. The MEs ascertained for 45 pesticides showed for each electrospray ion source the same pattern, i.e. the same number of characteristic signal suppressions at equivalent retention times in the chromatogram. The Turbo Ion Spray (off-axis geometry), Turbo V(TM) Source (orthogonal geometry) and the Standard Z-Spray Source (double orthogonal geometry) did not differ much in their susceptibility to MEs. The Jet Stream ESI (orthogonal geometry) reaches a higher sensitivity by an additional heated sheath gas, but suffers at the same time from significantly stronger signal suppressions than the comparable Standard ESI (orthogonal geometry) without sheath gas. No relation between source geometry and extent of signal suppression was found in this study.

  18. 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.

  19. 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.

  20. Highly ionised absorbers at high redshift

    NASA Astrophysics Data System (ADS)

    Bergeron, Jacqueline; Herbert-Fort, Stéphane

    2005-03-01

    We build a sample of O VI absorption systems in the redshift range 2.0 ≲ z ≲ 2.6 using high spectral resolution data of ten quasars from the VLT-UVES large programme. We investigate the existence of a metal-rich O VI population and define observational criteria for this class of absorbers under the assumption of photoionisation. The low temperatures of nearly half of all O VI absorbers, implied by their line widths, are too low for collisional ionisation to be a dominant process. We estimate the oxygen abundance under the assumption of photoionisation; a striking result is the bimodal distribution of [o/h] with median values close to 0.01 and 0.5 solar for the metal-poor and metal-rich populations, respectively. Using the line widths to fix the temperature or assuming a constant, low gas density does not drastically change the metallicities of the metal-rich population. We present the first estimate of the O VI column density distribution. Assuming a single power-law distribution, f(n) ∝ n-α, yields α ˜ 1.7 and a normalisation of f(n) =2.3× 10-13 at log n(O VI) ˜ 13.5, both with a ˜30% uncertainty. The value of α is similar to that found for C IV surveys, whereas the normalisation factor is about ten times higher. We use f(n) to derive the number density per unit z and cosmic density ωb(O VI), selecting a limited column density range not strongly affected by incompleteness or sample variance. Comparing our results with those obtained at z˜0.1 for a similar range of column densities implies some decline of dn/dz with z. The cosmic O VI density derived from f(n), ωb(O VI)≈ (3.5± 3.20.9) × 10-7, is 2.3 times higher than the value estimated using the observed O VI sample (of which the metal-rich population contributes ˜35%), easing the problem of missing metals at high z (˜ 1/4 of the produced metals) but not solving it. We find that the majori ty of the metal-rich absorbers are located within ˜ 450 km s-1 of strong Ly-α lines and show that

  1. Approaches towards the automated interpretation and prediction of electrospray tandem mass spectra of non-peptidic combinatorial compounds.

    PubMed

    Klagkou, Katerina; Pullen, Frank; Harrison, Mark; Organ, Andy; Firth, Alistair; Langley, G John

    2003-01-01

    Combinatorial chemistry is widely used within the pharmaceutical industry as a means of rapid identification of potential drugs. With the growth of combinatorial libraries, mass spectrometry (MS) became the key analytical technique because of its speed of analysis, sensitivity, accuracy and ability to be coupled with other analytical techniques. In the majority of cases, electrospray mass spectrometry (ES-MS) has become the default ionisation technique. However, due to the absence of fragment ions in the resulting spectra, tandem mass spectrometry (MS/MS) is required to provide structural information for the identification of an unknown analyte. This work discusses the first steps of an investigation into the fragmentation pathways taking place in electrospray tandem mass spectrometry. The ultimate goal for this project is to set general fragmentation rules for non-peptidic, pharmaceutical, combinatorial compounds. As an aid, an artificial intelligence (AI) software package is used to facilitate interpretation of the spectra. This initial study has focused on determining the fragmentation rules for some classes of compound types that fit the remit as outlined above. Based on studies carried out on several combinatorial libraries of these compounds, it was established that different classes of drug molecules follow unique fragmentation pathways. In addition to these general observations, the specific ionisation processes and the fragmentation pathways involved in the electrospray mass spectra of these systems were explored. The ultimate goal will be to incorporate our findings into the computer program and allow identification of an unknown, non-peptidic compound following insertion of its ES-MS/MS spectrum into the AI package. The work herein demonstrates the potential benefit of such an approach in addressing the issue of high-throughput, automated MS/MS data interpretation.

  2. 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.

  3. Analysis of intact bacteria using rapid evaporative ionisation mass spectrometry.

    PubMed

    Strittmatter, Nicole; Jones, Emrys A; Veselkov, Kirill A; Rebec, Monica; Bundy, Jacob G; Takats, Zoltan

    2013-07-14

    An identification system for microorganisms based on recently developed rapid evaporative ionisation mass spectrometry (REIMS) is presented. Nine bacterial species cultured on various growth media were correctly identified to family-, genus-, and species-level based on their different mass spectral fingerprints using a cross-validated maximum margin criterion model.

  4. 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. PMID:17630641

  5. A new method based on electrospray ionisation ion mobility spectrometry (ESI-IMS) for simultaneous determination of caffeine and theophylline.

    PubMed

    Jafari, M T; Rezaei, B; Javaheri, M

    2011-06-15

    In this work for the first time, simultaneous analysis of caffeine and theophylline was done by ion mobility spectrometry (IMS) only, without a powerful separation technique (e.g., HPLC). Ion mobility spectrometry with low cost, inexpensive maintenance and very fast analysis makes an attractive technique for the simultaneous determination of the caffeine and theophylline in foodstuff samples and biological matrices. In this study, the extraction protocol using molecular imprinted polymer-solid phase extraction (MIP-SPE) was successfully used to directly extract caffeine and theophylline from real samples. The results obtained provided the detection limits of 0.2 and 0.3μgmL(-1) for caffeine and theophylline, respectively. The linear dynamic range of about two orders of magnitude was obtained for these compounds. Also, the proposed method was used to analyse various real samples of green tea and spiked human plasma, and the obtained results confirmed the capability of ESI-IMS for simultaneous detection of caffeine and theophylline.

  6. Liquid chromatography/electrospray ionisation-tandem mass spectrometry quantification of GM2 gangliosides in human peripheral cells and plasma.

    PubMed

    Fuller, Maria; Duplock, Stephen; Hein, Leanne K; Rigat, Brigitte A; Mahuran, Don J

    2014-08-01

    GM2 gangliosidosis is a group of inherited neurodegenerative disorders resulting primarily from the excessive accumulation of GM2 gangliosides (GM2) in neuronal cells. As biomarkers for categorising patients and monitoring the effectiveness of developing therapies are lacking for this group of disorders, we sought to develop methodology to quantify GM2 levels in more readily attainable patient samples such as plasma, leukocytes, and cultured skin fibroblasts. Following organic extraction, gangliosides were partitioned into the aqueous phase and isolated using C18 solid-phase extraction columns. Relative quantification of three species of GM2 was achieved using LC/ESI-MS/MS with d35GM1 18:1/18:0 as an internal standard. The assay was linear over the biological range, and all GM2 gangliosidosis patients were demarcated from controls by elevated GM2 in cultured skin fibroblast extracts. However, in leukocytes only some molecular species could be used for differentiation and in plasma only one was informative. A reduction in GM2 was easily detected in patient skin fibroblasts after a short treatment with media from normal cells enriched in secreted β-hexosaminidase. This method may show promise for measuring the effectiveness of experimental therapies for GM2 gangliosidosis by allowing quantification of a reduction in the primary storage burden. PMID:24769373

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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

  15. 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

  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. 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...

  18. 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.

  19. 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.

  20. 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

    2012-03-01

    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.

  1. Electron impact ionisation cross sections for atomic and molecular allotropes of phosphorous and arsenic

    NASA Astrophysics Data System (ADS)

    Bhutadia, Harshad; Chaudhari, Ashok; Vinodkumar, Minaxi

    2015-12-01

    We report electron impact total ionisation cross sections for phosphorous (P), arsenic (As), diphosphorous (P2), diarsenic (As2), tetra phosphorous (P4) and tetra arsenic (As4) from the threshold of the target to 2000 eV. We employed spherical complex optical potential to compute total inelastic cross sections (Qinel). The total ionisation cross section is extracted from the total inelastic cross section using the complex scattering potential-ionisation contribution method. The results of most of the targets studied here compare well with the measurements and the theoretical data wherever available. The correlation between the peak of ionisation cross sections with the number of target electrons and polarisability is also reported. It is observed that the maximum ionisation cross sections depend linearly on the number of target electrons and polarisability of the target. This linear correlation is used to predict the maximum ionisation cross sections for the targets (I2, HI and PF3) where no experimental data are available.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Colloidal crystals by electrospraying polystyrene nanofluids

    PubMed Central

    2013-01-01

    This work introduces the electrospray technique as a suitable option to fabricate large-scale colloidal nanostructures, including colloidal crystals, in just a few minutes. It is shown that by changing the deposition conditions, different metamaterials can be fabricated: from scattered monolayers of polystyrene nanospheres to self-assembled three-dimensional ordered nanolayers having colloidal crystal properties. The electrospray technique overcomes the main problems encountered by top-down fabrication approaches, largely simplifying the experimental setup. Polystyrene nanospheres, with 360-nm diameter, were typically electrosprayed using off-the-shelf nanofluids. Several parameters of the setup and deposition conditions were explored, namely the distance between electrodes, nanofluid conductivity, applied voltage, and deposition rate. Layers thicker than 20 μm and area of 1 cm2 were typically produced, showing several domains of tens of microns wide with dislocations in between, but no cracks. The applied voltage was in the range of 10 kV, and the conductivity of the colloidal solution was in the range of 3 to 4 mS. Besides the morphology of the layers, the quality was also assessed by means of optical reflectance measurements showing an 80% reflectivity peak in the vicinity of 950-nm wavelength. PMID:23311494

  7. 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.

  8. 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.

  9. 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.

  10. A study of ionisation of free and clustered molecules under the action of femtosecond laser radiation

    SciTech Connect

    Apatin, V M; Kompanets, V O; Lokhman, V N; Ogurok, N-D D; Poydashev, D G; Ryabov, E A; Chekalin, S V

    2014-05-30

    We have investigated the processes of excitation and ionisation of monomers and clusters of CF{sub 3}I, IF{sub 2}CCOF and Fe(CO){sub 5} molecules under the action of femtosecond laser radiation at the wavelengths of 266, 400 and 800 nm. It is concluded that the nature of the excitation of free molecules and clustered molecules by femtosecond pulses is different. The simulation of the ionisation yield of the objects under study has shown that the multiphoton ionisation is the key mechanism in the case of free molecules, while the field ionisation may play a significant role for clusters, in particular, in the case of ionisation at the wavelength of λ = 800 nm. (interaction of radiation with matter)

  11. 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.

  12. 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

  13. 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. PMID:12590067

  14. 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.

  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. 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

  17. 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.

  18. Electron-impact excited term ionisation along the Boron isonuclear sequence

    NASA Astrophysics Data System (ADS)

    Ballance, C. P.; Lee, T.; Ludlow, J. A.; Loch, S. D.; Pindzola, M. S.

    2010-03-01

    Non-perturbative theoretical methods over the last decade have mainly focused on electron-impact ionization of the ground and first metastable states for light fusion related species [1]. However, collisional-radiative models predict that effective ionisation rates, which include the ionisation from excited levels of an atom, can be an order of magnitude greater greater than those which include the groundstate alone. For example, this stepwise ionisation has been experimentally confirmed by measurements taken at the DIII-D facility as part of a Li transport study, where excited state ionisation was found to be essential in describing Li transport [2]. We shall present in our poster an overview of excited state ionisation along the boron ionisation sequence. Using boron as a test case, we focus on the most appropriate use of computationally non-perturbative methods and simpler non-pertubative/semi-empirical methods to account for excited ionisation along other iso-nuclear sequences.[4pt] [1] Griffin D C and Pindzola M S, Adv. Atm. Mol. Opt. Phys. 54, 203 (2006)[0pt] [2] Allain J P, Whyte D G and Brooks J N, Nucl. Fusion 44 655 (2004)

  19. 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. PMID:17915237

  20. 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

  1. 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.

  2. Simple and double emulsions via electrospray

    NASA Astrophysics Data System (ADS)

    Barrero, Antonio; Loscertales, Ignacio G.

    2005-11-01

    Generation of nanoemulsions is of great interest in medical and pharmaceutical applications; drug delivery or antiviral emulsions are typical examples. The use of electrosprays for dispersing liquids inside liquid insulator baths have been recently reported, (Barrero et al. J. Colloid Interf. Sci. 272, 104, 2004). Capsules, nanotubes and coaxial nanofibers have been obtained from electrified coaxial jets (Loscertales et al. Science 295, n. 5560, 1695, 2002; J. American Chem. Soc. 126, 5376, 2004). Here we present a method for making double emulsions (both water-oil-water and o/w/o) based on the generation of compound electrosprays inside insulator liquid baths. Basically, a conducting liquid injected throughout a capillary needle is electroatomized in cone-jet mode inside a dielectric liquid bath. A third insulating liquid is injected inside the Taylor cone to form a second meniscus. Then, a steady coaxial jet, in which the insulating liquid is coated by the conducting one, develops. A double emulsion forms as a result of the jet breaking up into compound droplets electrically charged. Experimental results carried out with glycerine and different oils in a bath of heptane are reported.

  3. 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, FeHn 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 4s 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. Supplementary material in the form of one pdf file available from the Journal web page athttp://dx.doi.org/10.1140/epjd/e2016-70292-4

  4. Application of probe electrospray to direct ambient analysis of biological samples.

    PubMed

    Chen, Lee Chuin; Nishidate, Kentaro; Saito, Yuta; Mori, Kunihiko; Asakawa, Daiki; Takeda, Sen; Kubota, Takeo; Terada, Nobuo; Hashimoto, Yutaka; Hori, Hirokazu; Hiraoka, Kenzo

    2008-08-01

    Recently, we have developed probe electrospray ionization (PESI) that uses a solid needle. In this system, the probe needle moves up and down along the vertical axis by a motor-driven system. At the highest position of the probe needle, electrospray is generated by applying a high voltage. In this study, we applied PESI directly to biological samples such as urine, mouse brain, mouse liver, salmon egg, and fruits (orange, banana, etc.). Strong ion signals for almost all the samples were obtained. The amount of liquid sample picked up by the needle is as small as pL or less, making PESI a promising non-invasive technique for detecting biomolecules in living systems such as cells. Therefore, PESI may be useful as a versatile and ready-to-use semi-online analytical tool in the fields of medicine, pharmaceuticals, agriculture, food science, etc. PMID:18623622

  5. 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.

  6. 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.

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

    PubMed

    Marek, LeEtta J; Koskinen, William C

    2007-02-01

    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. PMID:17263443

  8. Non-uniform ionisation of the upper atmosphere due to the electromagnetic pulse from a horizontal lightning discharge

    NASA Astrophysics Data System (ADS)

    Cho, M.; Rycroft, M. J.

    2001-04-01

    The purpose of this paper is to model numerically the ionisation created in the mesosphere above a strong horizontal (cloud-to-cloud) lightning discharge, and thus to understand better the formation of elves and related columniform (spatially structured) sprites. Such ionisation depends upon height, via the ratio of the VLF//LF wave electric field (radiated by the current in the discharge) to the atmospheric neutral density. The simulation shows local maxima on the order of 10 km apart due to the interference between direct waves radiated by the discharge current, waves reflected by the ground and waves reflected by the ionosphere. Parametric studies are carried out varying the frequency, amplitude, height, length and duration of the current. For waves >=30kHz generated by a current >=50kA, localised peaks of electron density occur from 75 to 85km altitude, particularly for discharges longer than 15 km. From such peaks, time-varying ``stalactites'' on the bottom of the ionosphere, streamers could develop and propagate downwards. These could become columniform sprites in the presence of the quasi-electrostatic field due to the negative charge remaining in the thundercloud after a positive cloud-to-ground discharge.

  9. 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.

  10. 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.

  11. Dosimetry of ionising radiation in modern radiation oncology.

    PubMed

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

    2016-07-21

    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. PMID:27351409

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Evaluation of the ability of a 2D ionisation chamber array and an EPID to detect systematic delivery errors in IMRT plans

    NASA Astrophysics Data System (ADS)

    Bawazeer, Omemh; Gray, Alison; Arumugam, Sankar; Vial, Philip; Thwaites, David; Descallar, Joseph; Holloway, Lois

    2014-03-01

    Two clinical intensity modulated radiotherapy plans were selected. Eleven plan variations were created with systematic errors introduced: Multi-Leaf Collimator (MLC) positional errors with all leaf pairs shifted in the same or the opposite direction, and collimator rotation offsets. Plans were measured using an Electronic Portal Imaging Device (EPID) and an ionisation chamber array. The plans were evaluated using gamma analysis with different criteria. The gamma pass rates remained around 95% or higher for most cases with MLC positional errors of 1 mm and 2 mm with 3%/3mm criteria. The ability of both devices to detect delivery errors was similar.

  18. 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. PMID:27261097

  19. 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.

  20. 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

  1. Evaluations of the stability of sheathless electrospray ionization mass spectrometry emitters using electrochemical techniques.

    PubMed

    Nilsson, S; Svedberg, T M; Pettersson, J; Björefors, T F; Markides, K; Nyholm, L

    2001-10-01

    The processes that cause the failure of sheathless electrospray ionization (ESI) emitters, based on different kinds of gold coatings on fused-silica capillaries, are described and explained. The methods chosen for this study include electrochemical methods, ICPMS analysis of the electrolytes used, SEM studies, and electrospray experiments. Generally, the failure occurs by loss of the conductive coating. It is shown that emitters with sputter-coated gold lose their coatings because of mechanical stress caused by the gas evolution accompanying water oxidation or reduction. Emitters with gold coatings on top of adhesion layers of chromium and nickel alloy withstand this mechanical stress and have excellent durability when operating as cathodes. When operating as anodes, the adhesion layer is electrochemically dissolved through the gold film, and the gold film then flakes off. It is shown that the conductive coating behaves as a cathode even in the positive electrospray mode when the magnitude of a superimposed reductive electrophoretic current exceeds that of the oxidative electrospray current. Fairy-dust coatings developed in our laboratory (see Barnidge, D. R.; etal.Anal. Chem. 1999, 71, 4115-4118,) bygluing gold dust onto the emitter, are unaffected by the mechanical stress due to gas evolution. When oxidized, the fairy-dust coatings show an increased surface roughness and decreased conductivities due to the formation of gold oxide. The resistance of this oxide layer is however negligible in comparison with that of the gas phase in ESI. Furthermore, since no flaking and only negligible electrochemical etching of gold was found, practically unlimited emitter lifetimes may be achieved with fairy-dust coatings. PMID:11605837

  2. 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

  3. Frequency dependence of alternating current electrospray ionization mass spectrometry.

    PubMed

    Chetwani, Nishant; Cassou, Catherine A; Go, David B; Chang, Hsueh-Chia

    2011-04-15

    The novel effects resulting from the entrainment of low mobility ions during alternating current (ac) electrospray ionization are examined through mass spectrometry and voltage/current measurements. Curious phenomena such as pH modulation at high frequencies (>150 kHz) of an applied ac electric field are revealed and explained using simple mechanistic arguments. Current measurements are utilized to supplement these observations, and a simplified one-dimensional transient diffusion model for charge transport is used to arrive at a scaling law that provides better insight into the ac electrospray ionization process. Moreover, because of the different pathway for ion formation in comparison to direct current (dc) electrospray, ac electrospray (at frequencies >250 kHz) is shown to reduce the effects of ionization suppression in a mixture of two molecules with different surface activities. PMID:21417427

  4. 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

  5. Invasive oral cancer stem cells display resistance to ionising radiation.

    PubMed

    Gemenetzidis, Emilios; Gammon, Luke; Biddle, Adrian; Emich, Helena; Mackenzie, Ian C

    2015-12-22

    There is a significant amount of evidence to suggest that human tumors are driven and maintained by a sub-population of cells, known as cancer stem cells (CSC). In the case of head and neck cancer, such cells have been characterised by high expression levels of CD44 cell surface glycoprotein, while we have previously shown the presence of two diverse oral CSC populations in vitro, with different capacities for cell migration and proliferation. Here, we examined the response of oral CSC populations to ionising radiation (IR), a front-line measure for the treatment of head and neck tumors. We show that oral CSC initially display resistance to IR-induced growth arrest as well as relative apoptotic resistance. We propose that this is a result of preferential activation of the DNA damagerepair pathway in oral CSC with increased activation of ATM and BRCA1, elevated levels of DNA repair proteins RAD52, XLF, and a significantly faster rate of DNA double-strand-breaks clearance 24 hours following IR. By visually identifying CSC sub-populations undergoing EMT, we show that EMT-CSC represent the majority of invasive cells, and are more radio-resistant than any other population in re-constructed 3D tissues. We provide evidence that IR is not sufficient to eliminate CSC in vitro, and that sensitization of CD44hi/ESAlow cells to IR, followed by secondary EMT blockade, could be critical in order to reduce primary tumor recurrence, but more importantly to be able to eradicate cells capable of invasion and distant metastasis.

  6. 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.

  7. 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.

  8. Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry

    PubMed Central

    Fernández, Facundo M.

    2013-01-01

    Mass spectrometry imaging (MSI) provides untargeted molecular information with the highest specificity and spatial resolution for investigating biological tissues at the hundreds to tens of microns scale. When performed under ambient conditions, sample pre-treatment becomes unnecessary, thus simplifying the protocol while maintaining the high quality of information obtained. Desorption electrospray ionization (DESI) is a spray-based ambient MSI technique that allows for the direct sampling of surfaces in the open air, even in vivo. When used with a software-controlled sample stage, the sample is rastered underneath the DESI ionization probe, and through the time domain, m/z information is correlated with the chemical species' spatial distribution. The fidelity of the DESI-MSI output depends on the source orientation and positioning with respect to the sample surface and mass spectrometer inlet. Herein, we review how to prepare tissue sections for DESI imaging and additional experimental conditions that directly affect image quality. Specifically, we describe the protocol for the imaging of rat brain tissue sections by DESI-MSI. PMID:23892773

  9. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling. PMID:21598328

  10. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling.

  11. 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.

  12. 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.

  13. Uniform discotic wax particles via electrospray emulsification.

    PubMed

    Mejia, Andres F; He, Peng; Luo, Dawei; Marquez, Manuel; Cheng, Zhengdong

    2009-06-01

    We present a novel colloidal discotic system: the formation and self-assembling of wax microdisks with a narrow size distribution. Uniform wax emulsions are first fabricated by electrospraying of melt alpha-eicosene. The size of the emulsions can be flexibly tailored by varying the flow rate of the discontinuous phase, its electric conductivity, and the applied voltage. The process of entrainment of wax droplets, vital for obtaining uniform emulsions, is facilitated by the reduction of air-water surface tension and the density of the continuous phase. Then uniform wax discotic particles are produced via phase transition, during which the formation of a layered structure of the rotator phase of wax converts the droplets, one by one, into oblate particles. The time span for the conversion from spherical emulsions to disk particles is linearly dependent on the size of droplets in the emulsion, indicating the growth of a rotator phase from surface to the center is the limiting step in the shape transition. Using polarized light microscopy, the self-assembling of wax disks is observed by increasing disk concentration and inducing depletion attraction among disks, where several phases, such as isotropic, condensed, columnar stacking, and self-assembly of columnar rods are present sequentially during solvent evaporation of a suspension drop. PMID:19383560

  14. Uniform discotic wax particles via electrospray emulsification.

    PubMed

    Mejia, Andres F; He, Peng; Luo, Dawei; Marquez, Manuel; Cheng, Zhengdong

    2009-06-01

    We present a novel colloidal discotic system: the formation and self-assembling of wax microdisks with a narrow size distribution. Uniform wax emulsions are first fabricated by electrospraying of melt alpha-eicosene. The size of the emulsions can be flexibly tailored by varying the flow rate of the discontinuous phase, its electric conductivity, and the applied voltage. The process of entrainment of wax droplets, vital for obtaining uniform emulsions, is facilitated by the reduction of air-water surface tension and the density of the continuous phase. Then uniform wax discotic particles are produced via phase transition, during which the formation of a layered structure of the rotator phase of wax converts the droplets, one by one, into oblate particles. The time span for the conversion from spherical emulsions to disk particles is linearly dependent on the size of droplets in the emulsion, indicating the growth of a rotator phase from surface to the center is the limiting step in the shape transition. Using polarized light microscopy, the self-assembling of wax disks is observed by increasing disk concentration and inducing depletion attraction among disks, where several phases, such as isotropic, condensed, columnar stacking, and self-assembly of columnar rods are present sequentially during solvent evaporation of a suspension drop.

  15. Effect of Electrospray Ionization Source Conditions on the Tautomer Distribution of Deprotonated p-Hydroxybenzoic Acid in the Gas Phase.

    PubMed

    Xia, Hanxue; Attygalle, Athula B

    2016-06-01

    The deprotonation site of p-hydroxybenzoic acid upon electrospray ionization has been a subject of fervent debate in several articles in the Journal of the American Chemical Society and elsewhere. General consensus is that electrospray ionization mass spectrometry (ESI-MS) experimental results reflect the situation in solution to a considerable extent. Our research, using ion-mobility mass spectrometry, challenges the notion that ESI-MS results directly reflect solution-phase structures and demonstrates that the relative populations of the thermodynamically less favored gaseous carboxylate tautomer or the thermodynamically more favored gaseous phenoxide tautomer, generated from the same aqueous solution of p-hydroxybenzoic acid by ESI, can be varied back and forth by changing the probe position, capillary voltage, desolvation-gas temperature, sample infusion flow rate, and cone voltage. In other words, solvent effects are not the primary criteria that determine the relative population distributions of tautomeric carboxylate (C(-)) and phenoxide (P(-)) ions (m/z 137) generated by electrospray ionization of p-hydroxybenzoic acid. In addition, we propose that the observed ratio of the P(-) and C(-) forms indirectly reflects the relative contribution of the charge-residue or ion-evaporation process that occurs during the electrospray ion generation process.

  16. Effect of Electrospray Ionization Source Conditions on the Tautomer Distribution of Deprotonated p-Hydroxybenzoic Acid in the Gas Phase.

    PubMed

    Xia, Hanxue; Attygalle, Athula B

    2016-06-01

    The deprotonation site of p-hydroxybenzoic acid upon electrospray ionization has been a subject of fervent debate in several articles in the Journal of the American Chemical Society and elsewhere. General consensus is that electrospray ionization mass spectrometry (ESI-MS) experimental results reflect the situation in solution to a considerable extent. Our research, using ion-mobility mass spectrometry, challenges the notion that ESI-MS results directly reflect solution-phase structures and demonstrates that the relative populations of the thermodynamically less favored gaseous carboxylate tautomer or the thermodynamically more favored gaseous phenoxide tautomer, generated from the same aqueous solution of p-hydroxybenzoic acid by ESI, can be varied back and forth by changing the probe position, capillary voltage, desolvation-gas temperature, sample infusion flow rate, and cone voltage. In other words, solvent effects are not the primary criteria that determine the relative population distributions of tautomeric carboxylate (C(-)) and phenoxide (P(-)) ions (m/z 137) generated by electrospray ionization of p-hydroxybenzoic acid. In addition, we propose that the observed ratio of the P(-) and C(-) forms indirectly reflects the relative contribution of the charge-residue or ion-evaporation process that occurs during the electrospray ion generation process. PMID:27164186

  17. 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

  18. 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

  19. 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.

  20. Sizing up large protein complexes by electrospray ionisation-based electrophoretic mobility and native mass spectrometry: morphology selective binding of Fabs to hepatitis B virus capsids.

    PubMed

    Bereszczak, Jessica Z; Havlik, Marlene; Weiss, Victor U; Marchetti-Deschmann, Martina; van Duijn, Esther; Watts, Norman R; Wingfield, Paul T; Allmaier, Guenter; Steven, Alasdair C; Heck, Albert J R

    2014-02-01

    The capsid of hepatitis B virus (HBV) is a major viral antigen and important diagnostic indicator. HBV capsids have prominent protrusions ('spikes') on their surface and are unique in having either T = 3 or T = 4 icosahedral symmetry. Mouse monoclonal and also human polyclonal antibodies bind either near the spike apices (historically the 'α-determinant') or in the 'floor' regions between them (the 'β-determinant'). Native mass spectrometry (MS) and gas-phase electrophoretic mobility molecular analysis (GEMMA) were used to monitor the titration of HBV capsids with the antigen-binding domain (Fab) of mAb 3120, which has long defined the β-determinant. Both methods readily distinguished Fab binding to the two capsid morphologies and could provide accurate masses and dimensions for these large immune complexes, which range up to ~8 MDa. As such, native MS and GEMMA provide valuable alternatives to a more time-consuming cryo-electron microscopy analysis for preliminary characterisation of virus-antibody complexes.

  1. 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. PMID:19071613

  2. 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.

  3. 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.

  4. 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:

  5. 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.

  6. 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

  7. Charge and Size Distributions of Electrospray Drops

    PubMed

    de Juan L; de la Mora JF

    1997-02-15

    The distributions of charge q and diameter d of drops emitted from electrified liquid cones in the cone-jet mode are investigated with two aerosol instruments. A differential mobility analyzer (DMA, Vienna type) first samples the spray drops, selects those with electrical mobilities within a narrow band, and either measures the associated current or passes them to a second instrument. The drops may also be individually counted optically and sized by sampling them into an aerodynamic size spectrometer (API's Aerosizer). For a given cone-jet, the distribution of charge q for the main electrospray drops is some 2.5 times broader than their distribution of diameters d, with qmax/qmin approximately 4. But mobility-selected drops have relative standard deviations of only 5% for both d and q, showing that the support of the (q, d) distribution is a narrow band centered around a curve q(d). The approximate one-dimensionality of this support region is explained through the mechanism of jet breakup, which is a random process with only one degree of freedom: the wavelength of axial modulation of the jet. The observed near constancy of the charge over volume ratio (q approximately d3) shows that the charge is frozen in the liquid surface at the time scale of the breakup process. The charge over volume ratio of the primary drops varies between 98 and 55% of the ratio of spray current I over liquid flow rate Q, and decreases at increasing Q. I/Q is therefore an unreliable measure of the charge density of these drops.

  8. Determination of cathinones and related ephedrines in forensic whole-blood samples by liquid-chromatography-electrospray tandem mass spectrometry.

    PubMed

    Sørensen, Lambert K

    2011-04-01

    A liquid-chromatography-tandem-mass-spectrometry method using pneumatically assisted electrospray ionisation (LC-ESI-MS/MS) was developed for the simultaneous determination of cathinone, methcathinone, ethcathinone, amfepramone, mephedrone, flephedrone, methedrone, methylone, butylone, cathine, norephedrine, ephedrine, pseudoephedrine, methylephedrine and methylpseudoephedrine in human live and post-mortem whole blood. The blood proteins were precipitated by the addition of methanol, and the extract was purified by ultrafiltration. The separation of diastereomeric ephedrines was achieved on an ethyl-linked phenyl column. Matrix-matched calibrants combined with the isotope dilution of selected substances were used for quantitative analysis. The relative intra-laboratory reproducibility standard deviations were generally better than 7% at concentrations of 20 μg/L, and the mean true recoveries were 87-106% in the concentration range of 10-250 μg/L. The detection limits were in the range of 0.5-3 μg/L. The cathinones were unstable in whole blood and sample extracts under neutral conditions, but the stability could be improved by the acidification of the sample matrix. PMID:21376674

  9. 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.

  10. A compact high resolution electrospray ionization ion mobility spectrometer.

    PubMed

    Reinecke, T; Kirk, A T; Ahrens, A; Raddatz, C-R; Thoben, C; Zimmermann, S

    2016-04-01

    Electrospray is a commonly used ionization method for the analysis of liquids. An electrospray is a dispersed nebular of charged droplets produced under the influence of a strong electrical field. Subsequently, ions are produced in a complex process initiated by evaporation of neutral solvent molecules from these droplets. We coupled an electrospray ionization source to our previously described high resolution ion mobility spectrometer with 75 mm drift tube length and a drift voltage of 5 kV. When using a tritium source for chemical gas phase ionization, a resolving power of R=100 was reported for this setup. We replaced the tritium source and the field switching shutter by an electrospray needle, a desolvation region with variable length and a three-grid shutter for injecting ions into the drift region. Preliminary measurements with tetraalkylammonium halides show that the current configuration with the electrospray ionization source maintains the resolving power of R=100. In this work, we present the characterization of our setup. One major advantage of our setup is that the desolvation region can be heated separately from the drift region so that the temperature in the drift region stays at room temperature even up to desolvation region temperatures of 100 °C. We perform parametric studies for the investigation of the influence of temperature on solvent evaporation with different ratios of water and methanol in the solvent for different analyte substances. Furthermore, the setup is operated in negative mode and spectra of bentazon with different solvents are presented.

  11. 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

  12. 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.

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

    DOEpatents

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

    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.

  14. 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.

  15. 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.

  16. Plume collimation for laser ablation electrospray ionization mass spectrometry

    SciTech Connect

    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.

  17. Multiplexed electrospray deposition for protein microarray with micromachined silicon device

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Parijat

    2007-07-01

    Multiplexed electrospray deposition device capable of delivering picoliter volumes made by silicon micromachining technology has been developed as a deposition tool for making protein microarrays in a noncontact mode. Upon application of potential difference in the range of 7-9kV, biomolecules dissolved in suitable buffer with nonionic surfactant and loaded on the electrospray tips were dispensed on the substrate with microfabricated hydrogel features (1-10μm) in cone-jet mode. Schiff base chemistry followed by reductive amination was utilized for covalent immobilization.

  18. 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. PMID:27340617

  19. 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.

  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. 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…

  2. Calculations of electron-impact ionisation of {{Fe}}^{25+} and {{Fe}}^{24+}

    NASA Astrophysics Data System (ADS)

    Fursa, Dmitry V.; Bostock, Christopher J.; Bray, Igor; Fontes, Christopher J.

    2016-09-01

    Electron-impact ionisation cross sections for the hydrogen- and helium-like ions of iron are calculated. The convergent close-coupling and distorted-wave methods in the relativistic and nonrelativistic formulations are used. The cross sections are in very good agreement with the results of the corresponding methods, with the relativistic formulation establishing the benchmarks to few percent accuracy.

  3. Statistical fluctuations of the ionisation yield of low-energy electrons in He, Ne and Ar

    NASA Astrophysics Data System (ADS)

    Grosswendt, B.

    1984-04-01

    Using the Monte-Carlo method, the statistical fluctuations of the ionisation yield produced during the degradation of low energy electrons in the three noble gases He, Ne and Ar were studied. To do this, the probability P(T(0),j) for exact j ionisations generated upon the complete slowing down of electrons of initial energy T(0) was calculated in the energy range from 20 eV to 5 keV. The probability distributions in the number of ionisations produced were then used to determine moments M(v) and central moments m(v) up to the order v = 5 which is related to such well known quantities as the mean energy expended/ion pair formed, the Fano factor, and the generalised Fano factors introduced by Inokuti et al (1980), all of which are able to characterise a special property of the ionisation number distribution, as for instance its variance, its asymmetry, and its flatness near the center.

  4. 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…

  5. 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.

  6. 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.

  7. 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. PMID:26931427

  8. Oligosaccharide sequences in Quillaja saponins by electrospray ionization ion trap multiple-stage mass spectrometry.

    PubMed

    Broberg, Susanna; Nord, Lars I; Kenne, Lennart

    2004-06-01

    Ten different samples with 13 previously identified saponin structures from Quillaja saponaria Molina were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMS(n)) in positive and negative ion modes. Both positive and negative ion mode MS(1)-MS(4) spectra were analyzed, showing that structural information on the two oligosaccharide parts in the saponin can be obtained from positive ion mode spectra whereas negative ion mode spectra mainly gave information on one of the oligosaccharide parts. Analysis of MS(1)-MS(4) spectra identified useful key fragment ions important for the structural elucidation of Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from MS(1)-MS(3) spectra was constructed for the identification of structural elements in the saponin. Peak intensity ratios in MS(3) spectra were found to be correlated with structural features of the investigated saponins and are therefore of value for the identification of terminal monosaccharide residues.

  9. High-resolution mobility analysis of charge-reduced electrosprayed protein ions.

    PubMed

    Fernandez de la Mora, Juan

    2015-04-01

    Many mobility studies (IMS) of electrospray ions with charge states z reduced to unity have shown a singular ability to analyze large protein complexes and viruses, though with wide mobility peaks (fwhm ∼ 20%). Here we confirm that this limitation arises primarily when early charge reduction precedes drop evaporation (suppressing secondary atomization by the usual sequence of many Coulomb explosions). By drying before neutralizing, we achieve a protein fwhm of ∼3.7%. A positively biased electrospraying capillary is coaxial with a cylindrical charge-reduction (CR) chamber coated with radioactive Ni-63 (10 mCi) that fills the CR chamber with a bipolar ionic atmosphere. A screen interposed between the spraying capillary and the CR chamber limits penetration of the neutralizing anions into the electrospray (ES) chamber, precluding destabilization of the ES tip, even when brought very close to the grid to enhance ion transmission. As ES cations cross the grid, driven by their own space charge, they recombine with CR ions reducing their charge state as well as space charge dispersion. The setup is tested with the protein ovalbumin (MW ∼ 44.3 kDa) and its clusters up to the tetramer, by analyzing the charge-reduced ions with a differential mobility analyzer (DMA). At gas sample flow rates of ∼1 L/min, the dominant peaks are singly charged (z = 1). They are widened by clustering of involatile solution impurities, depending on spray quality and solution cleanness, with fwhm as small as 3.7% achieved in desalted and acidified solutions. When using sharp nanospray capillaries, the grid may be removed, resulting in ∼2-fold increased ion transmission. In the absence of the grid, however, spray stability and quality are often compromised, even with capillary tip diameters as small as 30 μm. PMID:25803189

  10. 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

  11. 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).

  12. Stabilization of a nutraceutical omega-3 fatty acid by encapsulation in ultrathin electrosprayed zein prolamine.

    PubMed

    Torres-Giner, Sergio; Martinez-Abad, Antonio; Ocio, Maria J; Lagaron, Jose M

    2010-08-01

    Docosahexaenoic acid (DHA) is a long chain polyunsaturated fatty acid of the omega-3 series (omega-3), which exerts strong positive influences on human health. The target of this study was the stabilization by encapsulation of this bioactive ingredient in zein ultrathin capsules produced by electrospraying. The zein ultrathin DHA encapsulation was observed by ATR-FTIR spectroscopy to be more efficient against degradation under both ambient conditions and in a confined space (so-called headspace experiment). In the latter case, that more closely simulates a sealed food packaging situation, the bioactive DHA was considerably more stable. By fitting the degradation data to a specific auto-decomposition food lipids kinetic model, it was seen that the encapsulated omega-3 fatty acid showed a 2.5-fold reduction in the degradation rate constant and also had much higher degradation induction time. Moreover, the ultrathin zein-DHA capsules resulted to be more stable across relative humidity and temperature. Finally, headspace analysis by gas chromatography coupled with mass spectrometry showed that the presence of 3 main flavor-influencing aldehydes in the headspace was much lower in the zein encapsulated DHA, suggesting that the encapsulated bioactive also releases much less off-flavors. Electrosprayed ultrathin capsules of zein are shown to exhibit potential in the design of novel functional foods or bioactive packaging strategies to enhance the stability of functional ingredients. Practical Application: This article presents a novel methodology for the stabilization by encapsulation of omega 3 nutraceuticals via electrospraying and has potential application in the development of functional foods.

  13. Identification of sulfoglycolipids from the alga Porphyridium purpureum by matrix-assisted laser desorption/ionisation quadrupole ion trap time-of-flight mass spectrometry.

    PubMed

    Naumann, Ivonne; Darsow, Kai H; Walter, Christian; Lange, Harald A; Buchholz, Rainer

    2007-01-01

    Sulfoglycolipids, isolated from different phototrophic organisms, particularly plants and algae, have already been identified as bioactive compounds. In addition to their antiviral activity their influence on the immune response in mammalian cells is the focus of many studies. For the first time it has been possible to investigate purified sulfoquinovosyldiacylglycerols (SQDGs) from the microalga Porphyridium purpureum by matrix-assisted laser desorption/ionisation (MALDI) in the negative ion reflectron mode. Thereby, different solid and ionic liquid matrices have been tested to improve signal intensity during the laser ionisation. By using the MALDI Trap time-of-flight (ToF) multiple-stage (MS(n)) hybrid mass spectrometer the fatty acid compositions of the SQDGs were analysed by MS, and confirmed by MS(2) and MS(3) experiments. Thereby, hexadecanoic acid (C16:0), octadecadienoic acid (C18:2), eicosatetraenoic acid (C20:4), and eicosapentaenoic acid (C20:5) were detected in the purified fraction of SQDGs. The localisation of hexadecanoic acid (C16:0) at the sn-2 position, and unsaturated fatty acids at the sn-1 position of the SQDGs, determined by specific enzymatic hydrolysis, marks a procaryotic biosynthesis of SQDGs in the eucaryotic alga cells.

  14. Desorption electrospray ionization-mass spectrometry of proteins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization-mass spectrometry (DESI-MS) was evaluated for the detection of proteins ranging in molecular mass from 12 to 66 kDa. Proteins were uniformly deposited on a solid surface without pretreatment and analyzed with a DESI source coupled to a quadrupole ion trap mass spec...

  15. 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…

  16. HCO+ and N2H+ as ionisation tracers in the low-mass protostar IRAS16293-2422

    NASA Astrophysics Data System (ADS)

    Quénard, D.; Bottinelli, S.; Caux, E.

    2016-05-01

    Ionisation in the molecular environment of star-forming regions gives important clues on the chemical processes that take place in the environment of a young protostar. Ionisation can be traced with molecules like HCO+ and N2H+ and it regulates the formation of larger molecules such as complex organic molecules (COMs). The ionisation degree can also play an important role in the free-fall timescale of the protostar since it prevents the neutral material to collapse through collisions with ions and electrons bound to the magnetic field of the central protostar.

  17. Improved precision and accuracy for high-performance liquid chromatography/Fourier transform ion cyclotron resonance mass spectrometric exact mass measurement of small molecules from the simultaneous and controlled introduction of internal calibrants via a second electrospray nebuliser.

    PubMed

    Herniman, Julie M; Bristow, Tony W T; O'Connor, Gavin; Jarvis, Jackie; Langley, G John

    2004-01-01

    The use of a second electrospray nebuliser has proved to be highly successful for exact mass measurement during high-performance liquid chromatography/Fourier transform ion cyclotron resonance mass spectrometry (HPLC/FTICRMS). Much improved accuracy and precision of mass measurement were afforded by the introduction of the internal calibration solution, thus overcoming space charge issues due to the lack of control over relative ion abundances of the species eluting from the HPLC column. Further, issues of suppression of ionisation, observed when using a T-piece method, are addressed and this simple system has significant benefits over other more elaborate approaches providing data that compares very favourably with these other approaches. The technique is robust, flexible and transferable and can be used in conjunction with HPLC, infusion or flow injection analysis (FIA) to provide constant internal calibration signals to allow routine, accurate and precise mass measurements to be recorded.

  18. Application of parallel gradient high performance liquid chromatography with ultra-violet, evaporative light scattering and electrospray mass spectrometric detection for the quantitative quality control of the compound file to support pharmaceutical discovery.

    PubMed

    Squibb, Anthony W; Taylor, Mark R; Parnas, Barry L; Williams, Gareth; Girdler, Richard; Waghorn, Peter; Wright, Adrian G; Pullen, Frank S

    2008-05-01

    The success of drug discovery assays, using plate-based technologies, relies heavily on the quality of the substrates being tested. Sample purity, identity and concentration must be assured for a screening hit to be validated. Most major pharmaceutical companies maintain large liquid screening files with often in excess of one million stock solutions, typically dissolved in DMSO. However, due to the inherent inaccuracies of high-throughput gravimetric analysis and automated dilution, stock solution concentrations can vary significantly from the assumed nominal value. Here, we present a rapid and effective method for measuring purity, identity and concentration of these stock solutions using four high-performance liquid chromatography (HPLC) columns with parallel ultraviolet spectrophotometry (UV), electrospray ionisation mass spectrometry (ESI-MS) and evaporative light scattering detection (ELSD) with a throughput of 1 min per sample.

  19. 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

  20. Analysis of wax ester molecular species by high performance liquid chromatography/atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Vrkoslav, Vladimír; Urbanová, Klára; Cvacka, Josef

    2010-06-18

    High chromatographic resolution of wax esters (WEs) was achieved by non-aqueous reversed-phase liquid chromatography on a Nova-Pak C18 column by optimising the acetonitrile/ethyl acetate mobile phase gradient. The retention behaviour of WEs was studied in this chromatographic system. The WEs eluted according to their equivalent carbon number (ECN) values; within the group of WEs with the identical ECN, the most unsaturated species tended to elute first. The isobaric WEs with different positions of the ester moiety were separated from each other whenever the lengths of the chains were sufficiently different. The methyl-branched esters eluted at shorter retention times than the straight-chained analogues, and the resolution among methyl-branched WEs depended on the position of the branching. The analytes were detected by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) using data-dependent scanning. WEs provided simple full-scan spectra with abundant protonated molecules and low-intensity fragments. Collision-induced dissociation (CID) promoted identification of the WE molecular species. The responses of WEs were found to be dependent on the number of double bonds and on the alkyl-chain length; the limits of the detection ranged from 20micromol/L to 200nmol/L. The HPLC/APCI-MS was applied for the analysis of the WEs isolated from honeycomb beeswax, jojoba oil and human hair. Good agreement between reported results and the literature data was achieved, with several novel polyunsaturated WEs also being found.

  1. Mass determination of megadalton-DNA electrospray ions using charge detection mass spectrometry.

    PubMed

    Schultz, J C; Hack, C A; Benner, W H

    1998-04-01

    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)ethylenediaminetetraacetic acid buffer, diluted in 50 vol. % acetonitrile, were obtained without cleanup of the sample. A CD 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.

  2. Electrosprayed nanocomposites based on hyaluronic acid derivative and Soluplus for tumor-targeted drug delivery.

    PubMed

    Lee, Song Yi; Lee, Jeong-Jun; Park, Ju-Hwan; Lee, Jae-Young; Ko, Seung-Hak; Shim, Jae-Seong; Lee, Jongkook; Heo, Moon Young; Kim, Dae-Duk; Cho, Hyun-Jong

    2016-09-01

    Nanocomposite (NC) based on hyaluronic acid-ceramide (HACE) and Soluplus (SP) was fabricated by electrospraying for the tumor-targeted delivery of resveratrol (RSV). Amphiphilic property of both HACE and SP has been used to entrap RSV in the internal cavity of NC. Electrospraying with established experimental conditions produced HACE/SP/RSV NC with 230nm mean diameter, narrow size distribution, negative zeta potential, and >80% drug entrapment efficiency. Sustained and pH-dependent drug release profiles were observed in drug release test. Cellular uptake efficiency of HACE/SP NC was higher than that of SP NC, mainly based on HA-CD44 receptor interaction, in MDA-MB-231 (CD44 receptor-positive human breast cancer) cells. Selective tumor targetability of HACE/SP NC, compared to SP NC, was also confirmed in MDA-MB-231 tumor-xenograted mouse model using a near-infrared fluorescence (NIRF) imaging. According to the results of pharmacokinetic study in rats, decreased in vivo clearance and increased half-life of RSV in NC group, compared to drug solution group, were shown. Given that these experimental results, developed HACE/SP NC can be a promising theranostic nanosystem for CD44 receptor-expressed cancers. PMID:27208440

  3. Factors influencing the electrospray intrasource separation and selective ionization of glycerophospholipids.

    PubMed

    Han, Xianlin; Yang, Kui; Yang, Jingyue; Fikes, Kora N; Cheng, Hua; Gross, Richard W

    2006-02-01

    The external electric field induces a separation of cations from negative electrolyte ions in the infusate while differential ionization of molecular species that possess differential electrical propensities can be induced in either the positive- or negative-ion mode during the electrospray ionization process. These physical and electrical processes that occur in the electrospray ion source have been used to selectively ionize lipid classes possessing different electrical propensities that are now known as "intrasource separation and selective ionization". However, the chemical principles underlying charge-dependent alterations in ionization efficiencies responsible for the selective ionization of lipid classes are not known with certainty. Herein, we examined the multiple factors that contribute to intrasource separation and selective ionization of lipid classes under optimal instrumental conditions. We demonstrated that many different lipid classes could be selectively ionized in the ion source and that intrasource resolution of distinct molecular constituents was independent of lipid concentration, flow rate, and residual ions under most experimental conditions. Moreover, the presence of alkaline conditions facilitates the selective ionization of many lipid classes through a mechanism independent of the design of the ESI ion source. Collectively, this study provides an empirical foundation for understanding the chemical mechanisms underlying intrasource separation and selective ionization of lipid classes that can potentially be used for global analysis of cellular lipidomes without the need for chromatographic separation.

  4. Direct observation of lipid hydroperoxides in phospholipid vesicles by electrospray mass spectrometry.

    PubMed

    Spickett, C M; Pitt, A R; Brown, A J

    1998-09-01

    Positive ion electrospray ionization mass spectrometry was used to obtain a lipid profile of vesicles prepared from egg yolk lethicin and enriched with arachidonylstearoyl phosphatidylcholine and dipalmitoyl phosphatidylcholine. The vesicles were oxidized by treatment with tert-butylhydroperoxide and iron (II) sulfate, and the formation of hydroperoxides of the polyunsaturated lipid arachidonylstearoyl phosphatidylcholine was observed. The native lipid signal at 832 a.m.u. decreased and new signals appeared at 864, 896, and 928 a.m.u., corresponding to the addition of one (+32), two (+64), and three (+96) molecules of dioxygen. The dihydroperoxide was found to be the most favourable peroxide product, but it appeared that a degradation of the hydroperoxides was occurring concomitant with their formation, and only their net formation was observed. The rate of depletion of the polyunsaturated lipid and the rate of accumulation of the hydroperoxides was found to increase with the Fe2+ concentration between 10 microM and 2 mM, and was also dependent on the tert-butylhydroperoxide concentration. This is the first report of analysis of lipid hydroperoxides by electrospray mass spectrometry, showing that technique offers a sensitive, direct, and informative approach to the study of oxidative damage to biological membranes. PMID:9741599

  5. 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.

  6. Potentiometric titrations in acetonitrile-water mixtures: evaluation of aqueous ionisation constant of ketoprofen.

    PubMed

    Herrador, M Angeles; González, A Gustavo

    2002-03-11

    Non ideality of acetonitrile-water mixtures was studied from data on the excess of molar volumes and viscosities. pH and autoprotolisis constants were evaluated at the standard state of the mixed solvent from titrations of a strong acid with a strong base. In order to illustrate the evaluation of the aqueous ionisation constant of water insoluble compounds from pH titrations in ACN-water mixtures, a typical insoluble arylpropionic acid, ketoprofen, was chosen. Ketoprofen was titrated in mixtures from 10 to 70% w/w of acetonitrile against a strong base. From the titration data, the ionisation constant of ketoprofen was evaluated at the standard state of the solvent mixture (pK(a)(*)). Aqueous pK(a) was determined by extrapolation, as the intercept of the plot of pK(a)(*) versus ACN mole fraction.

  7. Classification of the Spectra of Highly Ionised Atoms During the Last Seven Years

    NASA Astrophysics Data System (ADS)

    Fawcett, B. C.

    1981-10-01

    This review of recent contributions to the classification of the spectra of highly ionised atoms emphasises how major research projects have influenced progress. These projects include experiments on board orbiting space satellites and SKYLAB, those of fusion research (notably involving TOKAMAK devices), studies with giant pulse laser-produced-plasmas and beam-foil spectroscopy. In addition, the large volume of data gathered through the application of traditional methods and the impact of theoretical calculations are discussed. A comprehensive reference list of papers reporting emission line identifications for elements lighter than nickel and ionisation stages higher than the fourth is included, along with references to other bibliographies and compilations of energy levels, or wavelengths and identifications.

  8. 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.

  9. Chemical characterization of crude petroleum using nanospray desorption electrospray ionization coupled with high-resolution mass spectrometry.

    PubMed

    Eckert, Peter A; Roach, Patrick J; Laskin, Alexander; Laskin, Julia

    2012-02-01

    Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of the polar constituents 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 based on their solubility in solvents that are rarely used for petroleum characterization providing better coverage of the crude oil composition as compared to electrospray ionization (ESI). It also enables rapid characterization of water-soluble components of petroleum samples that is difficult to perform using traditional approaches.

  10. 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.

  11. 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

  12. Determination of sultopride and tiapride in serum by gas chromatography using a surface ionisation detector.

    PubMed

    Kamizono, A; Inotsume, N; Miyamoto, K; Ueda, K; Miyakawa, T; Arimoto, H; Nakano, M

    1991-06-14

    A sensitive and selective method has been developed for the determination of sultopride and tiapride in serum using gas chromatography with a surface ionisation detector. No interfering peaks from endogenous substances were observed. The method showed good reproducibility and accuracy, and the standard curve was linear up to 2 micrograms/ml with a correlation coefficient of 0.999. This method is applicable to pharmacokinetic studies and therapeutic drug monitoring of sultopride and tiapride.

  13. 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.

  14. Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives: a review.

    PubMed

    Paine, Martin R L; Barker, Philip J; Blanksby, Stephen J

    2014-01-15

    The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis.

  15. 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.

  16. 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.

  17. 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.

  18. Electrosprayed inulin microparticles for microbiota triggered targeting of colon.

    PubMed

    Jain, Arvind K; Sood, Vishesh; Bora, Meghali; Vasita, Rajesh; Katti, Dhirendra S

    2014-11-01

    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.

  19. Micro- and nanoparticles by electrospray: advances and applications in foods.

    PubMed

    Tapia-Hernández, José A; Torres-Chávez, Patricia I; Ramírez-Wong, Benjamín; Rascón-Chu, Agustín; Plascencia-Jatomea, Maribel; Barreras-Urbina, Carlos G; Rangel-Vázquez, Norma A; Rodríguez-Félix, Francisco

    2015-05-20

    Micro- and nanotechnology are tools being used strongly in the area of food technology. The electrospray technique is booming because of its importance in developing micro- and nanoparticles containing an active ingredient as bioactive compounds, enhancing molecules of flavors, odors, and packaging coatings, and developing polymers that are obtained from food (proteins, carbohydrates), as chitosan, alginate, gelatin, agar, starch, or gluten. The electrospray technique compared to conventional techniques such as nanoprecipitation, emulsion-diffusion, double-emulsification, and layer by layer provides greater advantages to develop micro- and nanoparticles because it is simple, low cost, uses a low amount of solvents, and products are obtained in one step. This technique could also be applied in the agrifood sector for the preparation of controlled and/or prolonged release systems of fertilizer or agrochemicals, for which more research must be conducted.

  20. Micro- and nanoparticles by electrospray: advances and applications in foods.

    PubMed

    Tapia-Hernández, José A; Torres-Chávez, Patricia I; Ramírez-Wong, Benjamín; Rascón-Chu, Agustín; Plascencia-Jatomea, Maribel; Barreras-Urbina, Carlos G; Rangel-Vázquez, Norma A; Rodríguez-Félix, Francisco

    2015-05-20

    Micro- and nanotechnology are tools being used strongly in the area of food technology. The electrospray technique is booming because of its importance in developing micro- and nanoparticles containing an active ingredient as bioactive compounds, enhancing molecules of flavors, odors, and packaging coatings, and developing polymers that are obtained from food (proteins, carbohydrates), as chitosan, alginate, gelatin, agar, starch, or gluten. The electrospray technique compared to conventional techniques such as nanoprecipitation, emulsion-diffusion, double-emulsification, and layer by layer provides greater advantages to develop micro- and nanoparticles because it is simple, low cost, uses a low amount of solvents, and products are obtained in one step. This technique could also be applied in the agrifood sector for the preparation of controlled and/or prolonged release systems of fertilizer or agrochemicals, for which more research must be conducted. PMID:25938374

  1. Electrosprayed inulin microparticles for microbiota triggered targeting of colon.

    PubMed

    Jain, Arvind K; Sood, Vishesh; Bora, Meghali; Vasita, Rajesh; Katti, Dhirendra S

    2014-11-01

    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. PMID:25129739

  2. Electrosprayed polyaniline as cathode material for lithium secondary batteries

    SciTech Connect

    Manuel, James; Raghavan, Prasanth; Shin, Chorong; Heo, Min-Yeong; Ahn, Jou-Hyeon; Noh, Jung-Pil; Cho, Gyu-Bong; Ryu, Ho-Suk; Ahn, Hyo-Jun

    2010-03-15

    Doped polyaniline with LiPF{sub 6} is electrosprayed onto aluminum foil using electrospinning technique, and evaluated as cathode active material for application in room-temperature lithium batteries. Doping level is characterized using FTIR and UV-vis spectroscopy. In FTIR Spectra, characteristic peaks of PANI are shifted to lower bands as a result of doping which indicates the effectiveness of doping. Doping level is also confirmed by UV-vis spectra. Surface morphology of the cathode is studied using scanning electron microscope. Electrochemical evaluation of the cell using electrosprayed PANI as cathode show good cycling properties. The cell delivers a high discharge value of 142.5 mAh/g which is about 100% of theoretical capacity, and the capacity is lowered during cycle and reached 61% of theoretical capacity after 50 cycles. The cell delivers a stable but lower discharge capacity at higher C-rates.

  3. The dynamics of a steady Taylor cone electrospray

    NASA Astrophysics Data System (ADS)

    Bell, Martin; Rutgers, Maarten A.

    1998-11-01

    A liquid drop at the tip of a needle will become conical if a high voltage is supplied to the needle. This is known as a Zeleny^1-Taylor^2 cone. Due to the finite conductivity of most liquids, a thin liquid jet will emerge from the cone tip. This jet can be thinner than 1 micrometer and move with speeds in excess of 10 m/s! The jet breaks up due to a Rayleigh instability into a stream of monodisperse droplets. The particles themselves carry charge and can cause the droplet stream to break up into a diverging conical spray. De La Mora^3 has calculated the relation between the liquid and spray cone angles, but less in known about the dynamics with which the droplets move from the initial jet into the final electrospray cone. We have observed electrosprayed droplets in a regime where the Taylor cone oscillates axisymmetrically, leading to an interrupted spray. By periodically driving the volume of the Taylor cone, and illuminating the spray stroboscopically at the same frequency, we can essentially `freeze' the evolution of a packet of droplets in the spray cone. We clearly observe the disintegration of the initial jet of droplets into a growing spherical cloud. The expanding clouds can be inscribed in the cone of an uninterrupted electrospray. ^1J. Zeleny, Phys. Rev. 3:69, (1914), ^2G.I. Taylor, J. Fluid Mech. 2:1, (1965) ^3J.F. De La Mora, J. Fluid Mech. 243:561, (1992)

  4. 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.

  5. Born total ionisation cross sections: An algebraic computing program using Maple

    NASA Astrophysics Data System (ADS)

    Bartlett, Philip L.; Stelbovics, Andris T.

    2003-08-01

    The software described in this paper uses the Maple algebraic computing environment to calculate an analytic form for the matrix element of the plane-wave Born approximation of the electron-impact ionisation of an atomic orbital, with arbitrary orbital and angular momentum quantum numbers. The atomic orbitals are approximated by Hartree-Fock Slater functions, and the ejected electron is modelled by a hydrogenic Coulomb wave, made orthogonal to all occupied orbitals of the target atom. Clenshaw-Curtis integration techniques are then used to calculate the total ionisation cross-section. For improved performance, the numerical integrations are performed using FORTRAN by automatically converting the analytic matrix element for each orbital into a FORTRAN subroutine. The results compare favourably with experimental data for a wide range of elements, including the transition metals, with excellent convergence at high energies. Program summaryTitle of program: BIX Catalogue identifier:ADRZ Program summary URL:http://www.cpc.cs.qub.ac.uk/cpc/summaries/ADRZ Program obtainable from:CPC Program Library, Queen's University of Belfast, N. Ireland Computers: Platform independent Operating systems: Tested on DEC Alpha Unix, Windows NT 4.0 and Windows XP Professional Edition Programming language used: Maple V Release 5.1 and FORTRAN 90 Memory required: 256 MB No. of processors used: 1 No. of bytes in distributed program, including test data, etc.:61754 Distributed format:tar gzip file Keywords: Born approximation, electron-impact ionisation cross-section, Maple, Hartree-Fock Nature of physical problem: Calculates the total electron impact ionisation cross-section for neutral and ionised atomic species using the first-Born approximation. The scattered electron is modelled by a plane wave, and the ejected electron is modelled by a hydrogenic Coulomb wave, which is made orthogonal to all occupied atomic orbitals, and the atomic orbitals are approximated by Hartree-Fock Slater

  6. Gas-phase and solution studies of three resorcin[4]arene derivatives using electrospray time-of-flight mass spectrometry.

    PubMed

    Reynolds, James C; Chew, Mei Q; Martin, Helen J; Stubbs, Emma C; Waters, Marguerite A; Crotty, Sarah C; Silvestre-Gonzalez, Vanessa; Chan, Yohan; Thomas, C L Paul; Page, Philip C Bulman; Creaser, Colin S; Heaney, Harry

    2013-01-01

    Electrospray ionisation mass spectrometry (ESI-MS) has been used to study the relative gas-phase proton and alkali metal (Li, Na, K and Cs) binding affinities of three different resorcin[4]arenes using the kinetic method. Collision-induced dissociation (CID) was used to study the fragmentation of resorcin[4]arene heterodimer sandwich complexes, allowing the relative binding affinity order to be established. All the alkali metal cations have the same gas-phase binding affinity order with the resorcin[4]arene host molecules. At collision energies of > or = 13eV, one of the [resorcin[4]arene+Metal]+, (Metal = Li, Na, K) ions fragmented through break-up of the resorcin[4]arene, whilst the other host resorcin[4]arene remained intact, causing an apparent change in binding affinity at high collision energy. This effect was not observed with caesium, since all complex ions dissociated readily under CID by displacement of the caesium cation. The binding affinity for the protonated resorcin[4]arenes was found to be different from the alkali metal cation binding affinity because of the higher proton affinity of the nitrogen-containing resorcin[4]arenes. It is shown that resorcin[4]arenes containing an oxazine ring can be converted into a ring-opened derivative via an Eschweiler-CLarke reaction in the presence of formic acid. A second ring-opening process also occurs, including a hydrolysis reaction that results in apparent Losses of 12 mass units from the intact resorcin[4]arene. Both these reactions occur in solution before mass spectrometric investigation and cannot be achieved by CID. This observation was confirmed by inducing the Eschweiter-CLarke reaction in a model benzoxazine compound.

  7. 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. PMID:17044124

  8. Profiling aged artisanal Cheddar cheese using secondary electrospray ionization mass spectrometry.

    PubMed

    Bean, Heather D; Mellors, Theodore R; Zhu, Jiangjiang; Hill, Jane E

    2015-05-01

    A number of direct injection mass spectrometry methods that can sample foods nondestructively and without sample preparation are being developed with applications ranging from the rapid assessment of food safety to the verification of protected designations of origin. In this pilot study, secondary electrospray ionization mass spectrometry (SESI-MS) in positive- and negative-ion modes was used to collect volatile fingerprints of artisanal Cheddar cheeses aged for one to three years. SESI-MS fingerprints were found to change in an aging-dependent manner and can be used to descriptively and predictively categorize Cheddars by their aging period, identify volatile components that increase or decrease with aging, and robustly discriminate individual batches of artisanal cheese. From these results, it was concluded that SESI-MS volatile fingerprinting could be used by artisanal food producers to characterize their products during production and aging, providing useful data to help them maximize the value of each batch. PMID:25865575

  9. 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.

  10. Electrospray ionization mass spectrometry fingerprinting of perfumes: Rapid classification and counterfeit detection.

    PubMed

    Marques, Lygia de Azevedo; Catharino, Rodrigo Ramos; Bruns, Roy E; Eberlin, Marcos N

    2006-01-01

    A fast procedure to classify perfumes and identify counterfeit samples is described. Dilution of a few microL of the sample in a 1:1 methanol/water solution is followed by detection of its major polar components via direct infusion electrospray ionization mass spectrometry (ESI-MS) in the positive ion mode. As proof-of-principle cases, three famous brands of perfumes were used. The ESI+-MS fingerprints of authentic samples were very characteristic, showing distinctive sets of polar markers for each sample. Principal component analysis (PCA) placed samples of the three perfume brands in well-defined groups. Counterfeit samples were also clearly detected owing to contrasting ESI-MS fingerprints, with PCA placing these samples far away from the authentic samples.

  11. Electrospray ionization ion-trap multiple-stage mass spectrometry of Quillaja saponins.

    PubMed

    Bankefors, Johan; Broberg, Susanna; Nord, Lars I; Kenne, Lennart

    2011-07-01

    Fifteen identified C-18 fatty acyl-containing saponin structures from Quillaja saponaria Molina have been investigated by electrospray ionization ion-trap multiple-stage mass spectrometry (ESI-IT-MS(n)) in positive ion mode. Their MS(1)-MS(3) spectra were analyzed and ions corresponding to useful fragments, important for the structural identification of Quillaja saponins, were recognized. A few key fragments could describe the structural variations in the C-3 and the C-28 oligosaccharides of the Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from the MS(1)-MS(3) spectra of these saponins, together with key fragments from these saponins and 13 previously investigated saponins, was constructed for the identification of structural elements in Quillaja saponins. Peak intensity ratios in MS(3) spectra were found to be correlated to structural features of the investigated saponins and is therefore of value for the identification of regioisomers.

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

    DOEpatents

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

    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.

  13. 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

  14. 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

  15. Comparison of Internal Energy Distributions of Ions Created by Electrospray Ionization and Laser Ablation-Liquid Vortex Capture-Electrospray Ionization

    DOE PAGESBeta

    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 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

  16. 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.

  17. 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. PMID:26141269

  18. 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.

  19. 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.

  20. Simultaneous determination of six bioactive flavonoids in Citri Reticulatae Pericarpium by rapid resolution liquid chromatography coupled with triple quadrupole electrospray tandem mass spectrometry.

    PubMed

    Liu, E-Hu; Zhao, Pan; Duan, Li; Zheng, Guo-Dong; Guo, Long; Yang, Hua; Li, Ping

    2013-12-15

    A rapid resolution liquid chromatography/electrospray ionisation tandem mass spectrometry (RRLC-ESI-MS(n)) method has been firstly developed and validated for simultaneous determination of six bioactive flavonoids in Citri Reticulatae Pericarpium (CRP). The antiproliferative activities of the six flavonoids in CRP, namely naringin, hesperidin, nobiletin, 3,5,6,7,8,3',4'-heptamethoxyflavone, tangeretin and 5-hydroxy-6,7,8,3',4'-pentamethoxyflavone, were evaluated and compared by Cell Counting Kit-8 Assay. Quantification was carried out on an Agilent triple quadrupole LC-MS system using multiple reaction monitoring mode. The established method was successfully applied for determination of the six flavonoids in samples collected from different regions in China. Compared with the reported analytical methods, the RRLC-ESI-MS(n) method is powerful in quantitative analysis of multi-component in terms of time savings and sensitivity. Hierarchical cluster analysis (HCA) was also performed to differentiate and classify the samples based on the contents of the six characteristic flavonoids. The HCA results indicated that Citrus reticulata 'Chachi' samples could be easily distinguished from other CRP samples. The developed RRLC-ESI-MS(n) method combined with HCA might be utilised as a quality control method for CRP. PMID:23993574

  1. 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

  2. Design and performance of an ionisation chamber for the measurement of low alpha-activities

    NASA Astrophysics Data System (ADS)

    Hartmann, A.; Hutsch, J.; Krüger, F.; Sobiella, M.; Wilsenach, H.; Zuber, K.

    2016-04-01

    A new ionisation chamber for alpha-spectroscopy has been built from radio-pure materials for the purpose of investigating long lived alpha-decays. The measurement makes use of pulse shape analysis to discriminate between signal and background events. The design and performance of the chamber is described in this paper. A background rate of (10.9 ± 0.6) counts per day in the energy region of 1-9 MeV was achieved with a run period of 30.8 days. The background is dominantly produced by radon daughters.

  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. Effet galvanique et spectroscopie d'ionisation multiphotonique à large bande : application à l'uranium

    NASA Astrophysics Data System (ADS)

    Gagné, Jean-Marie; Babin, François

    1992-04-01

    The uranium single colour multiphoton ionization spectrum, with high laser bandwidth excitation, was measured, in the spectral range of R6G, using the fast pulsed (sim 10^{-9} s) optogalvanic signal generated by photoionization in the dark space of a hollow cathode discharge. Results indicate that this spectrum is dense in the 570 to 610 nm spectral range. A list of the 74 most intense lines is given. The results of a try at explaining these lines by a three photon resonant or quasi-resonant scheme, using know levels of uranium, are presented. The multiphoton ionization line at 591.54 nm is a special case which is discussed more thoroughly. Grâce à l'effet optogalvanique pulsé rapide (sim 10^{-9} s) généré par la photoionisation dans l'espace sombre d'une décharge en régime cathode creuse, le spectre d'ionisation multiphotonique à large bande de l'uranium, dans le domaine spectral de la rhodamine 6G, a été mesuré. Les résultats indiquent que pour cette bande spectrale du laser, comprise entre 570 et 610 nm, ce spectre optogalvanique d'ionisation multiphotonique est très riche. Une liste de 74 raies photoioniques les plus significatives est présentée. Les résultats préliminaires d'une étude pour expliquer la présence de ces raies, en utilisant des schémas d'ionisation à trois photons résonnants ou quasi-résonnants, à partir d'une liste de niveaux publiés, sont également présentés. La raie d'ionisation associée à la longueur d'oride 591,54 nm est un cas spécial qui est discuté plus longuement.

  5. 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. PMID:26443545

  6. 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.

  7. Age determination of plutonium material in nuclear forensics by thermal ionisation mass spectrometry.

    PubMed

    Wallenius, M; Mayer, K

    2000-02-01

    Age is a key parameter when deducing the history of plutonium material, i.e. the plutonium produced in the nuclear reactors. This is of vital importance, when a smuggled plutonium sample has been seized and the origin has to be determined. A methodology is described which allows accurately to determine the age of plutonium material by thermal ionisation mass spectrometry using independent parent/daughter relations. This has been demonstrated for Reference Materials of known ages as well as for real samples. The already established method using gamma spectrometry is compared to this.

  8. Survey of Natural Cadmium Isotope Fractionation by Double Spike Thermal Ionisation Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schmitt, A.; Galer, S. J.; Abouchami, W.

    2006-12-01

    Wombacher et al. (2003) have shown recently that natural Cd isotope fractionations in terrestrial materials are extremely limited (~100 ppm/amu or less). Thus, excellent external precision is absolutely paramount if Cd isotope fractionations are to be adequately quantified. Here we present a new high-precision double spike (DS) technique for Cd isotopes in which the Cd is measured by thermal ionisation mass spectrometry (TIMS, ThermoElectron Triton), which draws on the pioneering work of Rosman et al. (1980). We observe pronounced anomalous odd-even isotope mass bias during TIMS measurement of Cd with silica gel activator, and avoid such effects by utilizing even isotopes of Cd only. The double spike and its composition were carefully optimized (cf. Galer, 1999), and the "natural" Cd isotope fractionation is expressed as the relative deviations in ^{112}Cd/^{110}Cd (in parts per 104) from our JMC Cd shelf standard. The external reproducibility for 100 ng loads of double-spiked JMC Cd shelf is ± 0.14 ɛ^{112/110}Cd (2SD, N=57) -- i.e. ±7 ppm/amu -- which is a factor of 4 to 10 times better than that reported in published studies using MC-ICP-MS techniques (e.g. Wombacher et al., 2003; Cloquet et al., 2005). The DS-TIMS method offers further benefits in terms of superior sensitivity, while Cd abundances are obtained as a biproduct by isotope dilution. We have analyzed ɛ^{112/110}Cd in over sixty samples from different terrestrial reservoirs and environments in order to delimit the extent of natural isotope fractionation of Cd. Most samples were duplicated or triplicated. To facilitate inter-lab comparison, our measured ɛ^{112/110}Cd for the standards "Münster Cd" and BAM-1012 averaged +21.46 and -7.42, respectively. On the whole, our study confirms the conclusions of Wombacher et al. (2003) that Cd isotope variations in terrestrial materials are limited -- nearly all samples fall within the range -1.0 to +1.0 in ɛ^{112/110}Cd. Nevertheless, we are able for the

  9. Facile identification by electrospray mass spectrometry of the insulin fragment A14-21-B17-30 produced by insulin proteinase.

    PubMed

    Vu, L; Stöcklin, R; Rose, K; Offord, R E

    1993-11-01

    We confirm the cleavage at position B16-17 of porcine insulin which occurs during in vitro digestion by insulin proteinase. The fragment A14-21-B17-30 was purified by reversed-phase high performance liquid chromatography and characterized by electrospray ionization mass spectrometry. Fast-atom bombardment mass spectrometry, on the other hand, failed to detect the presence of this fragment.

  10. Desorption electrospray ionization imaging of small organics on mineral surfaces.

    PubMed

    Bennett, Rachel V; Fernández, Facundo M

    2015-01-01

    Desorption electrospray ionization (DESI)-mass spectrometry facilitates the ambient chemical analysis of a variety of surfaces. Here we describe the protocol for using DESI imaging to measure the distributions of small prebiotically relevant molecules on granite surfaces. Granites that contain a variety of juxtaposed mineral species were reacted with formamide in order to study the role of local mineral environment on the production of purines and pyrimidines. The mass spectrometry imaging (MSI) methods described here can also be applied to the surface analysis of rock samples involved in other applications such as petroleum or environmental chemistries. PMID:25361668

  11. 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. PMID:23005852

  12. Desorption electrospray ionization imaging of small organics on mineral surfaces.

    PubMed

    Bennett, Rachel V; Fernández, Facundo M

    2015-01-01

    Desorption electrospray ionization (DESI)-mass spectrometry facilitates the ambient chemical analysis of a variety of surfaces. Here we describe the protocol for using DESI imaging to measure the distributions of small prebiotically relevant molecules on granite surfaces. Granites that contain a variety of juxtaposed mineral species were reacted with formamide in order to study the role of local mineral environment on the production of purines and pyrimidines. The mass spectrometry imaging (MSI) methods described here can also be applied to the surface analysis of rock samples involved in other applications such as petroleum or environmental chemistries.

  13. 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.

  14. Aspartame degradation study using electrospray ionization mass spectrometry.

    PubMed

    Pattanaargson, S; Sanchavanakit, C

    2000-01-01

    Electrospray mass spectrometry was used to simultaneously determine aspartame (APM) and five of its degradation products; aspartic acid, aspartylphenylalanine, 5-benzyl-3,6-dioxo-2-piperazieacetic acid (diketopiperazine), phenylalanine, and phenylalanine methyl ester. Under the ionization conditions used, there was no interfering fragmentation for any of the six compounds, i.e., no fragmentation of the compound being tested into other species also being monitored. A study of APM degradation in solution at various pH's and at various temperatures using this method was performed.

  15. Fragmentation of Electrospray-Produced Deprotonated Ions of Oligodeoxyribonucleotides Containing an Alkylated or Oxidized Thymidine

    NASA Astrophysics Data System (ADS)

    Wang, Pengcheng; Williams, Renee T.; Guerrero, Candace R.; Ji, Debin; Wang, Yinsheng

    2014-07-01

    Alkylation and oxidation constitute major routes of DNA damage induced by endogenous and exogenous genotoxic agents. Understanding the biological consequences of DNA lesions often necessitates the availability of oligodeoxyribonucleotide (ODN) substrates harboring these lesions, and sensitive and robust methods for validating the identities of these ODNs. Tandem mass spectrometry is well suited for meeting these latter analytical needs. In the present study, we evaluated how the incorporation of an ethyl group to different positions (i.e., O 2, N3, and O 4) of thymine and the oxidation of its 5-methyl carbon impact collisionally activated dissociation (CAD) pathways of electrospray-produced deprotonated ions of ODNs harboring these thymine modifications. Unlike an unmodified thymine, which often manifests poor cleavage of the C3'-O3' bond, the incorporation of an alkyl group to the O 2 position and, to a much lesser extent, the O 4 position, but not the N3 position of thymine, led to facile cleavage of the C3'-O3' bond on the 3' side of the modified thymine. Similar efficient chain cleavage was observed when thymine was oxidized to 5-formyluracil or 5-carboxyluracil, but not 5-hydroxymethyluracil. Additionally, with the support of computational modeling, we revealed that proton affinity and acidity of the modified nucleobases govern the fragmentation of ODNs containing the alkylated and oxidized thymidine derivatives, respectively. These results provided important insights into the effects of thymine modifications on ODN fragmentation.

  16. 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.

  17. 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.

  18. An electrospray ionization-ion mobility spectrometer as detector for high- performance liquid chromatography.

    PubMed

    Zühlke, Martin; Riebe, Daniel; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Zenichowski, Karl; Diener, Marc; Linscheid, Michael W

    2015-01-01

    The application of electrospray ionization (ESI) ion mobility (IM) spectrometry on the detection end of a high-performance liquid chromatograph has been a subject of study for some time. So far, this method has been limited to low flow rates or has required splitting of the liquid flow. This work presents a novel concept of an ESI source facilitating the stable operation of the spectrometer at flow rates between 10 μL mn(-1) and 1500 μL min(-1) without flow splitting, advancing the T-cylinder design developed by Kurnin and co-workers. Flow rates eight times faster than previously reported were achieved because of a more efficient dispersion of the liquid at increased electrospray voltages combined with nebulization by a sheath gas. Imaging revealed the spray operation to be in a rotationally symmetric multijet mode. The novel ESI-IM spectrometer tolerates high water contents (≤90%) and electrolyte concentrations up to 10mM, meeting another condition required of high-performance liquid chromatography (HPLC) detectors. Limits of detection of 50 nM for promazine in the positive mode and 1 μM for 1,3-dinitrobenzene in the negative mode were established. Three mixtures of reduced complexity (five surfactants, four neuroleptics, and two isomers) were separated in the millisecond regime in stand-alone operation of the spectrometer. Separations of two more complex mixtures (five neuroleptics and 13 pesticides) demonstrate the application of the spectrometer as an HPLC detector. The examples illustrate the advantages of the spectrometer over the established diode array detector, in terms of additional IM separation of substances not fully separated in the retention time domain as well as identification of substances based on their characteristic Ims.

  19. 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?

  20. 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.

  1. Studies on thermionic ionisation detection in comprehensive two-dimensional gas chromatography.

    PubMed

    Ryan, Danielle; Marriott, Philip

    2006-10-01

    This study explores the application of specific thermionic ionisation detection in comprehensive 2-D GC (GC x GC) and represents the first report of GC x GC with nitrogen phosphorus detection (GC x GC-NPD). Of particular interest is the performance of the NPD with respect to peak parameters of asymmetry and sensitivity. Since GC x GC produces much narrower peaks than obtained with fast GC (e.g. 100 ms vs. <1 s) the effect of detector response time and any lack of symmetry arising from the detection step is important if peak separation (resolution) is to be maintained. It was observed that detector gas flows had a significant impact on peak asymmetry and peak magnitude, and that optimisation of the detector was critical, particularly for complex sample analysis by GC x GC-NPD. Peak asymmetries ranging from As = 1.8 to 8.0 were observed under different conditions of detector gas flows. Comparison of GC x GC-NPD with GC x GC-flame ionisation detection (FID) showed the former to be approximately 20 times more sensitive for the detection of nitrogen-containing methoxypyrazines analytes, and GC x GC-NPD had a larger linear detection range compared to GC x GC-FID. Furthermore, comparison of GC x GC-NPD and GC x GC-TOFMS chromatograms for the analysis of coffee head-space demonstrated the benefits of selective detection, ultimately realised in a comparatively simplified contour plot.

  2. Comparison of Internal Energy Distributions of Ions Created by Electrospray Ionization and Laser Ablation-Liquid Vortex Capture/Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Cahill, John F.; Kertesz, Vilmos; Ovchinnikova, Olga S.; Van Berkel, Gary J.

    2015-09-01

    Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed noncontact liquid-vortex capture probe has been used to efficiently collect material ablated by a 355 nm UV laser 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 appears to be classic electrospray ionization spectra; however, the `softness' of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. In this work, a series of benzylpyridinium salts were employed as thermometer ions 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. These data, along with results from the analysis the biological molecules bradykinin and angiotensin III indicated that the ions or their fragments formed directly by UV laser ablation that survive the liquid capture/electrospray ionization process were likely to be an extremely small component of the total ion signal observed. Instead, the preponderate neutral molecules, clusters, and particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream, then electrosprayed, were the principal source of the ion signal observed. Thus, the electrospray ionization process used controls the overall `softness' of this technique.

  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. A broad area electrospray generated by a piezoelectric transformer

    NASA Astrophysics Data System (ADS)

    Ramshani, Zeinab; Johnson, Michael J.; Atashbar, Massood Z.; Go, David B.

    2016-07-01

    Electrosprays are typically formed by the application of a high (kilovolt) voltage to the flow exiting a small diameter capillary, and they have been used in applications ranging from material synthesis to spray coating because of the finely controlled plume of micron-sized droplets they produce. In this work, we report a similar but distinct spray directly off the surface of a piezoelectric transformer. Using a paper wick to deliver liquid to the surface of the piezoelectric crystal, a continuous, broad area spray is generated from the wick in contact with the transformer surface, only requiring input voltages on the order of 20 Vamp. Systematic variation of critical parameters indicate that this piezoelectric transformer-generated spray is similar to a conventional electrospray, with the spray current exhibiting a non-linear dependence on the solution conductivity, but distinct, as the spray exhibits little dependence on the solution surface tension. This innovative spray could potentially lead to uniform, large area spray coverage from a single device for a wide variety of applications.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. Comparative study of matrices for their use in the rapid screening of anabolic steroids by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Galesio, M; Rial-Otero, R; Capelo-Martínez, J-L

    2009-06-01

    New data on sample preparation and matrix selection for the fast screening of androgenic anabolic steroids (AAS) by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is presented. The rapid screening of 15 steroids included in the World Anti-Doping Agency (WADA) prohibited list using MALDI was evaluated. Nine organic and two inorganic matrices were assessed in order to determine the best matrix for steroid identification in terms of ionisation yield and interference by characteristic matrix ions. The best results were achieved for the organic matrices 2-(4-hydroxyphenylazo)benzoic acid (HABA) and trans-3-indoleacrylic acid (IAA). Good signals for all the steroids studied were obtained for concentrations as low as 0.010 and 0.050 microg/mL on the MALDI sample plate for the HABA and IAA matrices, respectively. For these two matrices, the sensitivity achieved by MALDI is comparable with the sensitivity achieved by gas chromatography/mass spectrometry (GC/MS), which is the conventional technique used for AAS detection. Furthermore, the accuracy and precision obtained with MALDI are very good, since an internal mass calibration is performed with the matrix ions. For the inorganic matrices, laser fluences higher than those used with organic matrices are required to obtain good MALDI signals. When inorganic matrices were used in combination with glycerol as a dispersing agent, an important reduction of the background noise was observed. Urine samples spiked with the study compounds were processed by solid-phase extraction (SPE) and the screening was consistently positive.

  14. A simple protocol for combinatorial cyclic depsipeptide libraries sequencing by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Gurevich-Messina, Juan M; Giudicessi, Silvana L; Martínez-Ceron, María C; Acosta, Gerardo; Erra-Balsells, Rosa; Cascone, Osvaldo; Albericio, Fernando; Camperi, Silvia A

    2015-01-01

    Short cyclic peptides have a great interest in therapeutic, diagnostic and affinity chromatography applications. The screening of 'one-bead-one-peptide' combinatorial libraries combined with mass spectrometry (MS) is an excellent tool to find peptides with affinity for any target protein. The fragmentation patterns of cyclic peptides are quite more complex than those of their linear counterparts, and the elucidation of the resulting tandem mass spectra is rather more difficult. Here, we propose a simple protocol for combinatorial cyclic libraries synthesis and ring opening before MS analysis. In this strategy, 4-hydroxymethylbenzoic acid, which forms a benzyl ester with the first amino acid, was used as the linker. A glycolamidic ester group was incorporated after the combinatorial positions by adding glycolic acid. The library synthesis protocol consisted in the following: (i) incorporation of Fmoc-Asp[2-phenylisopropyl (OPp)]-OH to Ala-Gly-oxymethylbenzamide-ChemMatrix, (ii) synthesis of the combinatorial library, (iii) assembly of a glycolic acid, (iv) couple of an Ala residue in the N-terminal, (v) removal of OPp, (vi) peptide cyclisation through side chain Asp and N-Ala amino terminus and (vii) removal of side chain protecting groups. In order to simultaneously open the ring and release each peptide, benzyl and glycolamidic esters were cleaved with ammonia. Peptide sequences could be deduced from the tandem mass spectra of each single bead evaluated. The strategy herein proposed is suitable for the preparation of one-bead-one-cyclic depsipeptide libraries that can be easily open for its sequencing by matrix-assisted laser desorption/ionisation MS. It employs techniques and reagents frequently used in a broad range of laboratories without special expertise in organic synthesis.

  15. {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.

  16. [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.

  17. Variable thrust/specific-impulse of multiplexed electrospray microthrusters

    NASA Astrophysics Data System (ADS)

    Lenguito, G.; Fernandez de la Mora, J.; Gomez, A.

    We report on the development of a single-propellant ElectroSpray (ES) microthruster able to: (a) cover a wide range of specific impulse (Isp) and thrust at high propulsion efficiency, and (b) provide macroscopic thrust via micro-fabricated emitter arrays. The electrospray is a mature technology for the emission of fast nanodroplets at a propulsive efficiency larger than 50% over the full Isp range. The size of the droplets depends on the propellant flow rate and the physical properties of the electrolyte, especially the electric conductivity. To achieve a useful thrust one needs to multiplex the ES by operating many in parallel, which we achieve via silicon microfabrication of arrays of multiple and identical nozzles. The Multiplexed Electrospray (MES) micro-thruster is composed mainly of two electrodes: a nozzle-array and an extractor electrode, between which the electric field needed to form the ES is established. We tested nozzle arrays with up to 37 capillaries, that are spaced 1mm apart, with ID/OD = 10/30μ m. The capillaries are filled with 2.01μ m silicon dioxide beads to increase the hydraulic impedance and ensure uniform flow rate through the different emitters. A third electrode (accelerator) is mounted downstream the extractor to accelerate the droplets, thereby increasing the microthruster performance. The system is packaged in an alumina casing for electrical insulation and propellant feed. Tests run in a vacuum chamber at a pressure ≤ 10-5 mbar demonstrated reliable operation for several hours with a relatively high beam energy of 7.56kV. The 37-nozzle MES device was tested with the ionic liquid ethylammonium nitrate (EAN), at estimated total flow rates between 1.2 and 14 μ L/h, emitted currents between 14.2 and 23.0 μ A, specific impulse ranging between 710 and 1930s, and thrust ranging between 7.5 and 33 μ N. EAN is well suited to cover a relatively broad range of charge/mass- at an average propulsion efficiency of 66%. With further scale

  18. Beer fingerprinting by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight Mass Spectrometry.

    PubMed

    Šedo, Ondrej; Márová, Ivana; Zdráhal, Zbyněk

    2012-11-15

    A method allowing parallel fingerprinting of proteins and maltooligosaccharides directly from untreated beer samples is presented. These two classes of compounds were detected by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight-Mass Spectrometry (MALDI-TOF-MS) analysis of beer mixed with 2,5-dihydroxybenzoic acid solution. The maltooligosaccharide profiles acquired from the MALDI sample spot center were not found characteristic for beers of different source and technology. On the other hand, according to profiles containing protein signals acquired from crystals formed on the border of the MALDI sample spot, we were able to distinguish beer samples of the same brand produced by different breweries. The discriminatory abilities of the method were further examined on a set of 17 lager beers, where the fingerprints containing protein signals enabled resolution of majority of examined brands. We propose MALDI-TOF-MS profiling as a rapid tool for beer brewing technology process monitoring, quality control, and determination of beer authenticity.

  19. Evidence For The Tongue of Ionisation In The Winter Dayside Ionosphere Over Svalbard

    NASA Astrophysics Data System (ADS)

    Pryse, S. E.; Sims, R. W.; Moen, J.

    Results are presented from a multi-instrument investigation of the dayside ionosphere at high latitudes, under conditions of Bz<0, that provide evidence for the tongue- of-ionisation (TOI) in winter over Svalbard. The TOI, transporting photoionisation from sub-auroral latitudes into the polar cap, has been identified in three successive tomography images at latitudes on the equatorward edge of the auroral region in the post-noon sector. Simultaneous observations by the ESR incoherent scatter radar re- veal cold plasma of increased density in the vicinity of the throat region where the TOI enters the polar cap. Supporting evidence for the feature is provided by optical emissions measured by meridian scanning photometers, together with plasma drift and particle observations from DMSP satellites. The observations are discussed in light of earlier modelling studies of the TOI.

  20. Electrospray as a tool for drug micro- and nanoparticle patterning.

    PubMed

    Scholten, Elke; Dhamankar, Himanshu; Bromberg, Lev; Rutledge, Gregory C; Hatton, T Alan

    2011-06-01

    Carbamazepine (CBZ) microparticles of different sizes and shapes, including spheres, q-tips, elongated spheres, and tear-shaped particles, were formed by electrospraying solutions of different CBZ concentrations. The particle characteristics were determined by the interplay between jet formation, droplet breakup, solvent evaporation, and eventual particle solidification. The average particle size increased with increasing CBZ concentration, with particles of different shapes being observed for different CBZ concentrations. The cascade of sizes and shapes observed was interpreted in terms of Rayleigh instability theory as applied to charged jets and droplets, with the final sizes depending upon the time needed to evaporate the solvent sufficiently for CBZ to solidify; the lower the initial concentration of CBZ, the smaller the final droplets/particles that are formed. PMID:21548568

  1. 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.

  2. Fabrication of silica nanocomposite-cups using electrospraying

    NASA Astrophysics Data System (ADS)

    Deotare, P. B.; Kameoka, J.

    2006-03-01

    We have investigated a new process for the fabrication of nanocomposite cups by electrospraying blended polymer-sol-gel solutions followed by calcination. Due to the low viscosity and high surface tension of the blended polymer-sol-gel solutions, the electrostatically extruded continuous liquid jet from the spray source became tiny droplets with diameters of less than 1 µm. These droplets dried in transit and were collected at the counter electrode. To eliminate polymers, as well as cross-link sol-gel material, they were calcined at 850 °C for 3 h. We also investigated a probable method to control the morphology of the nanocups by changing the ionic concentration of the polymer solution. This is a simple and efficient approach for producing nanocomposite cups, which cannot be made by the aggregation method. These nanocomposite cups may find applications in drug delivery and filtration media.

  3. Deposition of PLA/CDHA composite coating via electrospraying.

    PubMed

    Zhou, Huan; Bhaduri, Sarit B

    2013-01-01

    Composite coatings composed of carbonated calcium deficient hydroxyapatite (CDHA) and polylactic acid (PLA) were deposited on a PLA substrate surface via electrospraying. The operation parameters, structural properties, bioactivity, cell adhesion, and growth capability of as-fabricated PLA/CDHA coatings were investigated. The composite coating showed good biocompatibility and bioactivity. The deposited coating was also applied as a carrier to assist alendronate sodium (AS) local release. AS, an approved bisphosphonate drug used for the treatment of osteoporosis, was incorporated into a composite coating matrix via coelectrospraying. Its release behavior showed a long-term sustained release. This approach can be a potential coating technique for the surface modification of biopolymer implants. PMID:23594068

  4. 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.

  5. 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.

  6. Analysis of tear glucose concentration with electrospray ionization mass spectrometry.

    PubMed

    Taormina, Christopher R; Baca, Justin T; Asher, Sanford A; Grabowski, Joseph J; Finegold, David N

    2007-02-01

    We have developed a mass spectrometry-based method that allows one to accurately determine the glucose concentration of tear fluid. We used a 1 microL micro-capillary to collect tear fluid from the tear meniscus with minimal irritation of the eye. We analyzed the 1 muL volume of collected tear fluid with liquid-chromatography electrospray ionization mass spectrometry with the use of D-glucose-6,6-d2 as an internal standard. Repeated measurements and a recovery experiment on pooled, onion-induced tears showed that the analysis of the glucose in tears was precise (4% relative standard deviation) and provided 100% recovery. We found the tear glucose concentration of one fasting nondiabetic subject to be 13 to 51 microM while the onion-induced tear glucose concentration of a different nondiabetic subject to be 211 to 256 microM. PMID:17084090

  7. Analysis of Tear Glucose Concentration with Electrospray Ionization Mass Spectrometry

    PubMed Central

    Taormina, Christopher R.; Baca, Justin T.; Finegold, David N.; Asher, Sanford A.; Grabowski, Joseph J.

    2007-01-01

    We have developed a mass spectrometry-based method which allows one to accurately determine the glucose concentration of tear fluid. We used a 1 μL micro-capillary to collect tear fluid from the tear meniscus with minimal irritation of the eye. We analyzed the 1 μL volume of collected tear fluid with liquid-chromatography electrospray ionization mass spectrometry with the use of D-glucose-6,6-d2 as an internal standard. Repeated measurements and a recovery experiment on pooled, onion-induced tears showed that the analysis of the glucose in tears was precise (4% relative standard deviation) and provided 100% recovery. We found the tear glucose concentration of one fasting non-diabetic subject to be 13 to 51 μM while the onion-induced tear glucose concentration of a different non-diabetic subject to be 211 to 256 μM. PMID:17084090

  8. 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.

  9. 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.

  10. Effect of Mobile Phase on Electrospray Ionization Efficiency

    NASA Astrophysics Data System (ADS)

    Liigand, Jaanus; Kruve, Anneli; Leito, Ivo; Girod, Marion; Antoine, Rodolphe

    2014-08-01

    Electrospray (ESI) ionization efficiencies (IE) of a set of 10 compounds differing by chemical nature, extent of ionization in solution (basicity), and by hydrophobicity (tetrapropylammonium and tetraethylammonium ion, triethylamine, 1-naphthylamine, N,N-dimethylaniline, diphenylphthalate, dimethylphtahalate, piperidine, pyrrolidine, pyridine) have been measured in seven mobile phases (three acetonitrile percentages 20%, 50%, and 80%, and three different pH-adjusting additives, 0.1% formic acid, 1 mM ammonia, pH 5.0 buffer combination) using the relative measurement method. MS parameters were optimized separately for each ion. The resulting relative IE data were converted into comparable logIE values by anchoring them to the logIE of tetrapropylammonium ion taking into account the differences of ionization in different solvents and thereby making the logIE values of the compounds comparable across solvents. The following conclusions were made from analysis of the data. The compounds with pK a values in the range of the solution pH values displayed higher IE at lower pH. The sensitivity of IE towards pH depends on hydrophobicity being very strong with pyridine, weaker with N,N-dimethylaniline, and weakest with 1-naphthylamine. IEs of tetraalkylammonium ions and triethylamine were expectedly insensitive towards solution pH. Surprisingly high IEs of phthalate esters were observed. The differences in solutions with different acetonitrile content and similar pH were smaller compared with the pH effects. These results highlight the importance of hydrophobicity in electrospray and demonstrate that high hydrophobicity can sometimes successfully compensate for low basicity.

  11. Merits of online electrochemistry liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS).

    PubMed

    Looi, Wen Donq; Brown, Blake; Chamand, Laura; Brajter-Toth, Anna

    2016-03-01

    A new online electrochemistry/liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS) system with a simple electrochemical thin-layer flow-through cell was developed and tested using N,N-dimethyl-p-phenylenediamine (DMPA) as a model probe. Although oxidation of DMPA is observed as a result of ionization of LS in positive ion mode LS DESI, application of voltage to the online electrochemical (EC) cell in EC/LS DESI MS increases yields of oxidation products. An advantage of LS DESI MS is its sensitivity in aqueous electrolyte solutions, which improves efficiency of electrochemical reactions in EC/LS DESI MS. In highly conductive low pH aqueous buffer solutions, oxidation efficiency is close to 100%. EC/ESI MS typically requires mixed aqueous/organic solvents and low electrolyte concentrations for efficient ionization in MS, limiting efficiency of electrochemistry online with MS. Independently, the results verify higher electrochemical oxidation efficiency during positive mode ESI than during LS DESI.

  12. Study on ion formation in electrospray droplet impact secondary ion mass spectrometry.

    PubMed

    Asakawa, Daiki; Fujimaki, Susumu; Hashimoto, Yutaka; Mori, Kunihiko; Hiraoka, Kenzo

    2007-01-01

    A new type of cluster secondary ion mass spectrometry (SIMS), named electrospray droplet impact (EDI), has been developed in our laboratory. In general, rather strong negative ions as well as positive ions can be generated by EDI compared with conventional SIMS. In this work, various aspects of ion formation in EDI are investigated. The Brønsted bases (proton acceptor) and acids (proton donor) mixed in the analyte samples enhanced the signal intensities of deprotonated molecules (negative ions) and protonated molecules (positive ions), respectively, for analytes. This suggests the occurrence of heterogeneous proton transfer reactions (i.e. M + M' --> [M+H](+) + [M'-H](-)) in the shockwave-heated selvedge of the colliding interface between the water droplet and the solid sample deposited on the metal substrate. EDI-SIMS shows a remarkable tolerance to the large excess of salts present in samples. The mechanism for desorption/ionization in EDI is much simpler than those for MALDI and SIMS because only very thin sample layers take part in the shockwave-heated selvedge and complicated higher-order reactions are largely suppressed.

  13. An experimental and computational investigation on the fragmentation behavior of enaminones in electrospray ionization mass spectrometry.

    PubMed

    Guo, Cheng; Wan, Jieping; Hu, Nan; Jiang, Kezhi; Pan, Yuanjiang

    2010-11-01

    The dissociation pathways of protonated enaminones with different substituents were investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS) in positive ion mode. In mass spectrometry of the enaminones, ArCOCHCHN(CH(3) )(2) , the proton transfers from the thermodynamically favored site at the carbonyl oxygen to the dissociative protonation site at ipso-position of the phenyl ring or the double bond carbon atom adjacent to the carbonyl leading to the loss of a benzene or elimination of C(4) H(9) N, respectively. And the hydrogendeuterium (H/D) exchange between the added proton and the proton of the phenyl ring via a 1,4-H shift followed by hydrogen ring-walk was witnessed by the D-labeling experiments. The elemental compositions of all the ions were confirmed by ultrahigh resolution Fourier transform ion cyclotron resonance tandem mass spectrometry (FTICR-MS/MS). The enaminones studied here were para-monosubstituted on the phenyl ring and the electron-donating groups were in favor of losing the benzene, whereas the electron-attracting groups strongly favored the competing proton transfer reaction leading to the loss of C(4) H(9) N to form a benzoyl cation, Ar-CO(+) . The abundance ratios of the two competitive product ions were relatively well-correlated with the σ(p) (+) substituent constants. The mechanisms of these reactions were further investigated by density functional theory (DFT) calculations. PMID:20872893

  14. 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.

  15. Electrospray neutralization process and apparatus for generation of nano-aerosol and nano-structured materials

    DOEpatents

    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.

  16. Electrospray ionization-tandem mass spectrometry analysis of phospholipid molecular species from Antarctic and non-Antarctic yeasts.

    PubMed

    Bhuiyan, Mohammad; Tucker, David; Watson, Kenneth

    2014-10-01

    High performance liquid chromatography-electrospray ionization tandem mass spectrometry was applied to the comprehensive analysis of phospholipids from seven Antarctic and seven non-Antarctic yeasts. Identification of specific fatty acyl moieties to the sn-1 and sn-2 positions of phosphatidylethanolamine (PE), phosphatidylcholine (PC), phosphatidylserine (PS) and phosphatidylinositol (PI) were determined by relative abundance of fragment ions associated with formation of carboxylate anions and loss of fragment ions as free fatty carboxylic acid and ketene. Modulations with growth temperature in fatty acyl moieties in the sn-1 and sn-2 positions were characterized. Principal component analysis demonstrated that PE, PC and to a lesser extent PS, but not PI, were grouped into three distinct clusters consisting of seven Antarctic yeasts (Cryptococcus victoriae, Holtermanniella wattica, H. nyarrowii, Candida psychrophila, Leucosporidium fellii, Glaciozyma antarctica, Rhodotorula mucilaginosa), four non-Antarctic yeasts (C. albicans, Zygosaccharomyces rouxii, Cr. humicolus, R. mucilaginosa) and three strains of Saccharomyces cerevisiae.

  17. 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 compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

  18. Simultaneous quantification of 16 bioactive constituents in Common cnidium fruit by liquid chromatography-electrospray ionization-mass spectrometry.

    PubMed

    Song, Gengshen; Zhou, Li; Sheng, Ning; Zhang, Xiru; Xu, Yanmei; Zhang, Lantong; Li, Xiaoqian

    2015-03-25

    A novel quantitative method using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry was developed for simultaneous determination of the 16 important bioactive constituents including nine coumarins, and seven flavonoids in Common cnidium fruit samples from different regions. The separation was performed on a C18 column with linear gradient elution of acetonitrile and 0.1% acetic acid at a flow rate of 1.0 ml/min in 15 min. Quantification of the analytes was achieved by use of a hybrid quadrupole linear ion-trap mass spectrometer. Multiple-reaction monitoring scanning was employed with switching electrospray ion source polarity between positive and negative modes in a single run. The validation results of the method indicated that the method was simple, rapid, specific, and reliable. The results demonstrated that the quantitative difference in content of 16 bioactive constituents was useful not only for chemotaxonomy of many samples from different sources but also for the standardization and differentiation of many similar samples. Simultaneous quantification of bioactive components by high performance liquid chromatography-tandem mass spectrometric method would be a well acceptable strategy to comprehensively control the quality of C. cnidium fruit.

  19. Paired-ion electrospray ionization--triple quadrupole tandem mass spectrometry for quantification of anionic surfactants in waters.

    PubMed

    Santos, Inês C; Guo, Hongyue; Mesquita, Raquel B R; Rangel, António O S S; Armstrong, Daniel W; Schug, Kevin A

    2015-10-01

    A new paired ion electrospray ionization tandem mass spectrometry method for determination of anionic surfactants in water samples was developed. In this method, dicationic ion-pairing reagents were complexed with monoanionic analytes to facilitate analyte detection in positive mode electrospray ionization - mass spectrometry. Single ion monitoring and selected reaction monitoring on a triple quadrupole instrument were performed and compared. Four dicationic reagents were tested for the determination of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBS), and stearic acid (SA), among other common anions. The obtained limits of detection were compared with those from previous literature. Solid phase extraction using a C18 cartridge was performed in order to eliminate matrix interferences. A literature review was compiled for the methods published between 2010 and 2015 for determination of anionic surfactants. The optimized method was more sensitive than previously developed methods with LOD values of 2.35, 35.4, 37.0, 1.68, and 0.675 pg for SDS, SA, DBS, PFOS, and PFOA, respectively. The developed method was effectively applied for the determination of anionic surfactants in different water samples such as bottled drinking water, cooking water, tap water, and wastewater.

  20. Simultaneous sampling of volatile and non-volatile analytes in beer for fast fingerprinting by extractive electrospray ionization mass spectrometry.

    PubMed

    Zhu, Liang; Hu, Zhong; Gamez, Gerardo; Law, Wai Siang; Chen, HuanWen; Yang, ShuiPing; Chingin, Konstantin; Balabin, Roman M; Wang, Rui; Zhang, TingTing; Zenobi, Renato

    2010-09-01

    By gently bubbling nitrogen gas through beer, an effervescent beverage, both volatile and non-volatile compounds can be simultaneously sampled in the form of aerosol. This allows for fast (within seconds) fingerprinting by extractive electrospray ionization mass spectrometry (EESI-MS) in both negative and positive ion mode, without the need for any sample pre-treatment such as degassing and dilution. Trace analytes such as volatile esters (e.g., ethyl acetate and isoamyl acetate), free fatty acids (e.g., caproic acid, caprylic acid, and capric acid), semi/non-volatile organic/inorganic acids (e.g., lactic acid), and various amino acids, commonly present in beer at the low parts per million or at sub-ppm levels, were detected and identified based on tandem MS data. Furthermore, the appearance of solvent cluster ions in the mass spectra gives insight into the sampling and ionization mechanisms: aerosol droplets containing semi/non-volatile substances are thought to be generated via bubble bursting at the surface of the liquid; these neutral aerosol droplets then collide with the charged primary electrospray ionization droplets, followed by analyte extraction, desolvation, ionization, and MS detection. With principal component analysis, several beer samples were successfully differentiated. Therefore, the present study successfully extends the applicability of EESI-MS to the direct analysis of complex liquid samples with high gas content.

  1. Detection of the improvised explosives ammonium nitrate (AN) and urea nitrate (UN) using non-aqueous solvents with electrospray ionization and MS/MS detection.

    PubMed

    Corbin, Inge; McCord, Bruce

    2013-10-15

    In this study methods for the detection of trace levels of the improvised explosives urea nitrate and ammonium nitrate were developed using electrospray ionization with infusion. By using a non-aqueous solvent mixture containing 95% acetone with 5% 2-methoxyethanol we were able to preserve the urea and ammonium nitrate ion pairs and discriminate between these and other similar salts. Negative ion electrospray ionization was used for urea nitrate detection and positive ion electrospray ionization was used for ammonium nitrate. Two specific adduct ions were detected for each explosive with ammonium nitrate producing m/z 178 [2AN+NH4](+) and m/z 258 ions [3AN+NH4](+) while urea nitrate produced m/z 185 [UN+NO3](-) and m/z 248 [UN+HNO3+NO3](-) The specificity of the analysis was examined by mixing the different explosives with various salts and interferents. Adduct ions formed in the gas phase were found to be useful in distinguishing between ion pairs and mixed salts. Overall the method demonstrates the sensitive detection of both explosives, and more specifically the potential to determine intact urea nitrate.

  2. DEVELOPMENT OF AN ELECTROSPRAY MASS SPECTROMETRIC METHOD FOR DETERMINING PERCHLORATE IN FERTILIZERS

    EPA Science Inventory

    An electrospray mass spectrometric method has been developed for application to agricultural and horticultural fertilizers to determine perchlorate. After fertilizers are leached or dissolved in water, the method relies on the formation of stable ion pair complex of the perchlor...

  3. Poly(amidoamine)-Cholesterol Conjugate Nanoparticles Obtained by Electrospraying as Novel Tamoxifen Delivery System.

    PubMed

    Cavalli, R; Bisazza, A; Bussano, R; Trotta, M; Civra, A; Lembo, D; Ranucci, E; Ferruti, P

    2011-01-01

    A new poly(amidoamine)-cholesterol (PAA-cholesterol) conjugate was synthesized, characterized and used to produce nanoparticles by the electrospraying technique. The electrospraying is a method of liquid atomization that consists in the dispersion of a solution into small charged droplets by an electric field. Tuning the electrospraying process parameters spherical PAA-chol nanoparticles formed. The PAA-cholesterol nanoparticles showed sizes lower than 500 nm and spherical shape. The drug incorporation capacity was investigated using tamoxifen, a lipophilic anticancer drug, as model drug. The incorporation of the tamoxifen did not affect the shape and sizes of nanoparticles showing a drug loading of 40%. Tamoxifen-loaded nanoparticles exhibited a higher dose-dependent cytotoxicity than free tamoxifen, while blank nanoparticles did not show any cytotoxic effect at the same concentrations. The electrospray technique might be proposed to produce tamoxifen-loaded PAA-chol nanoparticle in powder form without any excipient in a single step. PMID:21785731

  4. The updated bottom up solution applied to atmospheric pressure photoionization and electrospray ionization mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Updated Bottom Up Solution (UBUS) was recently applied to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) of triacylglycerols (TAGs). This report demonstrates that the UBUS applies equally well to atmospheric pressure photoionization (APPI) MS and to electrospray ionizatio...

  5. Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

    NASA Astrophysics Data System (ADS)

    Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

    2016-09-01

    The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

  6. Controlled release behaviour of protein-loaded microparticles prepared via coaxial or emulsion electrospray

    PubMed Central

    Wang, Ying; Yang, Xiaoping; Liu, Wentao; Zhang, Feng; Cai, Qing; Deng, Xuliang

    2013-01-01

    Biodegradable poly (lactic-co-glycolic acid) (PLGA) microparticles are an effective way to achieve sustained drug release. In this study, we investigated a sustained release model of PLGA microparticles with incorporated protein via either emulsion or coaxial electrospray techniques. PLGA (75:25) was used as the carrier, and bovine serum albumin as a model protein. Coaxial electrospray resulted in a type of core–shell structure with mean diameters of 2.41 ± 0.60 µm and a centralised protein distribution within the core. Emulsion electrospray formed bigger microparticles with mean diameters of 22.75 ± 8.05 µm and a heterogeneous protein distribution throughout the microparticles. The coaxial electrospray microparticles presented a much slighter burst release than the emulsion electrospray microparticles. Loading efficiency was significantly higher (p < 0.05) in the coaxial group than emulsion group. This indicated that both emulsion and coaxial electrospray could produce protein-loaded microparticles with sustained release behaviour, but the former revealed a superior approach for drug delivery. PMID:23346923

  7. NOVEL COMPUTATIONAL SIMULATION OF REDOX REACTIONS WITHIN A METAL ELECTROSPRAY EMITTER

    SciTech Connect

    BULLOCK, J.S.IV; GILES, G.E.; GRAY, L.J.; VAN BERKEL, G.J.

    1999-01-13

    To further both our fundamental understanding implications of the electrolytic nature of the electrospray and our understanding of the analytical ion source, in the context of electrospray mass spectrometry (ES-MS), a computational simulation of the oxidation of chemical species inside a metal emitter has been developed. The analysis code employs a boundary integral method for the solution of the Laplace equation for the electric potential and current, and incorporates standard activation and concentration polarization functions for the redox active species in the system to define the boundary conditions. The specific system modeled consisted of a 100 {mu}m i .d., inert metal capillary CHICN/H2O (90/10 V/V). ES emitter and a spray solution comprised of an analyte dissolved in Variable parameters included the concentration (i.e., 5, 10, 20, and 50 ~M) of the easily oxidized analyte ferrocene (Fe, dicyclopentadienyl iron) in the solution, and solution conductivities of 1.9, 3.8, and 7.6 x 107 Mho/cm. ES currents were on the order of 0.05 {mu}A and the flow rate was 5 @A_nin. Under these defined conditions, the two most prominent reactions at the emitter metakolution interface were assumed to be H20 oxidation (2H20 = 02 + 4H+ + 4e") and Fe oxidation (Fe = Fe' +e-). Using this model it was possible to predict the inter-facial potentials, as well as the current density for each of the reactions, as a function of axial position from the emitter spray tip back upstream, under the various operational conditions. Computational fluid dynamics (CFD) calculations showed that the imposed flow rate through the emitter was adequate to prevent significant back-diffusion of Fe+ into the emitter against the flow direction. The computational simulations predict the same behavior for the ES ion source as has been observed experimentally and is consistent with the controlled-current electrolytic cell analogy of Van Berkel and Zhou (Anal. Chem. 1995, 67,.2916-2923). Furthermore, the

  8. Using the Electrochemistry of the Electrospray Ion Source

    SciTech Connect

    Van Berkel, Gary J; Kertesz, Vilmos

    2007-01-01

    Electrospray mass spectrometry (ES-MS) is one of the more widely used analysis methods in science today, impacting fields as diverse as conventional chemistry to biotechnology and materials science. , Even 20 years after bursting onto the mass spectrometry scene, the underlying processes in ES ionization continue to be better understood exposing new opportunities for the technique. , , , , Such is the case for the improved understanding related to the electrochemical processes inherent to the operation of this ion source, , , which is the topic of this report. Electrospray ionization involves three main steps prior to mass analysis: the generation and charging of the ES droplets; droplet evaporation and the production of gas-phase ions; and secondary processes that modify the gas-phase ions in the atmosphere and the sub-atmospheric pressure sampling regions of the mass spectrometer. Integral to the generation and charging of the ES droplets are electrochemical reactions that occur at the conductive contact/solution interface within or near the ES emitter to maintain the quasi-continuous production of charged droplets and ultimately gas-phase ions. The basic electrochemical phenomena concerning the ES ion source were first brought to wide attention in the mass spectrometry community by Kebarle and co-workers in the early 1990's,8 but the electrochemistry of electrostatic spray devices and possible analytical consequences resulting from this phenomenon were realized and discussed in the literature at least as far back as the mid-1970's. When asked to intercede in a debate on the significance of electrochemistry in the ES ionization (ESI) process, 2002 Nobel Laureate in Chemistry John Fenn noted that to him " the idea that electrochemical reactions might be taking place in an ES ion source was too obvious to mention. That products of such reactions are of vital significance in the overall ESI process was much less obvious. Indeed, it seems fair to say that with few

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

    PubMed

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

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. PMID:27471991

  10. Development of Non-proximate Probe Electrospray Ionization for Real-Time Analysis of Living Animal

    PubMed Central

    Yoshimura, Kentaro; Chen, Lee Chuin; Johno, Hisashi; Nakajima, Mayutaka; Hiraoka, Kenzo; Takeda, Sen

    2014-01-01

    Ambient ionization mass spectrometry is one of the most challenging analytical tools in the field of biomedical research. We previously demonstrated that probe electrospray ionization mass spectrometry (PESI-MS) could potentially be used in the rapid diagnosis of cancer. Although this technique does not require a tedious sample pretreatment process, it was not possible for our previously reported setup to be applied to cases involving the direct sampling of tissues from living animal and large animal subjects, because there would not be enough room to accommodate the larger bodies juxtaposed to the ion inlet. To make PESI-MS more applicable for the real-time analysis of living animals, a long auxiliary ion sampling tube has been connected to the ion inlet of the mass spectrometer to allow for the collection of ions and charged droplets from the PESI source (hereafter, referred to as non-proximate PESI). Furthermore, an additional ion sampling tube was connected to a small diaphragm pump to increase the uptake rate of air carrying the ions and charged droplets to the ion inlet. This modification allows for the extended ion sampling orifice to be positioned closer to the specimens, even when they are too large to be placed inside the ionization chamber. In this study, we have demonstrated the use of non-proximate PESI-MS for the real-time analysis for biological molecules and pharmacokinetic parameters from living animals. PMID:26819892

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

    PubMed

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

    2016-09-01

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

  12. Residual Agar Determination in Bacterial Spores by Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Wahl, Karen L.; Colburn, Heather A.; Wunschel, David S.; Petersen, Catherine E.; Jarman, Kristin H.; Valentine, Nancy B.

    2010-02-15

    Presented here is an analytical method to detect residual agar from a bacterial spore sample as an indication of culturing on an agar plate. This method is based on the resolubilization of agar polysaccharide from a bacterial spore sample, enzymatic digestion, followed by electrospray ionization tandem mass spectrometry (ESI-MSn) analysis for detection of a specific agar fragment ion. A range of Bacillus species and strains were selected to demonstrate the effectiveness of this approach. The characteristic agar fragment ion was detected in the spores grown on agar that were washed from 1 to 5 times, irradiated or non-irradiated and not in the spores grown in broth. A sample containing approximately 108 spores is currently needed for confident detection of residual agar from culture on agar plates in the presence of bacterial spores with a limit of detection of approximately 1 ppm agar spiked into a broth-grown spore sample. The results of a proficiency test with 42 blinded samples are presented demonstrating the utility of this method with no false positives and only 3 false negatives for samples that were below the detection level of the method as documented.

  13. Desorption Electrospray Ionization Mass Spectrometry Reveals Lipid Metabolism of Individual Oocytes and Embryos

    PubMed Central

    González-Serrano, Andrés Felipe; Pirro, Valentina; Ferreira, Christina R.; Oliveri, Paolo; Eberlin, Livia S.; Heinzmann, Julia; Lucas-Hahn, Andrea; Niemann, Heiner; Cooks, Robert Graham

    2013-01-01

    Alteration of maternal lipid metabolism early in development has been shown to trigger obesity, insulin resistance, type 2 diabetes and cardiovascular diseases later in life in humans and animal models. Here, we set out to determine (i) lipid composition dynamics in single oocytes and preimplantation embryos by high mass resolution desorption electrospray ionization mass spectrometry (DESI-MS), using the bovine species as biological model, (ii) the metabolically most relevant lipid compounds by multivariate data analysis and (iii) lipid upstream metabolism by quantitative real-time PCR (qRT-PCR) analysis of several target genes (ACAT1, CPT 1b, FASN, SREBP1 and SCAP). Bovine oocytes and blastocysts were individually analyzed by DESI-MS in both positive and negative ion modes, without lipid extraction and under ambient conditions, and were profiled for free fatty acids (FFA), phospholipids (PL), cholesterol-related molecules, and triacylglycerols (TAG). Principal component analysis (PCA) and linear discriminant analysis (LDA), performed for the first time on DESI-MS fused data, allowed unequivocal discrimination between oocytes and blastocysts based on specific lipid profiles. This analytical approach resulted in broad and detailed lipid annotation of single oocytes and blastocysts. Results of DESI-MS and transcript regulation analysis demonstrate that blastocysts produced in vitro and their in vivo counterparts differed significantly in the homeostasis of cholesterol and FFA metabolism. These results should assist in the production of viable and healthy embryos by elucidating in vivo embryonic lipid metabolism. PMID:24073231

  14. Design and Performance of a High-Flux Electrospray Ionization Source for Ion Soft-Landing

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Prabhakaran, Venkateshkumar; Ibrahim, Yehia M.; Norheim, Randolph V.; Johnson, Grant E.; Laskin, Julia

    2015-01-01

    We report the design and evaluation of a new high-intensity electrospray ionization source for ion soft-landing experiments. The source incorporates a dual ion funnel, which enables operation with a higher gas load through an expanded heated inlet into the additional first region of differential pumping. This capability allowed us to examine the effect of the inner diameter (ID) of the heated stainless steel inlet on the total ion current transmitted through the dual funnel interface and, more importantly, the mass-selected ion current delivered to the deposition target. The ion transmission of the dual funnel is similar to the transmission of the single funnel used in our previous soft landing studies. However, substantially higher ion currents were obtained using larger ID heated inlets and an orthogonal inlet geometry, in which the heated inlet is positioned perpendicular to the direction of ion propagation through the instrument. The highest ion currents were obtained using the orthogonal geometry and a 1.4 mm ID heated inlet. The corresponding stable deposition rate of ~1 μg of mass-selected ions per day will facilitate future studies focused on the controlled deposition of biological molecules on substrates and preparation of materials for studies in catalysis, energy storage, and self-assembly

  15. Electrospray ionization and collision induced dissociation mass spectrometry of primary fatty acid amides.

    PubMed

    Divito, Erin B; Davic, Andrew P; Johnson, Mitchell E; Cascio, Michael

    2012-03-01

    Primary fatty acid amides are a group of bioactive lipids that have been linked with a variety of biological processes such as sleep regulation and modulation of monoaminergic systems. As novel forms of these molecules continue to be discovered, more emphasis will be placed on selective, trace detection. Currently, there is no published experimental determination of collision induced dissociation of PFAMs. A select group of PFAM standards, 12 to 22 length carbon chains, were directly infused into an electrospray ionization source Quadrupole Time of Flight Mass Spectrometer. All standards were monitored in positive mode using the [M + H](+) peak. Mass Hunter Qualitative Analysis software was used to calculate empirical formulas of the product ions. All PFAMs showed losses of 14 m/z indicative of an acyl chain, while the monounsaturated group displayed neutral losses corresponding to H(2)O and NH(3). The resulting spectra were used to propose fragmentation mechanisms. Isotopically labeled PFAMs were used to validate the proposed mechanisms. Patterns of saturated versus unsaturated standards were distinctive, allowing for simple differentiation. This determination will allow for fast, qualitative identification of PFAMs. Additionally, it will provide a method development tool for selection of unique product ions when analyzed in multiple reaction monitoring mode.

  16. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment.

    PubMed

    Canuto, Marcus H; Rosa, Carlos A; de Moura, Fabiana; Augusti, Rodinei; Siebald, Helmuth G L

    2012-07-01

    Direct infusion electrospray ionization mass spectrometry in the negative ion mode (ESI(-)-MS) was employed to discriminate among fractions arising from the distillation of fermented sugarcane juice during the production of cachaça, a typical Brazilian alcoholic beverage. Aliquots were collected in the course of distillation and their ESI(-)-MS shown to be almost indistinguishable by a simple visual inspection. However, when the ESI(-)-MS data were treated by the principal component analysis (PCA) and hierarchical clustering analysis (HCA) statistical methods, four major groups were clearly determined, the so-called head (two distinct clusters), heart and tail fractions. Furthermore, the recognition of diagnostic ions (and their respective intensities) enabled a more confident establishment of the cutoff position (i.e. the initial and final points of each fraction). In conclusion, ESI-MS, in conjunction with PCA or HCA approaches, proved to be a quite efficient method that allowed for a prompt characterization of each fraction derived from the distillation of brewed sugarcane. The results described herein can, therefore, be useful not only to optimize the production of cachaça but also to improve the quality of the final product.

  17. Simultaneous determination of 15 nitroimidazoles in cosmetics by HPLC coupled with electrospray ionization- tandem mass spectrometry.

    PubMed

    Meng, Xian-Shuang; Bai, Hua; Zhang, Qing; Lv, Qing; Chen, Yun-Xia; Ma, Hui-Juan; Li, Jing-Rui; Ma, Qiang

    2014-01-01

    A sensitive and reliable analytical method based on HPLC/MSIMS has been developed for the simultaneous determination of 15 nitroimidazoles in cosmetics. A diversity of cosmetic samples, including powder, lotion, shampoo, and cream were collected. The samples were ultrasonically extracted with aqueous methanol, and the extracts were then subjected to cleanup bySPE using an Oasis HLB cartridge followed by filtration with a 0.20 pm membrane filter. Afterwards, chromatographic separation was performed on an XSelect CSH C18 column (2.1 x 150 mm, 3.5 pm) maintained at 30°C within 15 min by a gradient of acetonitrile-0.1% aqueous formic acid solution at a flow rate of 0.25 mL/min. The mass spectrometric detection was carried, out using electrospray positive ionization under the multiple reaction monitoring mode. A good linearity was observed over the concentration range from 0.5 to 500 ng/mL. The intraday and interday precisions, which were investigated by determining all target compounds in cosmetics seven times/day and on 7 consecutive days, were below 5.00%. The mean recoveries at three spiked levels ranged from 80.42 to 100.83% with the RSDs from 0.45 to 9.02%. The LOQs were determined to be between 0.01 and 0.1 mg/kg. The method was sufficiently rapid, reliable, and sensitive for the determination of 15 nitroimidazoles in cosmetics. PMID:25632431

  18. Chemical Analysis of Organic Aerosols Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2013-12-01

    Nanospray Desorption Electrospray Ionization (nano-DESI) technique integrated with high resolution mass spectrometry (HR-MS) enables molecular level analysis of organic aerosol (OA) samples. In nano-DESI, analyte is desorbed into a small volume solvent bridge formed between two capillaries positioned in contact with analyte and enables fast and efficient characterization of OA collected on substrates without sample preparation. We report applications of the nano-DESI/HR-MS approach in a number of our recent studies focused on molecular identification of organic compounds in laboratory and in field collected OA samples. Reactive nano-DESI approach where selected reagent is added to the solvent is used for examining the presence of individual species containing specific functional groups and for their quantification within complex mixtures of OA. Specifically, we use the Girard's reagent T (GT) to probe and quantify carbonyl compounds in the SOA mixtures. We estimate for the first time the amounts of dimers and trimers in the SOA mixtures. We found that the most abundant dimer in limonene/O3 SOA was detected at the ˜0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ˜11 pg. Understanding of the OA composition at the molecular level allowed us to identify key aging reactions, including the transformation of carbonyls to imines and carbonyl-imine oligomerization, that may contribute to the formation of brown carbon in the atmosphere.

  19. Simultaneous determination of 15 nitroimidazoles in cosmetics by HPLC coupled with electrospray ionization- tandem mass spectrometry.

    PubMed

    Meng, Xian-Shuang; Bai, Hua; Zhang, Qing; Lv, Qing; Chen, Yun-Xia; Ma, Hui-Juan; Li, Jing-Rui; Ma, Qiang

    2014-01-01

    A sensitive and reliable analytical method based on HPLC/MSIMS has been developed for the simultaneous determination of 15 nitroimidazoles in cosmetics. A diversity of cosmetic samples, including powder, lotion, shampoo, and cream were collected. The samples were ultrasonically extracted with aqueous methanol, and the extracts were then subjected to cleanup bySPE using an Oasis HLB cartridge followed by filtration with a 0.20 pm membrane filter. Afterwards, chromatographic separation was performed on an XSelect CSH C18 column (2.1 x 150 mm, 3.5 pm) maintained at 30°C within 15 min by a gradient of acetonitrile-0.1% aqueous formic acid solution at a flow rate of 0.25 mL/min. The mass spectrometric detection was carried, out using electrospray positive ionization under the multiple reaction monitoring mode. A good linearity was observed over the concentration range from 0.5 to 500 ng/mL. The intraday and interday precisions, which were investigated by determining all target compounds in cosmetics seven times/day and on 7 consecutive days, were below 5.00%. The mean recoveries at three spiked levels ranged from 80.42 to 100.83% with the RSDs from 0.45 to 9.02%. The LOQs were determined to be between 0.01 and 0.1 mg/kg. The method was sufficiently rapid, reliable, and sensitive for the determination of 15 nitroimidazoles in cosmetics.

  20. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment.

    PubMed

    Canuto, Marcus H; Rosa, Carlos A; de Moura, Fabiana; Augusti, Rodinei; Siebald, Helmuth G L

    2012-07-01

    Direct infusion electrospray ionization mass spectrometry in the negative ion mode (ESI(-)-MS) was employed to discriminate among fractions arising from the distillation of fermented sugarcane juice during the production of cachaça, a typical Brazilian alcoholic beverage. Aliquots were collected in the course of distillation and their ESI(-)-MS shown to be almost indistinguishable by a simple visual inspection. However, when the ESI(-)-MS data were treated by the principal component analysis (PCA) and hierarchical clustering analysis (HCA) statistical methods, four major groups were clearly determined, the so-called head (two distinct clusters), heart and tail fractions. Furthermore, the recognition of diagnostic ions (and their respective intensities) enabled a more confident establishment of the cutoff position (i.e. the initial and final points of each fraction). In conclusion, ESI-MS, in conjunction with PCA or HCA approaches, proved to be a quite efficient method that allowed for a prompt characterization of each fraction derived from the distillation of brewed sugarcane. The results described herein can, therefore, be useful not only to optimize the production of cachaça but also to improve the quality of the final product. PMID:22791258

  1. Design and performance of a high-flux electrospray ionization source for ion soft landing.

    PubMed

    Gunaratne, K Don D; Prabhakaran, Venkateshkumar; Ibrahim, Yehia M; Norheim, Randolph V; Johnson, Grant E; Laskin, Julia

    2015-05-01

    We report the design and evaluation of a new high-intensity electrospray ionization source for ion soft-landing experiments. The source incorporates a dual ion funnel, which enables operation with a higher gas load through an expanded diameter heated inlet into the additional first region of differential pumping. This capability allowed us to examine the effect of the inner diameter (ID) of the heated stainless steel inlet on the total ion current transmitted through the dual funnel interface and, more importantly, the mass-selected ion current delivered to the deposition target. The ion transmission of the dual funnel is similar to the transmission of the single funnel used in our previous soft landing studies. However, substantially higher ion currents were obtained using larger ID heated inlets and an orthogonal inlet geometry, in which the heated inlet was positioned perpendicular to the direction of ion propagation through the instrument. The highest ion currents were obtained using the orthogonal geometry and a 1.4 mm ID heated inlet. The corresponding stable deposition rate of ∼1 μg of mass-selected ions per day will facilitate future studies focused on the controlled deposition of complex molecules on substrates for studies in catalysis, energy storage, and self-assembly.

  2. Stretchability of Silver Films on Thin Acid-Etched Rough Polydimethylsiloxane Substrates Fabricated by Electrospray Deposition

    NASA Astrophysics Data System (ADS)

    Mehdi, S. M.; Cho, K. H.; Kang, C. N.; Choi, K. H.

    2015-07-01

    This paper investigates the fabrication of Ag films through the electrospray deposition (ESD) technique on sub-millimeter-thick acid-etched rough polydimethylsiloxane (PDMS) substrates having both low and high modulus of elasticity. The main focus of the study is on the stretchable behavior of ESD-deposited Ag nanoparticles-based thin films on these substrates when subjected to axial strains. Experimental results suggest that the as-fabricated films on thin acid-etched rough low modulus PDMS has an average stretchability of 5.6% with an average increase in the resistance that is 23 times that of the initial resistance at electrical failure (complete rupture of the films). Comparatively, the stretchability of Ag films on the high modulus PDMS was found to be 3 times higher with 4.65 times increase in the resistance at electrical failure. Also, a high positive value of the piezoresistive coefficient for these films suggests that the resistivity changes during stretching, and thus deviation from the simplified models is inevitable. Based on these results, new models are presented that quantify the changes in resistance with strain.

  3. Minimizing analyte electrolysis in electrospray ionization mass spectrometry using a redox buffer coated emitter electrode

    SciTech Connect

    Peintler-Krivan, Emese; Van Berkel, Gary J; Kertesz, Vilmos

    2010-01-01

    An emitter electrode with an electroactive poly(pyrrole) (PPy) polymer film coating was constructed for use in electrospray ionization mass spectrometry (ESI-MS). The PPy film acted as a surface-attached redox buffer limiting the interfacial potential of the emitter electrode. While extensive oxidation of selected analytes (reserpine and amodiaquine) was observed in positive ion mode ESI using a bare metal (gold) emitter electrode, the oxidation was suppressed for these same analytes when using the PPy-coated electrode. A semi-quantitative relationship between the rate of oxidation observed and the interfacial potential of the emitter electrode was shown. The redox buffer capacity, and therefore the lifetime of the redox buffering effect, correlated with the oxidation potential of the analyte and with the magnitude of the film charge capacity. Online reduction of the PPy polymer layer using negative ion mode ESI between analyte injections was shown to successfully restore the redox buffering capacity of the polymer film to its initial state.

  4. Control of Analyte Electrolysis in Electrospray Ionization Mass Spectrometry Using Repetitively Pulsed High Voltage

    SciTech Connect

    Kertesz, Vilmos; Van Berkel, Gary J

    2011-01-01

    Analyte electrolysis using a repetitively pulsed high voltage ion source was investigated and compared to that using a regular, continuously operating direct current high voltage ion source in electrospray ionization mass spectrometry. The extent of analyte electrolysis was explored as a function of the length and frequency of the high voltage pulse using the model compound reserpine in positive ion mode. Using +5 kV as the maximum high voltage amplitude, reserpine was oxidized to its 2, 4, 6 and 8-electron oxidation products when direct current high voltage was employed. In contrast, when using a pulsed high voltage, oxidation of reserpine was eliminated by employing the appropriate high voltage pulse length and frequency. This effect was caused by inefficient mass transport of the analyte to the electrode surface during the duration of the high voltage pulse and the subsequent relaxation of the emitter electrode/ electrolyte interface during the time period when the high voltage was turned off. This mode of ESI source operation allows for analyte electrolysis to be quickly and simply switched on or off electronically via a change in voltage pulse variables.

  5. Development of Non-proximate Probe Electrospray Ionization for Real-Time Analysis of Living Animal.

    PubMed

    Yoshimura, Kentaro; Chen, Lee Chuin; Johno, Hisashi; Nakajima, Mayutaka; Hiraoka, Kenzo; Takeda, Sen

    2014-01-01

    Ambient ionization mass spectrometry is one of the most challenging analytical tools in the field of biomedical research. We previously demonstrated that probe electrospray ionization mass spectrometry (PESI-MS) could potentially be used in the rapid diagnosis of cancer. Although this technique does not require a tedious sample pretreatment process, it was not possible for our previously reported setup to be applied to cases involving the direct sampling of tissues from living animal and large animal subjects, because there would not be enough room to accommodate the larger bodies juxtaposed to the ion inlet. To make PESI-MS more applicable for the real-time analysis of living animals, a long auxiliary ion sampling tube has been connected to the ion inlet of the mass spectrometer to allow for the collection of ions and charged droplets from the PESI source (hereafter, referred to as non-proximate PESI). Furthermore, an additional ion sampling tube was connected to a small diaphragm pump to increase the uptake rate of air carrying the ions and charged droplets to the ion inlet. This modification allows for the extended ion sampling orifice to be positioned closer to the specimens, even when they are too large to be placed inside the ionization chamber. In this study, we have demonstrated the use of non-proximate PESI-MS for the real-time analysis for biological molecules and pharmacokinetic parameters from living animals.

  6. [A plain method of prediction of visibility of peptides in mass spectrometry with electrospray ionization].

    PubMed

    Rybina, A V; Skvortsov, V S; Kopylov, A T; Zgoda, V G

    2014-01-01

    A new method for screening of essential peptides for protein detection and quantification analysis in the direct positive electrospray mass spectrometry has been proposed. Our method is based on the prediction of the normalized abundance of the mass spectrometric peaks using a linear regression model. This method has the following limitations: (i) selected peptides should be taken so that at pH 2.5 the tested peptides must be presented mainly as the 2+ and 3+ ions; (ii) only peptides having C-terminal lysine or arginine residues are considered. The amino acid composition of the peptide, the peptide concentration, the ratio of the polar surface of peptide to common surface and ratio of the polar volume to common volume are used as independent variables in equation. Several combinations of variables were considered and the best linear regression model had a determination coefficient in leave-one-out validation procedure equal 0.54. This model confidently discriminates peptides with high response ability and peptides with low response ability, and therefore it allows to select only the most promising peptides. This screening method, a plain and fast, can be successfully applied to reduce the list of observed peptides.

  7. Tandem Mass Spectrometry of Bilin Tetrapyrroles by Electrospray Ionization and Collision Induced Dissociation

    PubMed Central

    Quinn, Kevin D.; Nguyen, Nhu Q. T.; Wach, Michael M.; Wood, Troy D.

    2012-01-01

    Rationale Bilins are metabolic products of hosts and bacteria on porphyrins, and are markers of health state and human waste contamination. Although bilin tandem mass spectrometry reports exist, their fragmentation behavior as a function of structure has not been compared, nor has fragmentation been examined as a function of collision energy. Methods: The fragmentation of bilins generated by positive ion mode electrospray ionization is examined by collision induced dissociation (CID). CID on a quadrupole ion trap and on a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer as a function of collision energy is compared. Methyl esterification was used to deduce which product ions contain the inner pyrrole rings. FT-ICR high mass accuracy measurements were used to determine the formulas of the resultant product ions. Results The central carbon’s bonding to the inner pyrrole rings influences fragmentation. Bilirubin is unique because fragmentation adjacent to the central methylene group between innermost rings predominates, and loss of a terminal pyrrole is observed only with helium collision gas. The other bilins lose the terminal pyrroles first; as CID energy is increased, additional fragmentation due to neutral losses of small molecules such as H2O, CO, CO2, and methanol occurs. Conclusions Based on these observations, fragmentation schemes for the bilins are proposed that are strongly dependent on the molecular structure and collision energy; only bilirubin fragmentation is influenced significantly by the collision gas used. This report should have value in identification of this class of molecules for biomarker detection. PMID:22777778

  8. Electrospray ionization mass spectrometry fingerprinting of whisky: immediate proof of origin and authenticity.

    PubMed

    Møller, Jens K S; Catharino, Rodrigo R; Eberlin, Marcos N

    2005-06-01

    Authentic samples of whisky produced in Scotland and USA and counterfeit whisky samples commercialized in Brazil have been directly submitted to electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes to assess the potential of this technique for simple and rapid quality control and proof of authenticity of whisky samples. ESI in the negative ion mode yields the most characteristic whisky fingerprinting mass spectra in just a few seconds by direct infusion of the samples, detecting the most polar or acidic components of each sample in their deprotonated anionic forms. No pre-treatment of the sample, such as extraction or derivatization or even dilution, is required. The analysis of the ESI(-)-MS data both by simple visual inspection but more particularly by chemometric data treatment enables separation of the whisky samples into three unequivocally distinct groups: Scotch, American and counterfeit whisky, whereas single malt and blended Scotch whiskies are also distinguished to some extent. As indicated by ESI-MS/MS analysis, the diagnostic anions are simple sugars, disaccharides and phenolic compounds. Direct infusion ESI-MS therefore provides immediate chemical fingerprinting of whisky samples for type, origin and quality control, as demonstrated herein for American, Scottish and counterfeit samples, whereas ESI-MS/MS analysis of diagnostic ions adds a second dimension of fingerprinting characterization when improved selectivity is desired.

  9. Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species.

    PubMed

    Vessecchi, Ricardo; Emery, Flavio S; Galembeck, Sérgio E; Lopes, Norberto P

    2010-07-30

    Electrospray ionization mass spectrometric analysis of lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone) was accomplished in order to elucidate the gas-phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision-induced dissociation (CID) experiments. For the protonated molecule, the H(2)O and C(4)H(8) losses occur by two competitive channels. For the deprotonated molecule, the even-electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas-phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6-31+G(d,p) model. PMID:20552691

  10. Analysis of alkylphenol ethoxylate metabolites in the aquatic environment using liquid chromatography-electrospray mass spectrometry.

    PubMed

    Ferguson, P L; Iden, C R; Brownawell, B J

    2000-09-15

    A quantitative method is described for the analysis of the metabolites of alkylphenol ethoxylate (APEO) surfactants in estuarine water and sediment samples using reversed-phase high-performance liquid chromatography with electrospray mass spectrometry detection. Nonyl- and octylphenols, nonyl- and octylphenol mono-, di-, and triethoxylates, halogenated nonylphenols, and nonylphenol ethoxycarboxylates were concentrated from water samples using a C18 solid-phase extraction procedure. A novel, continuous-flow, high-temperature, sonicated extraction system was developed to isolate APEO metabolites from sediment samples. Quantitative LC-MS was performed in the negative ion mode for nonylphenols, octylphenols, and halogenated nonylphenols and in the positive ion mode for nonyl- and octylphenol ethoxylates using selected ion monitoring with isotopically labeled surrogate standards. Recoveries for sediment and water analyses ranged between 78 and 94%, and detection limits for APEO metabolites were between 1 and 20 pg injected on column. This is a significant improvement over previously reported methods. Suppression of analyte response was encountered in the presence of matrix components in sediment samples, but this effect was eliminated by careful selection of surrogate and internal standards. Individual APEO metabolite concentrations of 1-320 ng/L and 5-2000 ng/g are reported for water and sediment samples, respectively, from Jamaica Bay, NY. PMID:11008767

  11. Electrospray Charging of Minerals: Surface Chemistry and Applications to High-Velocity Microparticle Impacts

    NASA Astrophysics Data System (ADS)

    Daly, T.; Call, S.; Austin, D. E.

    2010-12-01

    Electrospray is a soft ionization technique commonly used to charge large biomolecules; it has, however, also been applied to inorganic compounds. We are extending this technique to mineral microparticles. Electrospray-charged mineral microparticles are interesting in the context of surface science because surface chemistry dictates where and how charge carriers can bond to mineral surfaces. In addition, using electrospray to charge mineral particles allows these particles to be electrostatically accelerated as projectiles in high- and hyper-velocity impacts. Since current techniques for producing high- and hyper-velocity microparticle impacts are largely limited to metal or metal-coated projectiles, using minerals as projectiles is a significant innovation. Electrospray involves three steps: creation of charged droplets containing solute/particles, evaporation and bifurcation of droplets, and desolvation of the solute/particles. An acidified solution is slowly pumped through a needle in a strong DC field, which causes the solution to break into tiny, charged droplets laden with protons. Solvent evaporates from the electrosprayed droplets as they move through the electric field toward a grounded plate, causing the charge on the droplet to increase relative to its mass. When the electrosprayed droplet’s charge becomes such that the droplet is no longer stable, it bifurcates, and each of the resulting droplets carries some of the original droplet’s charge. Evaporation and bifurcation continues until the solute particle is completely desolvated. The result is a protonated solute molecule or particle. We built an instrument that electrosprays particles into vacuum and measures them using an image charge detector. Mineral microparticles were prepared by grinding natural mineral samples to ~2 µm diameter. These microparticles are then added to a 4:1 methanol:water solution to create a 0.005% w/v suspension. The suspension is electrosprayed into vacuum, where the

  12. Qualitative and quantitative two-dimensional thin-layer chromatography/high performance liquid chromatography/diode-array/electrospray-ionization-time-of-flight mass spectrometry of cholinesterase inhibitors.

    PubMed

    Mroczek, Tomasz

    2016-09-10

    Recently launched thin-layer chromatography-mass spectrometry (TLC-MS) interface enabling extraction of compounds directly from TLC plates into MS ion source was unusually extended into two-dimensional thin-layer chromatography/high performance liquid chromatography (2D, TLC/HPLC) system by its a direct connection to a rapid resolution 50×2.1mm, I.D. C18 column compartment followed by detection by diode array (DAD) and electrospray ionisation time-of-flight mass spectrometry (ESI-TOF-MS). In this way, even not separated bands of complicated mixtures of natural compounds could be analysed structurally, only within 1-2min after development of TLC plates. In comparison to typically applied TLC-MS interface, no ion suppression for acidic mobile phases was observed. Also, substantial increase in ESI-TOF-MS sensitivities and quality of spectra, were noticed. It has been utilised in combination with TLC- based bioautographic approaches of acetylcholinesterase (AChE) inhibitors, However, it can be also applied in any other procedures related to bioactivity (e.g. 2,2-Diphenyl-1-picryl-hydrazyl-DPPH screen test for radicals). This system has been also used for determination of half maximal inhibitory concentration (IC50 values) of the active inhibitor-galanthamine, as an example. Moreover, AChE inhibitory potencies of some of purified plant extracts, never studied before, have been quantitatively measured. This is first report of usage such the 2D TLC/HPLC/MS system both for qualitative and quantitative evaluation of cholinesterase inhibitors in biological matrices.

  13. Ionisation differential cross section measurements for N2 at low incident energy in coplanar and non-coplanar geometries

    NASA Astrophysics Data System (ADS)

    Sakaamini, Ahmad; Amami, Sadek; Murray, Andrew James; Ning, Chuangang; Madison, Don

    2016-10-01

    Ionisation triple differential cross sections have been determined experimentally and theoretically for the neutral molecule N2 over a range of geometries from coplanar to the perpendicular plane. Data were obtained at incident electron energies ∼10 and ∼20 eV above the ionisation potential of the 3σ g, 1π u and 2σ g states, using both equal and non-equal outgoing electron energies. The data were taken with the incident electron beam in the scattering plane (ψ = 0°), at 45° to this plane and orthogonal to the plane (ψ = 90°). The set of nine measured differential cross sections at a given energy were then inter-normalised to each other. The data are compared to new calculations using various distorted wave methods, and differences between theory and experiment are discussed.

  14. Application and Analysis of Biological Electrospray in Tissue Engineering.

    PubMed

    Yunmin, Ma; Yuanyuan, Liu; Haiping, Chen; Qingxi, Hu

    2015-01-01

    Nan-fiber scaffolds are suitable tools for tissue engineering. Electro spinning materials together with cells presents not adequate to obtain a high cellular zing tissue constructs as the shear force, tensile force, and other physical effects excited in the electro spinning process, which are harmful to cellular differentiation, development and function. However, this limitation has been overcome by a micro integration system of simultaneously bio-electro spraying human adipose stem cells (ASCs) and electro spinning Polyvinyl alcohol (PVA). Then it was compared to the single electro spinning nan-fiber scaffolds in relation to cell viability, which showed that the scaffolds by micro integration approach has a larger number of surviving cells and more suitable for cell growth and proliferation. In addition, the relationship between different parameters of biological electrospray (voltage, flow rate and distance of the needle from the collecting board) and droplet size of cell suspension was elucidated and the droplets with a near-mono distribution (<50um) could be generated to deposit a single living cell within a droplet. The association of bio-electro spraying with electro spinning (a scaffold preparation technique) has been demonstrated to be a promising and suitable tissue engineering approach in producing nan-fiber based three-dimensional (3-D) cell seeded scaffolds.

  15. Amorphization of hard crystalline materials by electrosprayed nanodroplet impact

    SciTech Connect

    Gamero-Castaño, Manuel Torrents, Anna; Borrajo-Pelaez, Rafael; Zheng, Jian-Guo

    2014-11-07

    A beam of electrosprayed nanodroplets impacting on single-crystal silicon amorphizes a thin surface layer of a thickness comparable to the diameter of the drops. The phase transition occurs at projectile velocities exceeding a threshold, and is caused by the quenching of material melted by the impacts. This article demonstrates that the amorphization of silicon is a general phenomenon, as nanodroplets impacting at sufficient velocity also amorphize other covalently bonded crystals. In particular, we bombard single-crystal wafers of Si, Ge, GaAs, GaP, InAs, and SiC in a range of projectile velocities, and characterize the samples via electron backscatter diffraction and transmission electron microscopy to determine the aggregation state under the surface. InAs requires the lowest projectile velocity to develop an amorphous layer, followed by Ge, Si, GaAs, and GaP. SiC is the only semiconductor that remains fully crystalline, likely due to the relatively low velocities of the beamlets used in this study. The resiliency of each crystal to amorphization correlates well with the specific energy needed to melt it except for Ge, which requires projectile velocities higher than expected.

  16. Electrospray deposition of organic molecules on bulk insulator surfaces.

    PubMed

    Hinaut, Antoine; Pawlak, Rémy; Meyer, Ernst; Glatzel, Thilo

    2015-01-01

    Large organic molecules are of important interest for organic-based devices such as hybrid photovoltaics or molecular electronics. Knowing their adsorption geometries and electronic structures allows to design and predict macroscopic device properties. Fundamental investigations in ultra-high vacuum (UHV) are thus mandatory to analyze and engineer processes in this prospects. With increasing size, complexity or chemical reactivity, depositing molecules by thermal evaporation becomes challenging. A recent way to deposit molecules in clean conditions is Electrospray Ionization (ESI). ESI keeps the possibility to work with large molecules, to introduce them in vacuum, and to deposit them on a large variety of surfaces. Here, ESI has been successfully applied to deposit triply fused porphyrin molecules on an insulating KBr(001) surface in UHV environment. Different deposition coverages have been obtained and characterization of the surface by in-situ atomic force microscopy working in the non-contact mode shows details of the molecular structures adsorbed on the surface. We show that UHV-ESI, can be performed on insulating surfaces in the sub-monolayer regime and to single molecules which opens the possibility to study a variety of complex molecules.

  17. Micro-nano hierarchical superhydrophobic electrospray-synthesized silica layers.

    PubMed

    Kim, Ji-Yeong; Kim, Eun-Kyeong; Kim, Sang Sub

    2013-02-15

    This paper reports the preparation of superhydrophobic SiO(2) layers with a micro-nano hierarchical surface structure. SiO(2) layers, which were rough on the microscale, were prepared using an electrospraying method combined with a sol-gel chemical route. To create a nanoscale structure, the surface of the SiO(2) layers was coated with Au nanoparticles using an ultraviolet-enhanced chemical reduction process, resulting in a micro-nano hierarchical surface structure. A subsequent fluorination treatment with a solution containing trichloro(1H,1H,2H,2H-perfluorooctyl)silane resulted in fluorination of the micro-nano hierarchical SiO(2) layers. The resulting SiO(2) layers showed outstanding repellency toward a range of liquid droplets, for example, a water-repellency of 170°. The surface fraction and work of adhesion of the fluorinated, micro-nano hierarchical SiO(2) layers were estimated using the Cassie-Baxter and Young-Dupre equations, respectively. The long-term durability and ultraviolet resistance of the superhydrophobic SiO(2) layers prepared in this study highlight their potential in a range of practical applications.

  18. A New Electrospray Aerosol Generator with High Particle Transmission Efficiency.

    PubMed

    Fu, Huijing; Patel, Anand C; Holtzman, Michael J; Chen, Da-Ren

    2011-01-01

    A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed.

  19. Transient Ion-Pair Separations for Electrospray Mass Spectrometry.

    PubMed

    Liu, Hanghui; Lam, Lily; Chi, Bert; Kadjo, Akinde F; Dasgupta, Purnendu K

    2016-02-16

    We report a novel ion-pair chromatography (IPC) approach for liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS), where the eluent does not contain any ion-pairing reagent (IPR). The IPR is injected on the column, much like the sample, and moves down the column. Significant amounts of a high retention factor IPR is injected, resulting in a transient but reproducible regional coating that progresses along the column. The sample is injected after a brief interval. The sample components interact with the IPR coated region during their passage; the chosen eluent gradient elutes the analytes of interest into the mass spectrometer before the IPR. Following analyte elution, the gradient is steeply raised, the IPR is washed out, and the effluent is sent to waste via a diverter valve until it is fully removed. As the nature of the analyte retention continuously changes along the column and with time, we call this transient ion-pair separation (TIPS). As the IPR never enters the MS, TIPS addresses two major drawbacks of IPC for ESI-MS: it avoids both ion suppression and ion source contamination. The potential of the generic approach for other modes of separation is discussed. An illustrative separation of two small inorganic ions, iodate and nitrate, is demonstrated on a reverse phase column by a transient prior injection of hexadecyltrimethylammonium chloride as IPR. PMID:26765166

  20. Electrospray-printed nanostructured graphene oxide gas sensors.

    PubMed

    Taylor, Anthony P; Velásquez-García, Luis F

    2015-12-18

    We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors' response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%-60% relative humidity range while consuming <6 μW. Devices with GO layers printed by different deposition recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ∼5 × 10(-4) T) at ∼1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems. PMID:26579701

  1. Electrospray of multifunctional microparticles for image-guided drug delivery

    NASA Astrophysics Data System (ADS)

    Zhang, Leilei; Yan, Yan; Mena, Joshua; Sun, Jingjing; Letson, Alan; Roberts, Cynthia; Zhou, Chuanqing; Chai, Xinyu; Ren, Qiushi; Xu, Ronald

    2012-03-01

    Anti-VEGF therapies have been widely explored for the management of posterior ocular disease, like neovascular age-related macular degeneration (AMD). Loading anti-VEGF therapies in biodegradable microparticles may enable sustained drug release and improved therapeutic outcome. However, existing microfabrication processes such as double emulsification produce drug-loaded microparticles with low encapsulation rate and poor antibody bioactivity. To overcome these limitations, we fabricate multifunctional microparticles by both single needle and coaxial needle electrospray. The experimental setup for the process includes flat-end syringe needles (both single needle and coaxial needle), high voltage power supplies, and syringe pumps. Microparticles are formed by an electrical field between the needles and the ground electrode. Droplet size and morphology are controlled by multiple process parameters and material properties, such as flow rate and applied voltage. The droplets are collected and freezing dried to obtain multifunctional microparticles. Fluorescent beads encapsulated poly(DL-lactide-co-glycolide) acid (PLGA) microparticles are injected into rabbits eyes through intravitreal injection to test the biodegradable time of microparticles.

  2. Next Generation of Electrosprayed Fibers for Tissue Regeneration

    PubMed Central

    Hong, Jong Kyu

    2011-01-01

    Electrospinning is a widely established polymer-processing technology that allows generation of fibers (in nanometer to micrometer size) that can be collected to form nonwoven structures. By choosing suitable process parameters and appropriate solvent systems, fiber size can be controlled. Since the technology allows the possibility of tailoring the mechanical properties and biological properties, there has been a significant effort to adapt the technology in tissue regeneration and drug delivery. This review focuses on recent developments in adapting this technology for tissue regeneration applications. In particular, different configurations of nozzles and collector plates are summarized from the view of cell seeding and distribution. Further developments in obtaining thick layers of tissues and thin layered membranes are discussed. Recent advances in porous structure spatial architecture parameters such as pore size, fiber size, fiber stiffness, and matrix turnover are summarized. In addition, possibility of developing simple three-dimensional models using electrosprayed fibers that can be utilized in routine cell culture studies is described. PMID:21210761

  3. Advances in drug delivery via electrospun and electrosprayed nanomaterials.

    PubMed

    Zamani, Maedeh; Prabhakaran, Molamma P; Ramakrishna, Seeram

    2013-01-01

    Electrohydrodynamic (EHD) techniques refer to procedures that utilize electrostatic forces to fabricate fibers or particles of different shapes with sizes in the nano-range to a few microns through electrically charged fluid jet. Employing different techniques, such as blending, surface modification, and coaxial process, there is a great possibility of incorporating bioactive such molecules as drugs, DNA, and growth factors into the nanostructures fabricated via EHD techniques. By careful selection of materials and processing conditions, desired encapsulation efficiency as well as preserved bioactivity of the therapeutic agents can be achieved. The drug-loaded nanostructures produced can be applied via different routes, such as implantation, injection, and topical or oral administration for a wide range of disease treatment. Taking advantage of the recent developments in EHD techniques like the coaxial process or multilayered structures, individually controlled delivery of multiple drugs is achievable, which is of great demand in cancer therapy and growth-factor delivery. This review summarizes the most recent techniques and postmodification methods to fabricate electrospun nanofibers and electrosprayed particles for drug-delivery applications.

  4. Induction of protein conformational change inside the charged electrospray droplet.

    PubMed

    Banerjee, Shibdas

    2013-02-01

    The behavior of the analyte molecules inside the neutral core of the charged electrospray (ES) droplet is not unambiguously known to date. The possibility of protein conformational change inside the charged ES droplet has been investigated. The ES droplets encapsulating the protein molecules were exposed to the acetic acid vapor in the ionization chamber to absorb the acetic acid vapor. Because of the faster evaporation of water than that of acetic acid, the droplets became enriched with acetic acid and thus altered the solvent environment (e.g. pH and polarity) of the final charged droplets from where the naked charged analytes (proteins) are formed. Thus, the perturbation of the ES droplet solvent environment resulted in the protein conformational change (unfolding) during the short lifespan of the ES droplet and that is reflected by the multimodal charge state distribution in the corresponding mass spectra. Further, the extent of this conformational change inside the ES droplet was found to be related to the structural flexibility of the protein. Although the protein conformational change inside the ES droplet has been driven by using acetic acid vapor in the present study, the results would help in the near future to understand the spontaneity of the conformational change of the analyte on the millisecond timescale of phase transition in the natural way of ES process.

  5. Electrospray-printed nanostructured graphene oxide gas sensors

    NASA Astrophysics Data System (ADS)

    Taylor, Anthony P.; Velásquez-García, Luis F.

    2015-12-01

    We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors’ response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%-60% relative humidity range while consuming <6 μW. Devices with GO layers printed by different deposition recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ˜5 × 10-4 T) at ˜1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems.

  6. [Theory and practice of electrospray crystallization in particle size reduction].

    PubMed

    Szunyogh, Tímea; Ambrus, Rita; Szabóné Révész, Piroska

    2015-01-01

    Nowdays, one of the most challenges for the researchers is the formulation of poorly water soluble drugs. Reduction of particle size of active agents to submicron range could result in a faster dissolution rate and higher bioavailability. Integration as crystallization process is an often used particle size decreasing technique. The aim of this study was to show the theoretical background and practical application of the electros pray crystallization as an innovative particle size decreasing technique. Our model drug was the niflumic acid (NIF), which belongs to the BCS Class II. After the optimization of the process parameters, the physico-chemical properties of the samples were characterized. Particle size and shape were visualized by scanning electron microscopy (SEM). Crystalline state of NIF and the samples were investigated using differential scanning calorimetry (DSC) and X-ray powder diffraction. Physico-chemical properties were determined using dissolution test from simulated media. The electrospray crytallization resulted in particle size reduction but the aggregation of nanonized NIF crystals (NIF-nano) could not avoid without excipient. Aggregates with poor secondary forces are suitable for production of the interactive physical mixture. It was found that NIF-nano could be well distributed on the surface of the mannitol as carrier and the Poloxamer R protected the NIF-nano crystals (320 nm)from aggregation. Consequently, the physical mixture resulted in product with higher polarity, better wettability and faster dissolution rate of NIF as raw NIF or NIF-nano.

  7. Advances in drug delivery via electrospun and electrosprayed nanomaterials

    PubMed Central

    Zamani, Maedeh; Prabhakaran, Molamma P; Ramakrishna, Seeram

    2013-01-01

    Electrohydrodynamic (EHD) techniques refer to procedures that utilize electrostatic forces to fabricate fibers or particles of different shapes with sizes in the nano-range to a few microns through electrically charged fluid jet. Employing different techniques, such as blending, surface modification, and coaxial process, there is a great possibility of incorporating bioactive such molecules as drugs, DNA, and growth factors into the nanostructures fabricated via EHD techniques. By careful selection of materials and processing conditions, desired encapsulation efficiency as well as preserved bioactivity of the therapeutic agents can be achieved. The drug-loaded nanostructures produced can be applied via different routes, such as implantation, injection, and topical or oral administration for a wide range of disease treatment. Taking advantage of the recent developments in EHD techniques like the coaxial process or multilayered structures, individually controlled delivery of multiple drugs is achievable, which is of great demand in cancer therapy and growth-factor delivery. This review summarizes the most recent techniques and postmodification methods to fabricate electrospun nanofibers and electrosprayed particles for drug-delivery applications. PMID:23976851

  8. [Theory and practice of electrospray crystallization in particle size reduction].

    PubMed

    Szunyogh, Tímea; Ambrus, Rita; Szabóné Révész, Piroska

    2015-01-01

    Nowdays, one of the most challenges for the researchers is the formulation of poorly water soluble drugs. Reduction of particle size of active agents to submicron range could result in a faster dissolution rate and higher bioavailability. Integration as crystallization process is an often used particle size decreasing technique. The aim of this study was to show the theoretical background and practical application of the electros pray crystallization as an innovative particle size decreasing technique. Our model drug was the niflumic acid (NIF), which belongs to the BCS Class II. After the optimization of the process parameters, the physico-chemical properties of the samples were characterized. Particle size and shape were visualized by scanning electron microscopy (SEM). Crystalline state of NIF and the samples were investigated using differential scanning calorimetry (DSC) and X-ray powder diffraction. Physico-chemical properties were determined using dissolution test from simulated media. The electrospray crytallization resulted in particle size reduction but the aggregation of nanonized NIF crystals (NIF-nano) could not avoid without excipient. Aggregates with poor secondary forces are suitable for production of the interactive physical mixture. It was found that NIF-nano could be well distributed on the surface of the mannitol as carrier and the Poloxamer R protected the NIF-nano crystals (320 nm)from aggregation. Consequently, the physical mixture resulted in product with higher polarity, better wettability and faster dissolution rate of NIF as raw NIF or NIF-nano. PMID:26390735

  9. Thin Film Formation and Morphology of Electrosprayed Polydimethylsiloxane.

    PubMed

    Weiss, Florian M; Töpper, Tino; Osmani, Bekim; Deyhle, Hans; Kovacs, Gabor; Müller, Bert

    2016-04-01

    Low-voltage dielectric actuators (DEAs) can be fabricated using submicrometer-thin polydimethylsiloxane (PDMS) films. The two established techniques, namely spin coating and molecular beam deposition, however, are inappropriate to produce multistack DEAs in an efficient way. Therefore, we propose an alternative deposition technique, i.e., the alternating current electrospray deposition (ACESD) of 5 vol % PDMS in ethyl acetate solution and subsequent ultraviolet light curing. Atomic force microscopy makes possible the three-dimensional analysis of cured droplet-like islands. These circular islands, prepared on 2 in. Si(100) wafers from four polymers with molecular masses between 800 and 62,700 g/mol, reveal a characteristic morphology with an increasing height-to-diameter ratio. Using the 6000 g/mol polymer for ACESD, the film morphology evolution was tracked by applying conventional optical microscopy and spectroscopic ellipsometry. When the deposition was terminated after 13 s, circular islands with a mean height of 30 nm were found, while terminating the deposition after about 155 s led to a confluent layer with a mean height of 91 ± 10 nm. Potential electrostatic interactions between the droplets could not be identified through the analysis of spatial island distribution. Nevertheless, ACESD is a budget-priced and competitive deposition technique that can be employed to fabricate submicrometer-thin PDMS films with true nanometer roughness. PMID:26978236

  10. Application and Analysis of Biological Electrospray in Tissue Engineering

    PubMed Central

    Yunmin, Ma; Yuanyuan, Liu; Haiping, Chen; Qingxi, Hu

    2015-01-01

    Nan-fiber scaffolds are suitable tools for tissue engineering. Electro spinning materials together with cells presents not adequate to obtain a high cellular zing tissue constructs as the shear force, tensile force, and other physical effects excited in the electro spinning process, which are harmful to cellular differentiation, development and function. However, this limitation has been overcome by a micro integration system of simultaneously bio-electro spraying human adipose stem cells (ASCs) and electro spinning Polyvinyl alcohol (PVA). Then it was compared to the single electro spinning nan-fiber scaffolds in relation to cell viability, which showed that the scaffolds by micro integration approach has a larger number of surviving cells and more suitable for cell growth and proliferation. In addition, the relationship between different parameters of biological electrospray (voltage, flow rate and distance of the needle from the collecting board) and droplet size of cell suspension was elucidated and the droplets with a near-mono distribution (<50um) could be generated to deposit a single living cell within a droplet. The association of bio-electro spraying with electro spinning (a scaffold preparation technique) has been demonstrated to be a promising and suitable tissue engineering approach in producing nan-fiber based three-dimensional (3-D) cell seeded scaffolds. PMID:26089992

  11. Extractive electrospray ionization mass spectrometry for uranium chemistry studies.

    PubMed

    Chen, Huanwen; Luo, Mingbiao; Xiao, Saijin; Ouyang, Yongzhong; Zhou, Yafei; Zhang, Xinglei

    2013-01-01

    Uranium chemistry is of sustainable interest. Breakthroughs in uranium studies make serious impacts in many fields including chemistry, physics, energy and biology, because uranium plays fundamentally important roles in these fields. Substantial progress in uranium studies normally requires development of novel analytical tools. Extractive electrospray ionization mass spectrometry (EESI-MS) is a sensitive technique for trace detection of various analytes in complex matrices without sample pretreatment. EESI-MS shows excellent performance for monitoring uranium species in various samples at trace levels since it tolerates extremely complex matrices. Therefore, EESI-MS is an alternative choice for studying uranium chemistry, especially when it combines ion trap mass spectrometry. In this presentation, three examples of EESI-MS for uranium chemistry studies will be given, illustrating the potential applications of EESI-MS in synthesis chemistry, physical chemistry, and analytical chemistry of uranium. More specifically, case studies on EESI-MS for synthesis and characterization of novel uranium species, and for rapid detection of uranium and its isotope ratios in various samples will be presented. Novel methods based on EESI-MS for screening uranium ores and radioactive iodine-129 will be presented. PMID:24349940

  12. Is electrospray emission really due to columbic forces?

    SciTech Connect

    Aliotta, Francesco Ponterio, Rosina C.; Salvato, Gabriele; Vasi, Cirino; Calandra, Pietro; Pochylski, Mikolaj

    2014-09-15

    Electrospray ionization (ESI) is a widely adopted soft ionization method for mass spectroscopy (MS). In spite of the undeniable success of the technique, its mechanisms are difficult to be analytically modelled because the process is characterized by non-equilibrium conditions. The common belief is that the formation of gas-phase ions takes place at the apex of the Taylor cone via electrophoretic charging. The charge balance implies that a conversion of electrons to ions should occur at the metal-liquid interface of the injector needle. We have detected that the above description is based on unproved assumptions which are not consistent with the correct evaluation of the problem. The comparison between experiments performed under the usual geometry and observations obtained under symmetric field configurations suggests that the emitted droplets cannot be significantly charged or, at least, that any possible ionization mechanism is so poorly efficient to ensure that columbic forces cannot play a major role in jet formation, even in cases where the liquid consists of a solution of ionic species. Further work is required to clearly understand how ionization occurs in ESI-MS.

  13. Electrospray-ionization mass spectrometry of intact intrinsic membrane proteins.

    PubMed Central

    Whitelegge, J. P.; Gundersen, C. B.; Faull, K. F.

    1998-01-01

    Membrane proteins drive and mediate many essential cellular processes making them a vital section of the proteome. However, the amphipathic nature of these molecules ensures their detailed structural analysis remains challenging. A versatile procedure for effective electrospray-ionization mass spectrometry (ESI-MS) of intact intrinsic membrane proteins purified using reverse-phase chromatography in aqueous formic acid/isopropanol is presented. The spectra of four examples, bacteriorhodopsin and its apoprotein from Halobacterium and the D1 and D2 reaction-center subunits from spinach thylakoids, achieve mass measurements that are within 0.01% of calculated theoretical values. All of the spectra reveal lesser quantities of other molecular species that can usually be equated with covalently modified subpopulations of these proteins. Our analysis of bovine rhodopsin, the first ESI-MS study of a G-protein coupled receptor, yielded a complex spectrum indicative of extensive molecular heterogeneity. The range of masses measured for the native molecule agrees well with the range calculated based upon variable glycosylation and reveals further heterogeneity arising from other covalent modifications. The technique described represents the most precise way to catalogue membrane proteins and their post-translational modifications. Resolution of the components of protein complexes provides insights into native protein/protein interactions. The apparent retention of structure by bacteriorhodopsin during the analysis raises the potential of obtaining tertiary structure information using more developed ESI-MS experiments. PMID:9655347

  14. Electrospray ionization with aluminum foil: A versatile mass spectrometric technique.

    PubMed

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

    2014-03-19

    In this study, we developed a novel electrospray ionization (ESI) technique based on household aluminum foil (Al foil) and demonstated the desirable features and applications of this technique. Al foil can be readily cut and folded into desired configuration for effective ionization and for holding sample solution in bulk to allowing acquisition of durable ion signals. The present technique was demonstrated to be applicable in analysis of a wide variety of samples, ranging from pure chemical and biological compounds, e.g., organic compounds and proteins, to complex samples in liquid, semi-solid, and solid states, e.g., beverages, skincare cream, and herbal medicines. The inert, hydrophobic and impermeable surface of Al foil allows convenient and effective on-target extraction of solid samples and on-target sample clean-up, i.e., removal of salts and detergents from proteins and peptides, extending ESI device from usually only for sample loading and ionization to including sample processing. Moreover, Al foil is an excellent heat-conductor and highly heat-tolerant, permitting direct monitoring of thermal reactions, e.g., thermal denaturation of proteins. Overall, the present study showed that Al-foil ESI could be an economical and versatile method that allows a wide range of applications. PMID:24594810

  15. Analytical Properties of Solid-substrate Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

    Conventional electrospray ionization mass spectrometry (ESI-MS) uses a capillary for sample loading and ionization. Along with the development of ambient ionization techniques, ESI-MS using noncapillary emitters has attracted more interest in recent years. Following our recent report on ESI-MS using wooden tips ( Anal. Chem. 83, 8201-8207 (2011)), the technique was further investigated and extended in this study. Our results revealed that the wooden tips could serve as a chromatographic column for separation of sample components. Sequential and exhaustive ionization was observed for proteins and salts on wooden tips with salts ionized sooner and proteins later. Nonconductive materials that contain microchannels/pores could be used as tips for ESI-MS analysis with sample solutions loaded to the sharp-ends only, since rapid diffusion of sample solutions by capillary action would enable the tips to become conductive. Tips of inert materials such as bamboo, fabrics, and sponge could be used for sample loading and ionization, while samples such as tissue, mushroom, and bone could form tips to induce ionization for direct analysis with application of a high voltage. [Figure not available: see fulltext.

  16. A New Electrospray Aerosol Generator with High Particle Transmission Efficiency.

    PubMed

    Fu, Huijing; Patel, Anand C; Holtzman, Michael J; Chen, Da-Ren

    2011-01-01

    A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed. PMID:22829715

  17. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric and semi-empirical calculations study of five isoflavone aglycones.

    PubMed

    Madeira, Paulo J Amorim; Borges, Carlos M; Florêncio, M Helena

    2010-12-15

    Five isoflavones, daidzein, genistein, formononetin, prunetin and biochanin A, known for their biological properties, are investigated by electrospray ionization mass spectrometry in the positive ion mode. The most probable protonation sites are determined taking into account semi-empirical calculations using the PM6 Hamiltonian. Fragmentation mechanisms are proposed based on accurate mass measurements, MS(3) experiments and supported by the semi-empirical calculations. Some of the fragmentation pathways were found to be dependent on the substitution pattern of the B-ring and the ions afforded by these fragmentations can be considered as diagnostic. It was possible to distinguish between prunetin and biochanin A, two isobaric isoflavone aglycones included in this study. Furthermore, a comparison of the fragmentation patterns of genistein and biochanin A, two isoflavones, with those of their flavone counterparts, apigenin and acacetin, enabled us to identify some key ions mainly due to structural features, allowing distinction to be made between these two classes of compounds.

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

    PubMed

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

    2015-03-01

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

  19. Determination of diallyldimethylammonium chloride in drinking water by reversed-phase ion-pair chromatography-electrospray ionization mass spectrometry.

    PubMed

    Jin, Fen; Hu, Jianying; Yang, Min; Jin, Xiaohui; He, Wenjie; Han, Hongda

    2006-01-01

    A method for the direct determination of diallyldimethylammonium chloride (DADMAC) in water samples, using ion-pair liquid chromatography-mass spectrometry system was developed. The chromatographic separation was performed using a C18 column. The type, the concentration of ion-pair reagent and the pH were optimized to give good chromatographic retention and sensitivity for DADMAC. Quantification was achieved in the positive electrospray ionization mode using selected ion monitoring. The cone voltage was also studied to establish the optimal experimental conditions. Finally, the reproducibility of the proposed method was shown by good run-to-run and day-to-day precision values. No sample preparation was required and the detection limit was 0.1 microg/L. The method was used to detect residual DADMAC at drinking water treatment plants in Tianjin, north China. The concentration of DADMAC observed in drinking water ranged from below quantitation limit to 22.0 microg/L.

  20. 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.

  1. Les neuropeptides gastro-intestinaux cibles des effets des rayonnements ionisants : altérations fonctionnelles

    NASA Astrophysics Data System (ADS)

    Linard, C.; Esposito, V.; Wysocki, J.; Griffiths, N. M.

    1998-04-01

    The symptoms associated with exposure to ionizing radiation are nausea, vomiting, diarrhoea. The response of the gut is complex involving modifications of motility and fluid and electrolyte transport. Gastrointestinal regulatory peptides have an important role in these functions. This study showed that radiation-induced tissue variations of neuropeptides have some repercussions on intestinal biological activity of these peptides soon after irradiation. In addition such modifications are also seen a few years after irradiation. Les symptômes associés à l'exposition aux rayonnements ionisants sont des nausées, vomissements et diarrhées. La réponse du système digestif est complexe, impliquant des modifications de la motilité et du transport d'eau et d'électrolytes. les neuropeptides gastro-intestinaux ont un rôle important dans ces fonctions. Cette étude montre que les variations tissulaires de ces neuropeptides induites par l'irradiation ont des répercussions sur l'activité biologique intestinale pour des temps précoces mais que ces perturbations sont encore visibles quelques années après l'irradiation.

  2. An isotopic analysis of ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-06-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find an enrichment factor (δ34S) of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  3. An isotope view on ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-02-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find a δ34S value of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  4. An isotopic view of ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S. O.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-04-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism remains undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find a d34S value of 8.7 ± 0.4 ‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  5. A gas ionisation Direct-STIM detector for MeV ion microscopy

    NASA Astrophysics Data System (ADS)

    Norarat, Rattanaporn; Guibert, Edouard; Jeanneret, Patrick; Dellea, Mario; Jenni, Josef; Roux, Adrien; Stoppini, Luc; Whitlow, Harry J.

    2015-04-01

    Direct-Scanning Transmission Ion Microscopy (Direct-STIM) is a powerful technique that yields structural information in sub-cellular whole cell imaging. Usually, a Si p-i-n diode is used in Direct-STIM measurements as a detector. In order to overcome the detrimental effects of radiation damage which appears as a broadening in the energy resolution, we have developed a gas ionisation detector for use with a focused ion beam. The design is based on the ETH Frisch grid-less off-axis Geiger-Müller geometry. It is developed for use in a MeV ion microscope with a standard Oxford Microbeams triplet lens and scanning system. The design has a large available solid angle for other detectors (e.g. proton induced fluorescence). Here we report the performance for imaging ReNcells VM with μm resolution where energy resolutions of <24 keV fwhm could be achieved for 1 MeV protons using isobutane gas.

  6. Growth alteration and leaf biochemical responses in Phaseolus vulgaris exposed to different doses of ionising radiation.

    PubMed

    Arena, C; De Micco, V; De Maio, A

    2014-01-01

    Ionising radiation may have different effects on plant metabolism, growth and reproduction, depending on radiation dose, plant species, developmental stage and physiological traits. In this study, exposure of dwarf bean plants to different doses of X-rays (0.3, 10, 50, 100 Gy) was investigated with a multidisciplinary approach consisting of morphological, ecophysiological and biochemical analysis. Both mature and young leaves still growing during the X-rays exposure were compared with non-irradiated control leaves. In particular, leaf expansion, leaf anatomy and functional traits, as well as photosynthetic pigment content and Rubisco expression were analysed. Moreover, the activity of poly(ADP-ribose) polymerase (PARP) was also measured as an indicator of radiation-induced DNA damage. Our data showed that leaf growth is affected by high levels of radiation and demonstrate that mature leaves are more radio-resistant than young leaves, which experience severe dose-dependent changes in leaf functional traits. In particular, young leaves exhibited a reduction of area and an increase in specific mass and dry matter content, as well as a decline in Rubisco activity. Moreover, they showed elevated PARP activity and an increase in phenolic compounds in wall cells if compared with mature leaves. Both of these strategies have been interpreted as a way to help developing leaves withstand irradiation.

  7. Ion-pair states of the ClO radical observed by multiphoton ionisation spectroscopy

    NASA Astrophysics Data System (ADS)

    Cooper, Martin J.; Diez-Rojo, Trinidad; Rogers, Leon J.; Western, Colin M.; Ashfold, Michael N. R.; Hudgens, Jeffrey W.

    1997-06-01

    We present isotopically selected multiphoton ionisation spectra of the CIO radical following excitation in the wavelength range 276-261 nm, obtained using both a room-temperature sample and under the rotationally cold conditions in a pulsed molecular beam. In both cases high-resolution rotationally resolved spectra were obtained, with the 'cold' spectra showing discrete rovibrational bands. Analysis of the rotational structure leads to the identification of excited levels of ClO of 2Π symmetry resonant at the two-photon energy (72200-76200 cm -1). These we deduce to possess extended equilibrium bond lengths ( R ≈ 2.4 Å), and thus associate with one or more ion-pair states. Full interpretation of the observed spectra is complicated by the effects of additional wavelength-dependent intensity enhancements due to predissociated levels of the A 2Π state accidentally resonant at the energy of one absorbed photon. We report an isotopically resolved room-temperature 2 + 1 REMPI spectrum, involving a progression of vibrational levels of the previously documented C 2ɛ state of ClO. The observed CX two-photon transitions are well reproduced using known spectroscopic constants.

  8. 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.

  9. Genotoxicity in earthworm after combined treatment of ionising radiation and mercury.

    PubMed

    Ryu, Tae Ho; An, Kwang-Guk; Kim, Jin Kyu

    2014-06-01

    This study was performed to investigate the acute genotoxic effects of mercury and radiation on earthworms (Eisenia fetida). The levels of DNA damage and the repair kinetics in the coelomocytes of E. fetida treated with mercuric chloride (HgCl₂) and ionising radiation (gamma rays) were analysed by means of the comet assay. For detection of DNA damage and repair, E. fetida was exposed to HgCl₂ (0-160 mg kg(-1)) and irradiated with gamma rays (0-50 Gy) in vivo. The increase in DNA damage depended on the concentration of mercury or dose of radiation. The results showed that the more the oxidative stress induced by mercury and radiation the longer the repair time that was required. When a combination of HgCl₂ and gamma rays was applied, the cell damage was much higher than those treated with HgCl₂ or radiation alone, which indicated that the genotoxic effects were increased after the combined treatment of mercury and radiation. PMID:24870361

  10. Formation of enriched black tea extract loaded chitosan nanoparticles via electrospraying

    NASA Astrophysics Data System (ADS)

    Hammond, Samuel James

    Creating nanoparticles of beneficial nutraceuticals and pharmaceuticals has had a large surge of research due to the enhancement of absorption and bioavailability by decreasing their size. One of these ways is by electrohydrodynamic atomization, also known as electrospraying. In general, this novel process is done by forcing a liquid through a capillary nozzle and which is subjected to an electrical field. While there are different ways to create nanoparticles, the novel method of electrospraying can be beneficial over other types of nanoparticle formation. Reasons include high control over particle size and distribution by altering electrospray parameters (voltage, flow rate, distance, and time), higher encapsulation efficiency than other methods, and also it is a one step process without exposure to extreme conditions (Gomez-Estaca et. al. 2012, Jaworek and Sobcyzk 2008). The current study aimed to create a chitosan encapsulated theaflavin-2 enriched black tea extract (BTE) nanoparticles via electrospraying. The first step of this process was to create the smallest chitosan nanoparticles possible by altering the electrospray parameters and the chitosan-acetic acid solution parameters. The solution properties altered include chitosan molecular weight, acetic acid concentration, and chitosan concentration. Specifically, the electrospray parameters such as voltage, flow rate and distance from syringe to collector are the most important in determining particle size. After creating the smallest chitosan particles, the TF-2 enriched black tea extract was added to the chitosan-acetic acid solution to be electrosprayed. The particles were assessed with the following procedures: Atomic force microscopy (AFM) and scanning electron microscopy (SEM) for particle morphology and size, and loading efficiency with ultraviolet--visible spectrophotometer (UV-VIS). Chitosan-BTE nanoparticles were successfully created in a one step process. Diameter of the particles on average

  11. Electrospray ionization mass spectrometry and its environmental applications

    SciTech Connect

    Long, J.M.

    1993-01-01

    An electrospray ionization (ESI) source was designed, fabricated and then installed on a VG TRIO-2 quadrupole mass spectrometer. A gold coated 50-[mu]m fused silica capillary was used instead of the conventional stainless steel needle. Analytes are desorbed into the gas phase via a heated metal transport capillary and are focused through a set of five electrostatic lenses into the analyzer region of the mass spectrometer. Environmentally significant compounds such as pesticides and herbicides that are polar, nonvolatile and thermally labile are not readily analyzed by conventional gas chromatography/mass spectrometry (GC/MS). Thirty pesticides from the 13 classes of carbamate, organophosphorus, organochlorine, bipyridyl, phthalimide, urea, carboxyllic acid, hydroxycoumarin, triazine, indandione, dinitroaniline, pyrethrin, and thiocarbamate were analyzed using this method. Analysis of these samples showed that addition of acid to the neat sample did not appreciably increase the protonated analyte signal nor the total ion current for any of the samples analyzed. This observation together with the extremely low pKa values of these pesticides, calculated by SPARC, indicates that the protonated analytes are formed in the gas rather than in the condensed phase. Sodium and ammonium ions were added to these pesticides but in no case was the total ion current increased over that from the neat sample. Solvent studies showed that 50/50 mixtures of methanol/water and acetonitrile/water are both suitable solvent systems but that a methanol fraction of 30% appears to be ideal for some of the pesticides studied. Evidence of radical cation formation was observed when pure acetonitrile was used. It was demonstrated, by spiking 5 carbamate pesticides into Yellowstone River water, that ESI/MS by the direct injection method is a potential candidate as a rapid screening method for pesticides in natural waters.

  12. Surface effects and electrochemical cell capacitance in desorption electrospray ionization.

    PubMed

    Volný, Michael; Venter, Andre; Smith, Scott A; Pazzi, Marco; Cooks, R Graham

    2008-04-01

    Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte. PMID

  13. Aerosol Analysis via Electrostatic Precipitation-Electrospray Ionization Mass Spectrometry.

    PubMed

    He, Siqin; Li, Lin; Duan, Hongxu; Naqwi, Amir; Hogan, Christopher J

    2015-07-01

    Electrospray ionization (ESI) is the preferred mode of ion generation for mass analysis of many organic species, as alternative ionization techniques can lead to appreciable analyte fragmentation. For this reason, ESI is an ideal method for the analysis of species within aerosol particles. However, because of their low concentrations (∼10 μg/m(3)) in most environments, ESI has been applied sparingly in aerosol particle analysis; aerosol mass spectrometers typically employ analyte volatilization followed by electron ionization or chemical ionization, which can lead to a considerable degree of analyte fragmentation. Here, we describe an approach to apply ESI to submicrometer and nanometer scale aerosol particles, which utilizes unipolar ionization to charge particles, electrostatic precipitation to collect particles on the tip of a Tungsten rod, and subsequently, by flowing liquid over the rod, ESI and mass analysis of the species composing collected particles. This technique, which we term electrostatic precipitation-ESI-MS (EP-ESI-MS), is shown to enable analysis of nanogram quantities of collected particles (from aerosol phase concentrations as low as 10(2) ng m(-3)) composed of cesium iodide, levoglucosan, and levoglucosan within a carbon nanoparticle matrix. With EP-ESI-MS, the integrated mass spectrometric signals are found to be a monotonic function of the mass concentration of analyte in the aerosol phase. We additionally show that EP-ESI-MS has a dynamic range of close to 5 orders of magnitude in mass, making it suitable for molecular analysis of aerosol particles in laboratory settings with upstream particle size classification, as well as analysis of PM 2.5 particles in ambient air. PMID:26024017

  14. Multistage Reactive Transmission-Mode Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Peters, Kevin C.; Comi, Troy J.; Perry, Richard H.

    2015-09-01

    Elucidating reaction mechanisms is important for advancing many areas of science such as catalyst development. It is often difficult to probe fast reactions at ambient conditions with high temporal resolution. In addition, systems involving reagents that cross-react require analytical methods that can minimize interaction time and specify their order of introduction into the reacting system. Here, we explore the utility of transmission mode desorption electrospray ionization (TM-DESI) for reaction monitoring by directing a microdroplet spray towards a series of meshes with micrometer-sized openings coated with reagents, an approach we call multistage reactive TM-DESI (TM n -DESI, where n refers to the number of meshes; n = 2 in this report). Various stages of the reaction are initiated at each mesh surface, generating intermediates and products in microdroplet reaction vessels traveling towards the mass spectrometer. Using this method, we investigated the reactivity of iron porphyrin catalytic hydroxylation of propranolol and other substrates. Our experimental results indicate that TM n -DESI provides the ability to spatially separate reagents and control their order of introduction into the reacting system, thereby minimizing unwanted reactions that lead to catalyst deactivation and degradation products. In addition, comparison with DESI-MS analyses (the Zare and Latour laboratories published results suggesting accessible reaction times <1 ms) of the reduction of dichlorophenolindophenol by L-ascorbic acid suggest that TM 1 -DESI can access reaction times less than 1 ms. Multiple meshes allow sequential stages of desorption/ionization per MS scan, increasing the number of analytes and reactions that can be characterized in a single experiment.

  15. Surface effects and electrochemical cell capacitance in desorption electrospray ionization.

    PubMed

    Volný, Michael; Venter, Andre; Smith, Scott A; Pazzi, Marco; Cooks, R Graham

    2008-04-01

    Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte.

  16. Electrospray deposition of carbon nanotube thin films for flexible transparent electrodes.

    PubMed

    Meng, Yinan; Xin, Guoqing; Nam, Jaewook; Cho, Sung Min; Chae, Heeyeop

    2013-09-01

    Flexible transparent carbon nanotube (CNT) electrodes were fabricated by electrospray deposition, a large-area scalable and cost-effective process. The carbon nanotubes were dispersed in N,N-dimethylformamide (DMF) and deposited on polyethylene terephthalate (PET) substrates by electrospray deposition process at room temperature and atmospheric pressure. Major process variables were characterized and optimized for the electrospray process development such as electric field between nozzle and substrates, CNT solution flowrate, gap between nozzle and substrates, solution concentration, solvent properties and surface temperature. The sheet resistance of the electrospray deposited CNT films were reduced by HNO3 doping process. 169 Omega/sq sheet resistance and 86% optical transmittance was achieved with low surface roughness of 1.2 nm. The films showed high flexibility and transparency, making them potential replacements of ITO or ZnO in such as solid state lighting, touch panels, and solar cells. Electrospray process is a scalable process and we believe that this process can be applied for large area carbon nanotube film formation.

  17. Electrospray deposition of carbon nanotube thin films for flexible transparent electrodes.

    PubMed

    Meng, Yinan; Xin, Guoqing; Nam, Jaewook; Cho, Sung Min; Chae, Heeyeop

    2013-09-01

    Flexible transparent carbon nanotube (CNT) electrodes were fabricated by electrospray deposition, a large-area scalable and cost-effective process. The carbon nanotubes were dispersed in N,N-dimethylformamide (DMF) and deposited on polyethylene terephthalate (PET) substrates by electrospray deposition process at room temperature and atmospheric pressure. Major process variables were characterized and optimized for the electrospray process development such as electric field between nozzle and substrates, CNT solution flowrate, gap between nozzle and substrates, solution concentration, solvent properties and surface temperature. The sheet resistance of the electrospray deposited CNT films were reduced by HNO3 doping process. 169 Omega/sq sheet resistance and 86% optical transmittance was achieved with low surface roughness of 1.2 nm. The films showed high flexibility and transparency, making them potential replacements of ITO or ZnO in such as solid state lighting, touch panels, and solar cells. Electrospray process is a scalable process and we believe that this process can be applied for large area carbon nanotube film formation. PMID:24205613

  18. Biases in Ion Transmission Through an Electrospray Ionization-Mass Spectrometry Capillary Inlet

    SciTech Connect

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

    2009-12-01

    The standard heated capillary inlet of an electrospray ionization mass spectrometry (ESI-MS) interface was compared with shorter versions of the inlet to determine the effects on transmission and ionization efficiencies for low-flow electrosprays. The primary finding of the study was a large bias towards higher mobility species in the electrospray current losses to the inside walls of the inlet. The transmission efficiency increased with decreasing capillary length due to reduced losses along the capillary. A decrease in transmission efficiency was also confirmed for electrosprays of higher conductivity solvents. A direct correlation between mass spectrometry sensitivity and the transmitted electrospray current was not observed as some analytes showed little to no increase in sensitivity while others showed as high as a 15 – fold increase. The variation was shown to at least be partially dependent on the analytes’ mobilities. Higher mobility analytes demonstrated a larger increase in sensitivity when shorter inlets were used. The results indicate that considerable biases against higher mobility species can be produced by the use of long capillary inlets in the ESI-MS interface and strategies are provided to minimize the bias against higher mobility species for efficient ion transmission through the heated capillary interface.

  19. Elastomeric Microchip Electrospray Emitter for Stable Cone-Jet Mode Operation in the Nanoflow Regime.

    SciTech Connect

    Kelly, Ryan T.; Tang, Keqi; Irimia, Daniel; Toner, Mehmet; Smith, Richard D.

    2008-05-15

    Despite widespread interest in applying lab-on-a-chip technologies to mass spectrometry (MS)-based analyses, the coupling of microfluidics to electrospray ionization (ESI)-MS remains challenging. We report a robust, integrated poly(dimethylsiloxane) microchip interface for ESI-MS using simple and widely accessible microfabrication procedures. The interface uses an auxiliary channel to provide electrical contact in the Taylor cone of the electrospray without sample loss or dilution. The electric field at the channel terminus is enhanced by two vertical cuts that cause the interface to taper to a line rather than to a point, and the formation of small Taylor cones at the channel exit ensures sub-nL post-column dead volumes. While comparable ESI-MS sensitivities were achieved using both microchip and conventional fused silica capillary emitters, stable cone-jet mode electrospray could be established over a far broader range of flow rates (from 50–1000 nL/min) and applied potentials using the microchip emitters. This special feature of the microchip emitter should minimize the fine tuning required for electrospray optimization and make the stable electrospray more resistant to external perturbations.

  20. Fabrication of Polymeric Coatings with Controlled Microtopographies Using an Electrospraying Technique

    PubMed Central

    Guo, Qiongyu; Mather, Jason P.; Yang, Pine; Boden, Mark; Mather, Patrick T.

    2015-01-01

    Surface topography of medical implants provides an important biophysical cue on guiding cellular functions at the cell-implant interface. However, few techniques are available to produce polymeric coatings with controlled microtopographies onto surgical implants, especially onto implant devices of small dimension and with complex structures such as drug-eluting stents. Therefore, the main objective of this study was to develop a new strategy to fabricate polymeric coatings using an electrospraying technique based on the uniqueness of this technique in that it can be used to produce a mist of charged droplets with a precise control of their shape and dimension. We hypothesized that this technique would allow facile manipulation of coating morphology by controlling the shape and dimension of electrosprayed droplets. More specifically, we employed the electrospraying technique to coat a layer of biodegradable polyurethane with tailored microtopographies onto commercial coronary stents. The topography of such stent coatings was modulated by controlling the ratio of round to stretched droplets or the ratio of round to crumped droplets under high electric field before deposition. The shape of electrosprayed droplets was governed by the stability of these charged droplets right after ejection or during their flight in the air. Using the electrospraying technique, we achieved conformal polymeric coatings with tailored microtopographies onto conductive surgical implants. The approach offers potential for controlling the surface topography of surgical implant devices to modulate their integration with surrounding tissues. PMID:26090663

  1. Electrospray synthesis and properties of hierarchically structured PLGA TIPS microspheres for use as controlled release technologies.

    PubMed

    Malik, Salman A; Ng, Wing H; Bowen, James; Tang, Justin; Gomez, Alessandro; Kenyon, Anthony J; Day, Richard M

    2016-04-01

    Microsphere-based controlled release technologies have been utilized for the long-term delivery of proteins, peptides and antibiotics, although their synthesis poses substantial challenges owing to formulation complexities, lack of scalability, and cost. To address these shortcomings, we used the electrospray process as a reproducible, synthesis technique to manufacture highly porous (>94%) microspheres while maintaining control over particle structure and size. Here we report a successful formulation recipe used to generate spherical poly(lactic-co-glycolic) acid (PLGA) microspheres using the electrospray (ES) coupled with a novel thermally induced phase separation (TIPS) process with a tailored Liquid Nitrogen (LN2) collection scheme. We show how size, shape and porosity of resulting microspheres can be controlled by judiciously varying electrospray processing parameters and we demonstrate examples in which the particle size (and porosity) affect release kinetics. The effect of electrospray treatment on the particles and their physicochemical properties are characterized by scanning electron microscopy, confocal Raman microscopy, thermogravimetric analysis and mercury intrusion porosimetry. The microspheres manufactured here have successfully demonstrated long-term delivery (i.e. 1week) of an active agent, enabling sustained release of a dye with minimal physical degradation and have verified the potential of scalable electrospray technologies for an innovative TIPS-based microsphere production protocol. PMID:26803601

  2. PCR-Electrospray Ionization Mass Spectrometry for Direct Detection of Pathogens and Antimicrobial Resistance from Heart Valves in Patients with Infective Endocarditis

    PubMed Central

    Brinkman, Cassandra L.; Vergidis, Paschalis; Uhl, James R.; Pritt, Bobbi S.; Cockerill, Franklin R.; Steckelberg, James M.; Baddour, Larry M.; Maleszewski, Joseph J.; Edwards, William D.; Sampath, Rangarajan

    2013-01-01

    Microbiological diagnosis is pivotal to the appropriate management and treatment of infective endocarditis. We evaluated PCR-electrospray ionization mass spectrometry (PCR/ESI-MS) for bacterial and candidal detection using 83 formalin-fixed paraffin-embedded heart valves from subjects with endocarditis who had positive valve and/or blood cultures, 63 of whom had positive valvular Gram stains. PCR/ESI-MS yielded 55% positivity with concordant microbiology at the genus/species or organism group level (e.g., viridans group streptococci), 11% positivity with discordant microbiology, and 34% with no detection. PCR/ESI-MS detected all antimicrobial resistance encoded by mecA or vanA/B and identified a case of Tropheryma whipplei endocarditis not previously recognized. PMID:23596241

  3. Ionised concentrations in calcium and magnesium buffers: Standards and precise measurement are mandatory.

    PubMed

    McGuigan, John A S; Kay, James W; Elder, Hugh Y

    2016-09-01

    In Ca(2+) and Mg(2+) buffer solutions the ionised concentrations ([X(2+)]) are either calculated or measured. Calculated values vary by up to a factor of seven due to the following four problems: 1) There is no agreement amongst the tabulated constants in the literature. These constants have usually to be corrected for ionic strength and temperature. 2) The ionic strength correction entails the calculation of the single ion activity coefficient, which involves non-thermodynamic assumptions; the data for temperature correction is not always available. 3) Measured pH is in terms of activity i.e. pHa. pHa measurements are complicated by the change in the liquid junction potentials at the reference electrode making an accurate conversion from H(+) activity to H(+) concentration uncertain. 4) Ligands such as EGTA bind water and are not 100% pure. Ligand purity has to be measured, even when the [X(2+)] are calculated. The calculated [X(2+)] in buffers are so inconsistent that calculation is not an option. Until standards are available, the [X(2+)] in the buffers must be measured. The Ligand Optimisation Method is an accurate and independently verified method of doing this (McGuigan & Stumpff, Anal. Biochem. 436, 29, 2013). Lack of standards means it is not possible to compare the published [Ca(2+)] in the nmolar range, and the apparent constant (K(/)) values for Ca(2+) and Mg(2+) binding to intracellular ligands amongst different laboratories. Standardisation of Ca(2+)/Mg(2+) buffers is now essential. The parameters to achieve this are proposed. PMID:26975789

  4. The Vertical Structure of Warm Ionised Gas in the Milky Way

    NASA Astrophysics Data System (ADS)

    Gaensler, B. M.; Madsen, G. J.; Chatterjee, S.; Mao, S. A.

    2008-11-01

    We present a new joint analysis of pulsar dispersion measures and diffuse Hα emission in the Milky Way, which we use to derive the density, pressure and filling factor of the thick disk component of the warm ionised medium (WIM) as a function of height above the Galactic disk. By excluding sightlines at low Galactic latitude that are contaminated by Hii regions and spiral arms, we find that the exponential scale-height of free electrons in the diffuse WIM is 1830-250+120 pc, a factor of two larger than has been derived in previous studies. The corresponding inconsistent scale heights for dispersion measure and emission measure imply that the vertical profiles of mass and pressure in the WIM are decoupled, and that the filling factor of WIM clouds is a geometric response to the competing environmental influences of thermal and non-thermal processes. Extrapolating the properties of the thick-disk WIM to mid-plane, we infer a volume-averaged electron density 0.014 +/- 0.001 cm-3, produced by clouds of typical electron density 0.34 +/- 0.06 cm-3 with a volume filling factor 0.04 +/- 0.01. As one moves off the plane, the filling factor increases to a maximum of ~30% at a height of ~1-1.5 kpc, before then declining to accommodate the increasing presence of hot, coronal gas. Since models for the WIM with a ~1 kpc scale-height have been widely used to estimate distances to radio pulsars, our revised parameters suggest that the distances to many high-latitude pulsars have been substantially underestimated.

  5. Ionised concentrations in calcium and magnesium buffers: Standards and precise measurement are mandatory.

    PubMed

    McGuigan, John A S; Kay, James W; Elder, Hugh Y

    2016-09-01

    In Ca(2+) and Mg(2+) buffer solutions the ionised concentrations ([X(2+)]) are either calculated or measured. Calculated values vary by up to a factor of seven due to the following four problems: 1) There is no agreement amongst the tabulated constants in the literature. These constants have usually to be corrected for ionic strength and temperature. 2) The ionic strength correction entails the calculation of the single ion activity coefficient, which involves non-thermodynamic assumptions; the data for temperature correction is not always available. 3) Measured pH is in terms of activity i.e. pHa. pHa measurements are complicated by the change in the liquid junction potentials at the reference electrode making an accurate conversion from H(+) activity to H(+) concentration uncertain. 4) Ligands such as EGTA bind water and are not 100% pure. Ligand purity has to be measured, even when the [X(2+)] are calculated. The calculated [X(2+)] in buffers are so inconsistent that calculation is not an option. Until standards are available, the [X(2+)] in the buffers must be measured. The Ligand Optimisation Method is an accurate and independently verified method of doing this (McGuigan & Stumpff, Anal. Biochem. 436, 29, 2013). Lack of standards means it is not possible to compare the published [Ca(2+)] in the nmolar range, and the apparent constant (K(/)) values for Ca(2+) and Mg(2+) binding to intracellular ligands amongst different laboratories. Standardisation of Ca(2+)/Mg(2+) buffers is now essential. The parameters to achieve this are proposed.

  6. Low-dose ionising radiation and cardiovascular diseases--Strategies for molecular epidemiological studies in Europe.

    PubMed

    Kreuzer, Michaela; Auvinen, Anssi; Cardis, Elisabeth; Hall, Janet; Jourdain, Jean-Rene; Laurier, Dominique; Little, Mark P; Peters, Annette; Raj, Ken; Russell, Nicola S; Tapio, Soile; Zhang, Wei; Gomolka, Maria

    2015-01-01

    It is well established that high-dose ionising radiation causes cardiovascular diseases. In contrast, the evidence for a causal relationship between long-term risk of cardiovascular diseases after moderate doses (0.5-5 Gy) is suggestive and weak after low doses (<0.5 Gy). However, evidence is emerging that doses under 0.5 Gy may also increase long-term risk of cardiovascular disease. This would have major implications for radiation protection with respect to medical use of radiation for diagnostic purposes and occupational or environmental radiation exposure. Therefore, it is of great importance to gain information about the presence and possible magnitude of radiation-related cardiovascular disease risk at doses of less than 0.5 Gy. The biological mechanisms implicated in any such effects are unclear and results from epidemiological studies are inconsistent. Molecular epidemiological studies can improve the understanding of the pathogenesis and the risk estimation of radiation-induced circulatory disease at low doses. Within the European DoReMi (Low Dose Research towards Multidisciplinary Integration) project, strategies to conduct molecular epidemiological studies in this field have been developed and evaluated. Key potentially useful European cohorts are the Mayak workers, other nuclear workers, uranium miners, Chernobyl liquidators, the Techa river residents and several diagnostic or low-dose radiotherapy patient cohorts. Criteria for informative studies are given and biomarkers to be investigated suggested. A close collaboration between epidemiology, biology and dosimetry is recommended, not only among experts in the radiation field, but also those in cardiovascular diseases. PMID:26041268

  7. Investigation of the Impact of Desorption Electrospray Ionization Sprayer Geometry on Its Performance in Imaging of Biological Tissue.

    PubMed

    Tillner, Jocelyn; McKenzie, James S; Jones, Emrys A; Speller, Abigail V M; Walsh, James L; Veselkov, Kirill A; Bunch, Josephine; Takats, Zoltan; Gilmore, Ian S

    2016-05-01

    In this study, the impact of sprayer design and geometry on performance in desorption electrospray ionization mass spectrometry (DESI-MS) is assessed, as the sprayer is thought to be a major source of variability. Absolute intensity repeatability, spectral composition, and classification accuracy for biological tissues are considered. Marked differences in tissue analysis performance are seen between the commercially available and a lab-built sprayer. These are thought to be associated with the geometry of the solvent capillary and the resulting shape of the primary electrospray. Experiments with a sprayer with a fixed solvent capillary position show that capillary orientation has a crucial impact on tissue complex lipid signal and can lead to an almost complete loss of signal. Absolute intensity repeatability is compared for five lab-built sprayers using pork liver sections. Repeatability ranges from 1 to 224% for individual sprayers and peaks of different spectral abundance. Between sprayers, repeatability is 16%, 9%, 23%, and 34% for high, medium, low, and very low abundance peaks, respectively. To assess the impact of sprayer variability on tissue classification using multivariate statistical tools, nine human colorectal adenocarcinoma sections are analyzed with three lab-built sprayers, and classification accuracy for adenocarcinoma versus the surrounding stroma is assessed. It ranges from 80.7 to 94.5% between the three sprayers and is 86.5% overall. The presented results confirm that the sprayer setup needs to be closely controlled to obtain reliable data, and a new sprayer setup with a fixed solvent capillary geometry should be developed.

  8. Investigation of the Impact of Desorption Electrospray Ionization Sprayer Geometry on Its Performance in Imaging of Biological Tissue.

    PubMed

    Tillner, Jocelyn; McKenzie, James S; Jones, Emrys A; Speller, Abigail V M; Walsh, James L; Veselkov, Kirill A; Bunch, Josephine; Takats, Zoltan; Gilmore, Ian S

    2016-05-01

    In this study, the impact of sprayer design and geometry on performance in desorption electrospray ionization mass spectrometry (DESI-MS) is assessed, as the sprayer is thought to be a major source of variability. Absolute intensity repeatability, spectral composition, and classification accuracy for biological tissues are considered. Marked differences in tissue analysis performance are seen between the commercially available and a lab-built sprayer. These are thought to be associated with the geometry of the solvent capillary and the resulting shape of the primary electrospray. Experiments with a sprayer with a fixed solvent capillary position show that capillary orientation has a crucial impact on tissue complex lipid signal and can lead to an almost complete loss of signal. Absolute intensity repeatability is compared for five lab-built sprayers using pork liver sections. Repeatability ranges from 1 to 224% for individual sprayers and peaks of different spectral abundance. Between sprayers, repeatability is 16%, 9%, 23%, and 34% for high, medium, low, and very low abundance peaks, respectively. To assess the impact of sprayer variability on tissue classification using multivariate statistical tools, nine human colorectal adenocarcinoma sections are analyzed with three lab-built sprayers, and classification accuracy for adenocarcinoma versus the surrounding stroma is assessed. It ranges from 80.7 to 94.5% between the three sprayers and is 86.5% overall. The presented results confirm that the sprayer setup needs to be closely controlled to obtain reliable data, and a new sprayer setup with a fixed solvent capillary geometry should be developed. PMID:27014929

  9. Neutral loss analysis of amino acids by desorption electrospray ionization using an unmodified tandem quadrupole mass spectrometer.

    PubMed

    Corso, Gaetano; Paglia, Giuseppe; Garofalo, Daniela; D'Apolito, Oceania

    2007-01-01

    A new method to analyze free amino acids using desorption electrospray ionization (DESI) has been implemented. The method is based on the neutral loss mode determination of underivatized amino acids using a tandem quadrupole mass spectrometer equipped with an unmodified atmospheric interface. Qualitative and quantitative optimization of DESI parameters, including ESI voltage, solvent flow rate, angle of collection and incidence, gas flow and temperatures, was performed for amino acids detection. The parameters for DESI analysis were evaluated using a mixture of valine, leucine, methionine, phenylalanine and tyrosine standards. A few microliters of this mixture were deposited on a slide, dried and analyzed at a flow rate of 2 microL/min. The optimal ionization response was obtained using laboratory glass slides and an equivalent solution of water/methanol doped with 2% of formic acid. The method specificity was evaluated by comparing product ion spectra and neutral loss analysis of amino acids obtained either by DESI or by electrospray ionization flow injection analysis (ESI-FIA). To evaluate the quantitative response on amino acids analyzed by DESI, calibration curves were performed on amino acid standard solutions spiked with a fixed amount of labelled amino acids. The method was also employed to analyze free amino acids from blood spots, after a rapid solvent extraction without other sample pretreatment, from positive and negative subjects. The method enables one to analyze biological samples and to discriminate healthy subjects from patients affected by inherited metabolic diseases. The intrinsic high-throughput analysis of DESI represents an opportunity, because of its potential application in clinical chemistry, for the expanded screening of some inborn errors of metabolism.

  10. A study of inter-species ion suppression in electrospray ionization-mass spectrometry of some phospholipid classes.

    PubMed

    Khoury, Spiro; El Banna, Nadine; Tfaili, Sana; Chaminade, Pierre

    2016-02-01

    Phospholipid quantification in biological samples is crucial and is increasingly studied in lipidomics. Quantitative studies are often performed using commercially available standards of phospholipid classes in order to mimic the composition of biological samples. For this, studies are conducted by liquid chromatography coupled to electrospray ionization-mass spectrometry. In liquid chromatography coupled to mass spectrometry (LC-MS) analysis, the matrix components and the co-elution of several phospholipid species lead to the phenomenon of ion suppression. As a result, a decrease in the response of phospholipid species in mass spectrometry MS is observed. In fact, inter-species ion suppression affects the efficiency of phospholipid (PL) ionization and might also influence the quantitative results. The aim of this work is to study the PL inter-species ion suppression phenomenon in electrospray ionization (ESI)-mass spectrometry on a triple quadrupole TQ and an LTQ-Orbitrap in order to improve quantification in natural and biological samples. Thus, the phospholipid MS response was evaluated to study the effect of acyl chain length, the degree, and the position of unsaturation on acyl chain and the effect of the polar head group structure. A number of saturated and unsaturated phospholipid species and mixtures were analyzed in different ionization modes to a better understanding of inter-species ion suppression phenomenon. PL molecular species responded differently according to the length of fatty acid chains, the number of unsaturation, and the nature of the polar head group. Fatty acid chain length showed to have the most marked effect on MS response.

  11. Titanium dioxide thin film deposited on flexible substrate by multi-jet electrospraying

    NASA Astrophysics Data System (ADS)

    Ni, Daihong; Yi, Wuming; Cao, Zhoubin; Gu, Wenhua

    2015-10-01

    Titanium dioxide thin film plays an important role in thin film solar cells, and has promising future in everyday applications including air cleaning and self-cleaning glass. With the concepts of flexible solar cells and wearable devices being more and more popular, there is increasing interest to coat titanium dioxide thin films on flexible substrates, such as aluminum foils. Many methods have been used to fabricate titanium dioxide thin films, such as dip-coating, spin coating, aerosol spray, plasma-assisted coating, electrospraying, and so on. Among them, electrospraying is especially suitable for thin film deposition on flexible substrates. This work reports fabrication of dense and uniform titanium dioxide thin films on glass as well as flexible aluminum foil using multi-jet electrospraying technique.

  12. Studies on the controlled morphology and wettability of PS surfaces by electrospinning or electrospraying.

    NASA Astrophysics Data System (ADS)

    Zheng, Jianfen; He, Aihua; Han, Charles

    2007-03-01

    Electrospinning/electrospraying is a simple and effective way to fabricate various polymer surfaces such as beads, fibers and other shapes in the range of micro- to nanometer. Various surface morphologies have been produced by electrospinning or electrospraying: beads with different sizes and shapes, bead-on-string structure with different aspect ratios and fibers with different diameters and shapes. Physical properties of the PS solutions such as viscosity, surface tension and conductivity greatly influence the electrospun or electrosprayed PS morphology. The wettability of a solid surface is greatly influenced by its surface morphology: A spin-coated PS membrane has a water contact angle of 97^o, while electrospun PS membranes have water contact angles around 150^o. The most hydrophobic membrane has a water CA of 159.5^o.

  13. Secondary electrospray ionization ion mobility spectrometry/mass spectrometry of illicit drugs.

    PubMed

    Wu, C; Siems, W F; Hill, H H

    2000-01-15

    A secondary electrospray ionization (SESI) method was developed as a nonradioactive ionization source for ion mobility spectrometry (IMS). This SESI method relied on the gas-phase interaction between charged particles created by electrospray ionization (ESI) and neutral gaseous sample molecules. Mass spectrometry (MS) was used as the detection method after ion mobility separation for ion identification. Preliminary investigations focussed on understanding the ionization process of SESI. The performance of ESI-IMS and SESI-IMS for illicit drug detection was evaluated by determining the analytical figures of merit. In general, SESI had a higher ionization efficiency for small volatile molecules compared with the electrospray method. The potential of developing a universal interface for both GC- and LC-MS with an addition stage of mobility separation was demonstrated.

  14. Molecular ions and protonated molecules observed in the atmospheric solids analysis probe analysis of steroids.

    PubMed

    Ray, Andrew D; Hammond, Janet; Major, Hilary

    2010-01-01

    Atmospheric pressure chemical ionisation (APCI) has often been used to ionise steroids in mass spectrometry, usually when interfaced to high-performance liquid chromatography (HPLC). However, in positive ion mode, a dehydrated protonated molecule is often observed with a loss of structural information. The recently introduced technique of atmospheric solids analysis probe (ASAP) has the advantage that the sample can be analysed directly and does not need to be interfaced to HPLC. Existing ionisation sources such as direct analysis in real time (DART) and desorption electrospray ionisation (DESI) have shown the advantage of direct analysis techniques in a variety of applications. ASAP can be performed on commercial atmospheric pressure ionisation (API) mass spectrometers with only simple modifications to API sources. The samples are vaporised by hot nitrogen gas from the electrospray desolvation heater and ionised by a corona discharge. A range of commercially available steroids were analysed by ASAP to investigate the mechanism of ionisation. ASAP analysis of steroids generally results in the formation of the parent molecular ion as either the radical cation M+* or the protonated molecule MH+. The formation of the protonated molecule is a result of proton transfer from ionised water clusters in the source. However, if the source is dry, then formation of the radical cation is the primary ionisation mechanism.

  15. Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

    PubMed

    Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

    2013-09-01

    From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). PMID:23937937

  16. Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

    PubMed

    Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

    2013-09-01

    From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI).

  17. Electrospray liquid chromatography quadrupole ion trap mass spectrometry determination of phenyl urea herbicides in water.

    PubMed

    Draper, W M

    2001-06-01

    Phenyl urea herbicides were determined in water by electrospray quadrupole ion trap liquid chromatography-mass spectrometry (ES-QIT-LC-MS). Over a wide concentration range [M - H](-) and MH(+) ions were prominent in ES spectra. At high concentrations dimer and trimer ions appeared, and sodium, potassium, and ammonium adducts also were observed. In the case of isopturon, source collision-induced dissociation (CID) fragmentation with low offset voltages increased the ion current associated with MH(+) and diminished dimer and trimer ion abundance. In the mass analyzer CID involved common pathways, for example, daughter ions of [M - H](-) resulted from loss of R(2)NH in N',N'-dialkyl ureas or loss of C(3)H(5)NO(2) (87 amu) in N'-methoxy ureas. A 2 mm (i.d.) x 15 cm C(18) reversed phase column was used for LC-MS with a linear methanol/water gradient and 0.5 mL/min flow rate. Between 1 and 100 pg/microg/L the response was highly linear with instrument detection limits ranging from <10 to 50 pg injected. Whereas the positive ES signal intensity was greater for each of the compounds except fluometuron, negative ion monitoring gave the highest signal-to-noise ratio. Analysis of spiked Colorado River water, a source high in total dissolved solids and total organic carbon, demonstrated that ES-QIT-LC-MS was routinely capable of quantitative analysis at low nanogram per liter concentrations in conjunction with a published C(18) SPE method. Under these conditions experimental method detection limits were between 8.0 and 36 ng/L, and accuracy for measurements in the 20-50 parts per trillion range was from 77 to 96%. Recoveries were slightly lower in surface water (e.g., 39-76%), possibly due to suppression of ionization. PMID:11409961

  18. Extractive electrospray ionization mass spectrometry toward in situ analysis without sample pretreatment.

    PubMed

    Li, Ming; Hu, Bin; Li, Jianqiang; Chen, Rong; Zhang, Xie; Chen, Huanwen

    2009-09-15

    A homemade novel nanoextractive electrospray ionization (nanoEESI) source has been characterized for in situ mass spectrometric analysis of ambient samples without sample pretreatment. The primary ions generated using a nanospray emitter interact with the neutral sample plume created by manually nebulizing liquid samples, allowing production of the analyte ions in the spatial cross section of the nanoEESI source. The performance of nanoEESI is experimentally investigated by coupling the nanoEESI source to a commercial LTQ mass spectrometer for rapid analysis of various ambient samples using positive/negative ion detection modes. Compounds of interest in actual samples such as aerosol drug preparations, beverages, milk suspensions, farmland water, and groundwater were unambiguously detected using tandem nanoEESI ion trap mass spectrometry. The limit of detection was low picogram per milliliter levels for the compounds tested. Acceptable relative standard deviation (RSD) values (5-10%) were obtained for direct measurement of analytes in complex matrixes, providing linear dynamic signal responses using manual sample introduction. A single sample analysis was completed within 1.2 s. Requiring no sheath gas for either primary ion production or neutral sample introduction, the nanoEESI has advantages including readiness for miniaturization and integration, simple maintenance, easy operation, and low cost. The experimental data demonstrate that the nanoEESI is a promising tool for high-throughput, sensitive, quantitative, in situ analysis of ambient complex samples, showing potential applications for in situ analysis in multiple disciplines including but not limited to pharmaceutical analysis, food quality control, pesticides residue detection, and homeland security.

  19. Search for liquids electrospraying the smallest possible nanodrops in vacuo

    SciTech Connect

    Alonso-Matilla, R.; Fernández-García, J.; Congdon, H.; Fernández de la Mora, J.

    2014-12-14

    Prior work with electrosprays in vacuum of mixtures of ionic liquids (ILs) and the moderately high boiling point (T{sub b}) solvents formamide (FM) and propylene carbonate (PC) (T{sub b} of 210 and 241 °C) has shown that the charged drops produced have reasonably narrow charge/mass distributions, controllable over a wide mass/charge range. This enables their use as propellants in electrical propulsion with specific impulse I{sub sp} varying from a few hundred to a few thousand seconds (10 kV beam energy) and with excellent propulsion efficiency. However, some limitations are imposed by the finite room temperature volatility of FM and PC. Here, we seek improved performance from propellants based on the polar but viscous solvent Sulfolane (SF; ε = 43.2, μ = 10.3 cP) and the low viscosity but less polar solvent tributyl phosphate (TBP; ε = 8.9, μ = 3.4 cP), both with T{sub b} > 280 °C. Neither TBP nor its low viscosity mixtures with SF achieve the electrical conductivities needed to yield high I{sub sp}. Most ILs used in SF/IL mixtures tested were based on the 1-ethyl-3-methylimidazolium (EMI) or 1,3-dimethylimidazolium (DMI) cations, including EMI-BF{sub 4}, EMI-N(CN){sub 2}, and DMI-N(CN){sub 2}. These combinations reach high conductivities, some approaching 3 S/m, but have limited propulsive performance because evaporation of ions directly from the electrified meniscus produces undesirable mixed beams of drops and ions. Exceptional characteristics are found in mixtures of SF with ethylammonium nitrate (EAN), where the small EA{sup +} cation is strongly bound to the solvent, greatly delaying ion evaporation from the meniscus. Evidence on the formation of nano-jets with diameters as small as 1 nm is seen. Although unprecedented, this finding agrees with what would be expected if ion evaporation were suppressed. SF/EAN mixtures thus provide the best available sources to produce the smallest possible nanodrops, minimally polluted by

  20. Enhanced Raman Scattering from Aromatic Dithiols Electrosprayed into Plasmonic Nanojunctions

    SciTech Connect

    El-Khoury, Patrick Z.; Johnson, Grant E.; Novikova, Irina V.; Gong, Yu; Joly, Alan G.; Evans, James E.; Zamkov, Mikhail; Laskin, Julia; Hess, Wayne P.

    2015-12-01

    We describe surface enhanced Raman spectroscopy (SERS) experiments in which molecular coverage is systematically varied from 3.8 x 105 to 3.8 x 102 to 0.38 molecules/μm2 using electrospray deposition of ethanolic 4,4’-dimercaptostilbene (DMS) solutions. The plasmonic SERS substrate used herein consists of a well-characterized 2-dimensional (2D) array of silver nanospheres [see El-Khoury et al., J. Chem. Phys., 2014, 141, 214308], previously shown to feature uniform topography and plasmonic response, as well as intense SERS activity. When compared to their ensemble averaged analogues, the spatially and temporally averaged spectra of a single molecule exhibit several unique features including: (i) distinct relative intensities of the observable Raman-active vibrational states, (ii) more pronounced SERS backgrounds, and (iii) broader Raman lines indicative of faster vibrational dephasing. The first observation may be understood on the basis of an intuitive physical picture in which removal of averaging over multiple molecules exposes the tensorial nature of Raman scattering. When an oriented single molecule gives rise to the recorded SERS spectra, the relative orientation of the molecule with respect to vector components of the local electric field determines the relative intensities of the observable vibrational states. Using a single molecule SERS framework described herein, we derive a unique molecular orientation in which a single DMS molecule is isolated at a nanojunction formed between two silver nanospheres in the 2D array. The DMS molecule is found lying nearly flat with respect to the metal surface. The derived orientation of a single molecule at a plasmonic nanojunction is consistent with observations (ii) and (iii). In particular, a careful inspection of the temporal spectral variations along the recorded single molecule SERS time sequences reveals that the time-averaged SERS backgrounds arise from individual molecular events, marked by broadened SERS

  1. Rapid differentiation of refined fuels using negative electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.; Hostettler, F.D.

    2005-01-01

    An application of electrospray ionization/mass spectrometry for identification of various commercially refined fuels using the unique signature of polar components, was investigated. The samples were analyzed by mass spectrometry using negative electrospray on an Agilent Series 1100 liquid chromatograph/mass spectrometer. These analysis were applied to hydrocarbon samples from a large, long-term fuel spill which were taken from the subsurface and different extent of biodegradation or weathering. The technique provided rapid identification of hydrocarbons released into the environment because these polar compounds are unique in different fuels.

  2. A novel method for the analysis of the substitution pattern of O-methyl-[alpha]- and [beta]-1,4-glucans by means of electrospray ionisation-mass spectrometry/collision induced dissociation

    NASA Astrophysics Data System (ADS)

    Adden, Roland; Mischnick, Petra

    2005-03-01

    The substitution pattern of O-methyl amylose and O-methyl cellulose was analysed after per-O-methylation (Me-d3), and partial hydrolysis by subsequent ESI-MS/CID of the sodium (MS2) and the lithium adducts (MS3). Based on previous studies about the influence of regioselective O-methylation on the fragmentation pathways of malto- and cello-oligosaccharides, we could calculate the contribution of a certain methyl pattern to a distinct signal in the reproducible ESI-MS2 daughter spectrum. Signal intensities obtained from each O-methyl-O-methyl-d3 disaccharide were distributed on the corresponding methyl patterns and accumulated for all peaks of the mother mass spectrum. Data from ESI-MS2 were not sufficient for disaccharides bearing methyl and deuteromethyl groups in the combination 2 and 4, 3 and 3, or 4 and 2. Further independent information was obtained by ESI-MS3 of the lithium adducts. Monomer composition of methyl celluloses and methyl amyloses obtained by this novel approach were in very good agreement with reference data from GLC of the partially methylated glucitol acetates after complete hydrolysis, reduction and acetylation.

  3. Lightning-driven inner radiation belt energy deposition into the atmosphere: implications for ionisation-levels and neutral chemistry

    NASA Astrophysics Data System (ADS)

    Rodger, C. J.; Enell, C.-F.; Turunen, E.; Clilverd, M. A.; Thomson, N. R.; Verronen, P. T.

    2007-08-01

    Lightning-generated whistlers lead to coupling between the troposphere, the Van Allen radiation belts and the lower-ionosphere through Whistler-induced electron precipitation (WEP). Lightning produced whistlers interact with cyclotron resonant radiation belt electrons, leading to pitch-angle scattering into the bounce loss cone and precipitation into the atmosphere. Here we consider the relative significance of WEP to the lower ionosphere and atmosphere by contrasting WEP produced ionisation rate changes with those from Galactic Cosmic Radiation (GCR) and solar photoionisation. During the day, WEP is never a significant source of ionisation in the lower ionosphere for any location or altitude. At nighttime, GCR is more significant than WEP at altitudes <68 km for all locations, above which WEP starts to dominate in North America and Central Europe. Between 75 and 80 km altitude WEP becomes more significant than GCR for the majority of spatial locations at which WEP deposits energy. The size of the regions in which WEP is the most important nighttime ionisation source peaks at ~80 km, depending on the relative contributions of WEP and nighttime solar Lyman-α. We also used the Sodankylä Ion Chemistry (SIC) model to consider the atmospheric consequences of WEP, focusing on a case-study period. Previous studies have also shown that energetic particle precipitation can lead to large-scale changes in the chemical makeup of the neutral atmosphere by enhancing minor chemical species that play a key role in the ozone balance of the middle atmosphere. However, SIC modelling indicates that the neutral atmospheric changes driven by WEP are insignificant due to the short timescale of the WEP bursts. Overall we find that WEP is a significant energy input into some parts of the lower ionosphere, depending on the latitude/longitude and altitude, but does not play a significant role in the neutral chemistry of the mesosphere.

  4. Liquid chromatography-flame ionisation detection using a nebuliser/spray chamber interface. Part 1. Design and testing.

    PubMed

    Young, Erepamowei; Smith, Roger M; Sharp, Barry L; Bone, Joanne R

    2012-05-01

    A nebuliser and spray chamber have been used to link a flow injection analyser to a flame ionisation detector, with the potential for the combination to be used as a universal detector for liquid chromatography. The hydrogen and air flows were adjusted to achieve a stable system. The detector responded to both volatile and involatile analytes and to compounds with and without chromophores, including alkanes, alkanols, aromatic amides and acids, phenols, amino-acids and carbohydrates and gave a linear response for many analytes. However, for involatile polar analytes it was necessary to add traces of acid or salt to the carrier stream to obtain a linear response. PMID:22410156

  5. Liquid chromatography-flame ionisation detection using a nebuliser/spray chamber interface. Part 2. Comparison of functional group responses.

    PubMed

    Young, Erepamowei; Smith, Roger M; Sharp, Barry L; Bone, Joanne R

    2012-05-01

    The application of a LC-nebuliser/spray chamber interface-flame ionisation detection has been demonstrated for the superheated water liquid chromatography of a wide range of aliphatic and aromatic analytes. The linearity and sensitivity of the response of volatile and involatile analytes have been compared. The response of the detector toward different analytes is similar to that in GC-FID and for volatile analytes was comparable to UV detection. However, the responses from involatile analytes, such as amino acids and carbohydrates, were poor and often lower than for a refractive index detector. PMID:22420954

  6. Nanostructured weathering steel for matrix-free laser desorption ionisation mass spectrometry and imaging of metabolites, drugs and complex glycans.

    PubMed

    Etxebarria, Juan; Calvo, Javier; Reichardt, Niels-Christian

    2014-06-01

    Weathering steel has been employed for the first time to prepare sample plates for matrix-free laser desorption ionisation mass spectrometry (LDI-MS) of small molecules up to a mass range of around 1500 Da. The effective UV absorption, heat conductivity and porosity of the nanostructured inner rust layer formed during passivation determine the excellent performance in LDI-MS for a broad range of different analyte classes. The inexpensive material was evaluated in a series of relevant analytical applications ranging from the matrix-free detection of serum metabolites, lactose quantification, lipid analysis in milk to the glycoprofiling of antibodies and imaging mass spectrometry of brain tissue samples. PMID:24737011

  7. Predicting the effects of ionising radiation on ecosystems by a generic model based on the Lotka-Volterra equations.

    PubMed

    Monte, Luigi

    2009-06-01

    The present work describes a model for predicting the population dynamics of the main components (resources and consumers) of terrestrial ecosystems exposed to ionising radiation. The ecosystem is modelled by the Lotka-Volterra equations with consumer competition. Linear dose-response relationships without threshold are assumed to relate the values of the model parameters to the dose rates. The model accounts for the migration of consumers from areas characterised by different levels of radionuclide contamination. The criteria to select the model parameter values are motivated by accounting for the results of the empirical studies of past decades. Examples of predictions for long-term chronic exposure are reported and discussed.

  8. Quantum-mechanical calculations of residual current density excited during gas ionisation by an intense two-colour laser pulse

    NASA Astrophysics Data System (ADS)

    Vvedenskii, N. V.; Romanov, A. A.; Silaev, A. A.

    2016-05-01

    By solving analytically and numerically the three-dimensional time-dependent Schrödinger equation, we have studied the excitation of a residual current density during gas ionisation by a two-colour laser pulse containing a field at the fundamental frequency and an additional field at the doubled frequency. We have found the dependences of the residual current density on the phase shift between the components of the field and on the intensity of the fundamental harmonic. It is shown that the strong-field approximation taking into account the interaction of freed electrons with the parent ion yields a good quantitative agreement with the results of direct numerical simulation.

  9. Current status of matrix-assisted laser desorption ionisation-time of flight mass spectrometry in the clinical microbiology laboratory.

    PubMed

    Kok, Jen; Chen, Sharon C A; Dwyer, Dominic E; Iredell, Jonathan R

    2013-01-01

    The integration of matrix-assisted laser desorption ionisation-time of flight mass spectrometry (MALDI-TOF MS) into many clinical microbiology laboratories has revolutionised routine pathogen identification. MALDI-TOF MS complements and has good potential to replace existing phenotypic identification methods. Results are available in a more clinically relevant timeframe, particularly in bacteraemic septic shock. Novel applications include strain typing and the detection of antimicrobial resistance, but these are not widely used. This review discusses the technical aspects, current applications, and limitations of MALDI-TOF MS.

  10. Laser ablation and ionisation by laser plasma radiation in the atmospheric-pressure mass spectrometry of organic compounds

    SciTech Connect

    Pento, A V; Nikiforov, S M; Simanovsky, Ya O; Grechnikov, A A; Alimpiev, S S

    2013-01-31

    A new method was developed for the mass spectrometric analysis of organic and bioorganic compounds, which involves laser ablation with the ionisation of its products by laser-plasma radiation and enables analysing gaseous, liquid, and solid substances at atmospheric pressure without sample preparation. The capabilities of this method were demonstrated by the examples of fast pharmaceutical composition screening, real-time atmosphere composition analysis, and construction of the mass spectrometric images of organic compound distributions in biological materials. (interaction of laser radiation with matter)

  11. Simulation of ultra thin film SOI transistors using a non-local ballistic model for impact ionisation

    NASA Astrophysics Data System (ADS)

    Armstrong, G. A.; French, W. D.

    1992-12-01

    To model bipolar snapback in thin film SOI transistors accurately, it is necessary to employ a non-local model of impact ionisation. Such a model, based on the "Lucky electron" theory, has been incorporated in a two-dimensional device simulator. Accurate prediction of bipolar holding voltage has been obtained for SOI transistors with sub-micron gate lengths. The model has been applied to analyse separately the effects of both lightly doped source and lightly doped drain in maximising the holding voltage. The advantage of using ultra thin highly doped SOI films in conjunction with a lightly doped drain is discussed.

  12. Electrospray deposition of chalcogenide glass films for gradient refractive index and quantum dot incorporation

    NASA Astrophysics Data System (ADS)

    Novak, Spencer

    Chalcogenide glasses (ChGs) are well-known for their optical properties, making them ideal candidates for emerging applications of mid-infrared microphotonic devices, such as lab-on-a-chip chemical sensing devices, which currently demand additional flexibility in processing and materials available to realize new device designs. Solution-derived processing of ChG films, initially developed in the 1980s by Chern and Lauks, has consisted mainly of spin-coating and offers unique advantages over the more traditional physical vapor deposition techniques. In the present effort, the nanoparticles of interest are luminescent quantum dots (QDs), which can be used as an on-chip source of light for a planar chemical sensing device. Prior efforts of QD incorporation have exposed limitations of spin-coating of ChG solutions, namely QD aggregation and material waste, along with incompatibility with larger scale manufacturing methods such roll-to-roll processing. This dissertation has evaluated electrospray (ES) as an alternative method of solution-derived chalcogenide glass film deposition. While employed in other materials systems, deposition of optical quality ChG films via electrospray has not been previously attempted, nor have parameters until now, been defined. This study has defined pre-cursor solution chemistry, electrospray jet process parameters required for formation of stable films, annealing protocols and resulting film attributes, yielding important correlations needed to realize high optical quality films. Electrosprayed films attributes were compared to those seen for spin coating and trade-offs in processing route and resulting quality, were identified. Optical properties of importance to device applications were defined, including surface roughness, refractive index, and infrared transmission. The use of a serpentine path of the spray over the substrate was demonstrated to obtain uniform thickness, blanket films, and demonstrates process compatibility with roll

  13. Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

    USGS Publications Warehouse

    Thurman, E.M.; Ferrer, I.; Barcelo, D.

    2001-01-01

    An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

  14. Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.; Leenheer, J.A.

    2004-01-01

    Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed.Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra. ?? 2004 Elsevier B.V. All rights reserved.

  15. Lithium Formate Ion Clusters Formation during Electrospray Ionization: Evidence of Magic Number Clusters by Mass Spectrometry and ab initio Calculations

    SciTech Connect

    Shukla, Anil K.; Bogdanov, Bogdan

    2015-02-10

    Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry. Singly as well as multiply charged clusters were formed with the general formulae, (HCOOLi)nLi+, (HCOOLi)nLimm+, (HCOOLi)nHCOO- and (HCOOLi)n(HCOO)mm-. Several magic number cluster ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)3Li+ being the most abundant and stable cluster ions. Fragmentations of singly charged clusters proceed first by the loss of a dimer unit ((HCOOLi)2) followed by sequential loss of monomer units (HCOOLi). In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)3Li+ at higher collision energies which later fragments to dimer and monomer ions in lower abundance. Quantum mechanical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

  16. Lipid A structure of Pseudoalteromonas haloplanktis TAC 125: use of electrospray ionization tandem mass spectrometry for the determination of fatty acid distribution.

    PubMed

    Corsaro, Maria Michela; Piaz, Fabrizio Dal; Lanzetta, Rosa; Parrilli, Michelangelo

    2002-05-01

    The use of electrospray Ionization (ESI) tandem mass spectrometry (MS/MS) for the structural determination of the lipid A components of the psychrophilic bacterium Pseudoalteromonas haloplanktis TAC 125 is reported. The lipid A contains the classical bisphosphorylated beta-(1' --> 6)-linked D-glucosamine disaccharide with 3-hydroxydodecanoyl residues (12 : 0 (3-OH)) linked both as esters and amides to 2', 3' (distal glucosamine) and 2, 3 positions (proximal glucosamine) of the sugar backbone. The hydroxyl of 12 : 0 (3-OH) fatty acid linked at the 3' position is esterified by a dodecanoyl residue (12 : 0). In addition to the pentaacyl component, a minor tetraacyl lipid A, lacking the acyl residue at position 3, was also found in the lipid A fraction. The advantage of this MS technique for the investigation of the intra-ring fragmentation, which is useful for the determination of fatty acyl residue distribution on each glucosamine unit, is emphasized.

  17. γH2AX Foci Form Preferentially in Euchromatin after Ionising-Radiation

    PubMed Central

    Cowell, Ian G.; Sunter, Nicola J.; Singh, Prim B.; Austin, Caroline A.; Durkacz, Barbara W.; Tilby, Michael J.

    2007-01-01

    Background The histone variant histone H2A.X comprises up to 25% of the H2A complement in mammalian cells. It is rapidly phosphorylated following exposure of cells to double-strand break (DSB) inducing agents such as ionising radiation. Within minutes of DSB generation, H2AX molecules are phosphorylated in large chromatin domains flanking DNA double-strand breaks (DSBs); these domains can be observed by immunofluorescence microscopy and are termed γH2AX foci. H2AX phosphorylation is believed to have a role mounting an efficient cellular response to DNA damage. Theoretical considerations suggest an essentially random chromosomal distribution of X-ray induced DSBs, and experimental evidence does not consistently indicate otherwise. However, we observed an apparently uneven distribution of γH2AX foci following X-irradiation with regions of the nucleus devoid of foci. Methodology/Principle Findings Using immunofluorescence microscopy, we show that focal phosphorylation of histone H2AX occurs preferentially in euchromatic regions of the genome following X-irradiation. H2AX phosphorylation has also been demonstrated previously to occur at stalled replication forks induced by UV radiation or exposure to agents such as hydroxyurea. In this study, treatment of S-phase cells with hydroxyurea lead to efficient H2AX phosphorylation in both euchromatin and heterochromatin at times when these chromatin compartments were undergoing replication. This suggests a block to H2AX phosphorylation in heterochromatin that is at least partially relieved by ongoing DNA replication. Conclusions/Significance We discus a number of possible mechanisms that could account for the observed pattern of H2AX phosphorylation. Since γH2AX is regarded as forming a platform for the recruitment or retention of other DNA repair and signaling molecules, these findings imply that the processing of DSBs in heterochromatin differs from that in euchromatic regions. The differential responses of

  18. New laboratory atomic data for neutral, singly and doubly ionised iron group elements for astrophysics applications

    NASA Astrophysics Data System (ADS)

    Pickering, Juliet C.; Nave, Gillian; Liggins, Florence; Clear, Christian; Ruffoni, Matthew; Sansonetti, Craig

    2015-08-01

    We present new laboratory spectroscopic measurements to produce atomic data for astrophysically important species: neutral, singly and doubly ionised iron group elements.We use high resolution Fourier Transform Spectrometry (FTS) (resolving power up to 2x106 at 200nm) to measure atomic spectra, giving accurate line wavelengths (to a few parts in 108), atomic energy levels, hyperfine structure splitting and log gfs (accurate to a few %) (Ruffoni et al this meeting). These data are vital for astrophysical spectral analyses for: line identification, spectrum synthesis, elemental abundance determinations [eg 1], and disentangling of blends etc. It is not possible to theoretically calculate these atomic data to the accuracy needed for modern astrophysics applications.At Imperial College we have a unique visible-VUV FT spectrometer with short wavelength cut-off of 135nm. We supplement FTS data at shorter wavelengths with spectra recorded on the NIST 10.7m grating spectrograph (with phosphor image or photographic plates) and at longer wavelengths in the IR we use the NIST IR FT spectrometer.An elemental spectrum may contain thousands of spectral lines from the IR to VUV. We use these wavelengths to correct known atomic energy levels, and search for new atomic levels. The result is a classified linelist and accurate atomic energy levels.We present progress on iron group element atomic energy levels and wavelengths for V I and V II [2,3], Co III [4], Cr I, Mn I and Mn II, and Ni II.This work is supported by STFC(UK), The Leverhulme Trust, The Royal Society and NASA.References[1] Bergemann M, Pickering JC & Gehren T,“NLTE analysis of Co I/Co II lines in spectra of cool stars with new laboratory hyperfine splitting constants",MNRAS 401(2) 1334 (2010)[2] Thorne AP, Pickering JC & Semeniuk J,“The spectrum and term analysis of V II”, ApJS 207,13 (2013)[3] Thorne AP, Pickering JC & Semeniuk J,“The spectrum and term analysis of V I",ApJS 192,11 (2011)[4] Smillie DG

  19. A numerical tool for the calculation of non-equilibrium ionisation states in the solar corona and other astrophysical plasma environments

    NASA Astrophysics Data System (ADS)

    Bradshaw, S. J.

    2009-07-01

    Context: The effects of non-equilibrium processes on the ionisation state of strongly emitting elements in the solar corona can be extremely difficult to assess and yet they are critically important. For example, there is much interest in dynamic heating events localised in the solar corona because they are believed to be responsible for its high temperature and yet recent work has shown that the hottest (≥107 K) emission predicted to be associated with these events can be observationally elusive due to the difficulty of creating the highly ionised states from which the expected emission arises. This leads to the possibility of observing instruments missing such heating events entirely. Aims: The equations describing the evolution of the ionisaton state are a very stiff system of coupled, partial differential equations whose solution can be numerically challenging and time-consuming. Without access to specialised codes and significant computational resources it is extremely difficult to avoid the assumption of an equilibrium ionisation state even when it clearly cannot be justified. The aim of the current work is to develop a computational tool to allow straightforward calculation of the time-dependent ionisation state for a wide variety of physical circumstances. Methods: A numerical model comprising the system of time-dependent ionisation equations for a particular element and tabulated values of plasma temperature as a function of time is developed. The tabulated values can be the solutions of an analytical model, the output from a numerical code or a set of observational measurements. An efficient numerical method to solve the ionisation equations is implemented. Results: A suite of tests is designed and run to demonstrate that the code provides reliable and accurate solutions for a number of scenarios including equilibration of the ion population and rapid heating followed by thermal conductive cooling. It is found that the solver can evolve the ionisation

  20. Revision of capillary cone-jet physics: electrospray and flow focusing.

    PubMed

    Gañán-Calvo, Alfonso M; Montanero, José M

    2009-06-01

    Capillary cone jets are natural microfluidic structures arising in steady capillary tip streaming, whose paradigms are electrospray and flow focusing phenomena. In this work, we make a profound revision of the basic underlying physics of generic cone jets from thousands of experimental measurements, most of them reported in the literature. First, the boundaries of the stability region of steady jetting are calculated. We describe these limitations by instability mechanisms associated with the local flow structure in the tip and the issuing jet and with the global behavior of the meniscus. Second, to undertake a general physical treatment of cone jets in steady regime, we analyze the energy balance taking place in the tips of both flow focusing and electrospray. This analysis yields a fundamental result: if the electrospray data are expressed in terms of an effective pressure drop, both phenomena satisfy the same scaling law for the droplet size, which exhibits nearly complete similarity in the parameter window where quasimonodisperse sprays are produced. That effective pressure drop is a function of the liquid properties exclusively, i.e., it does not depend on the operational parameters (flow rate and applied voltage). Moreover, the stability limits of the operational regimes are analyzed in detail, finding fundamental coincidences between flow focusing and electrospray as well. These results provide most useful general description and predictive scaling laws for nearly monodisperse microspraying or nanospraying based on steady cone jets, of immediate applicability in analytical chemistry, chemical engineering, biochemistry, pharmaceutical and food technologies, painting, and many other technological fields. PMID:19658592

  1. Electrospray painted article containing thermally exfoliated graphite oxide and method for their manufacture

    NASA Technical Reports Server (NTRS)

    Korkut, Sibel (Inventor); Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor)

    2011-01-01

    A painted polymer part containing a conductive polymer composition containing at least one polymer and a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the painted polymer part has been electrospray painted.

  2. Design, simulation, and fabrication of a MEMS-based air amplifier for electrospray ionization

    NASA Astrophysics Data System (ADS)

    Jurčíček, Petr; Zou, Helin; Gao, Shuai

    2013-04-01

    Recent developments in electrospray ionization mass spectrometry (ESI-MS) show that air amplifiers can be utilized to significantly enhance droplet desolvation and to focus gas-phase ions when provided between an electrospray (ES) source and the mass spectrometer (MS). However, these devices are bulky and expensive, which may be a factor prohibiting their broader utilization. We have developed a simple but effective method based on Bernoulli's principle, the Coanda effect and MEMS processing to focus electrosprayed droplets and liberated gas-phase ions. We demonstrate a computer simulation and fabrication process for a micromachined air amplifier. The simulation results are used to optimize the geometry and to meet performance requirements. The optimized results then provide a design guideline for the device's fabrication. The air amplifier is formed from two bonded polydimethylsiloxane (PDMS) casts. Each PDMS cast is fabricated through a molding process using a micromachined two-layer SU-8 mold. Experimental results show a 30-fold improvement in the ES current for certain operation conditions while the air amplifier is incorporated in the nano-electrospray ionization (nano-ESI) process. Compared with traditional air amplifiers, the micro-electro-mechanical systems (MEMS) based air amplifier provides good performance while keeping the fabrication process simple and cost effective.

  3. Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

    ERIC Educational Resources Information Center

    Stock, Naomi L.; March, Raymond E.

    2014-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

  4. Extractive Electrospray Ionization Mass Spectrometry of Heterogeneous Particles: Implications for Applications to Complex Atmospheric Aerosol

    NASA Astrophysics Data System (ADS)

    Longin, T.; Waring-Kidd, C.; Wingen, L. M.; Lyster, K.; Anderson, C.; Kumbhani, S.; Finlayson-Pitts, B. J.

    2015-12-01

    Extractive electrospray ionization mass spectrometry (EESI-MS) is a direct, real time technique for obtaining mass spectra of gases, liquid droplets, solid particles, and aerosols with little sample processing. EESI-MS involves the interaction of charged electrospray droplets with a separate spray containing the analyte of interest, but the exact mechanism by which the solvent droplets extract analyte from the sample is unclear. Possible mechanisms include complete coalescence of the sample particle with the solvent droplet in which all of the analyte is incorporated into the solvent or a more temporary interaction such that only some of the analyte is transferred to the solvent. Previous studies of the mechanism of EESI-MS on homogeneous particles indicate that both mechanisms are possible. We studied the behavior of EESI-MS toward heterogeneous particles created by coating NaCl particles with various thicknesses of organic diacids. Our results indicate that the signal strength depends on the solubility of the organic acid in the electrospray solvent, in agreement with previous studies, and also that the outer 10-15 nm of the particles are most susceptible to extraction into the electrospray droplets. Our results combined with those of previous studies suggest that the mass spectra obtained with EESI will not necessarily reflect the overall particle composition, especially for particles that are spatially inhomogeneous, and hence caution in interpretation of the data is advised for application to complex atmospheric aerosol.

  5. Surface modification and characterization of electrosprayed Sn-doped In2O3 thin films.

    PubMed

    Koo, Bon-Ryul; Ahn, Hyo-Jin

    2014-12-01

    We synthesized Sn-doped In2O3 (Indium tin oxide, ITO) thin films using electrospray and spin-coating. Scanning electron microscopy, atomic force spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Hall-effect measurement, and UV-vis spectrophotometry measurements were performed to investigate the morphological, structural, chemical, electrical, and optical properties of the electrosprayed ITO films with a sol-layer coating for surface modification. To obtain the optimum performance of the resultant ITO thin films after surface modification, we heat-treated them at four different temperatures of 450 degrees C (sample A), 550 degrees C (sample B), 650 degrees C (sample C), and 750 degrees C (sample D) using microwave heating. Surface modified ITO thin films calcined at 550 degrees C (sample B) using electrospray and spin-coating are observed to have superior resistivity (9.9 x 10(-3) 2 Ω x cm) and optical transmittance (-92.08%) owing to the improved densification of the ITO surface by spin-coating and the formation of uniform ITO thin films by electrospraying. PMID:25971111

  6. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    SciTech Connect

    Johnson, S.

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  7. Electrospray deposition of titanium dioxide (TiO{sub 2}) nanoparticles

    SciTech Connect

    Halimi, Siti Umairah Bakar, Noor Fitrah Abu Ismail, Siti Norazian Hashib, Syafiza Abd; Naim, M. Nazli

    2014-02-24

    Deposition of titanium dioxide (TiO{sub 2}) nanoparticles was conducted by using eletrospray method. 0.05wt% of titanium dioxide suspension was prepared and characterized by using Malvern Zetasizer prior to the experiment. From Zetasizer results, stable suspension condition was obtained which is at pH 2 with zeta potential value of ±29.0 mV. In this electrospraying, the suspension was pumped at flowrate of 5 ml/hr by using syringe pump. The input voltage of 2.1 kV was applied at the nozzle tip and counter electrode. Electrosprayed particles were collected on the grounded aluminium plate substrate which was placed at 10–20 cm from counter electrode. Particles were then characterized using FESEM and average size of electrosprayed particles obtained. Initial droplet size was calculated by scaling law and compared with FE-SEM results in order to prove droplet fission occur during electrospray. Due to the results obtained, as the working distance increase from 10–20 cm the deposited TiO{sub 2} droplet size decrease from 247–116 nm to show droplet fission occur during the experiment.

  8. Revision of capillary cone-jet physics: Electrospray and flow focusing

    NASA Astrophysics Data System (ADS)

    Gañán-Calvo, Alfonso M.; Montanero, José M.

    2009-06-01

    Capillary cone jets are natural microfluidic structures arising in steady capillary tip streaming, whose paradigms are electrospray and flow focusing phenomena. In this work, we make a profound revision of the basic underlying physics of generic cone jets from thousands of experimental measurements, most of them reported in the literature. First, the boundaries of the stability region of steady jetting are calculated. We describe these limitations by instability mechanisms associated with the local flow structure in the tip and the issuing jet and with the global behavior of the meniscus. Second, to undertake a general physical treatment of cone jets in steady regime, we analyze the energy balance taking place in the tips of both flow focusing and electrospray. This analysis yields a fundamental result: if the electrospray data are expressed in terms of an effective pressure drop, both phenomena satisfy the same scaling law for the droplet size, which exhibits nearly complete similarity in the parameter window where quasimonodisperse sprays are produced. That effective pressure drop is a function of the liquid properties exclusively, i.e., it does not depend on the operational parameters (flow rate and applied voltage). Moreover, the stability limits of the operational regimes are analyzed in detail, finding fundamental coincidences between flow focusing and electrospray as well. These results provide most useful general description and predictive scaling laws for nearly monodisperse microspraying or nanospraying based on steady cone jets, of immediate applicability in analytical chemistry, chemical engineering, biochemistry, pharmaceutical and food technologies, painting, and many other technological fields.

  9. Revision of capillary cone-jet physics: electrospray and flow focusing.

    PubMed

    Gañán-Calvo, Alfonso M; Montanero, José M

    2009-06-01

    Capillary cone jets are natural microfluidic structures arising in steady capillary tip streaming, whose paradigms are electrospray and flow focusing phenomena. In this work, we make a profound revision of the basic underlying physics of generic cone jets from thousands of experimental measurements, most of them reported in the literature. First, the boundaries of the stability region of steady jetting are calculated. We describe these limitations by instability mechanisms associated with the local flow structure in the tip and the issuing jet and with the global behavior of the meniscus. Second, to undertake a general physical treatment of cone jets in steady regime, we analyze the energy balance taking place in the tips of both flow focusing and electrospray. This analysis yields a fundamental result: if the electrospray data are expressed in terms of an effective pressure drop, both phenomena satisfy the same scaling law for the droplet size, which exhibits nearly complete similarity in the parameter window where quasimonodisperse sprays are produced. That effective pressure drop is a function of the liquid properties exclusively, i.e., it does not depend on the operational parameters (flow rate and applied voltage). Moreover, the stability limits of the operational regimes are analyzed in detail, finding fundamental coincidences between flow focusing and electrospray as well. These results provide most useful general description and predictive scaling laws for nearly monodisperse microspraying or nanospraying based on steady cone jets, of immediate applicability in analytical chemistry, chemical engineering, biochemistry, pharmaceutical and food technologies, painting, and many other technological fields.

  10. Regiospecific analysis of diricinoleoylacylglycerols in castor (Ricinus communis L.) oil by electrospray ionization-mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    HPLC fractions of diricinoleoyl-acyl-glycerols containing one non-ricinoleoyl chain from castor oil were used to identify the regiospecific location of this non-ricinoleoyl chain on glycerol backbone using electrospray ionization-MS3 of lithium adducts. The regiospecific ions used were from the loss...

  11. Identification of tetraacylglycerols in lesquerella oil by electrospray ionization mass spectrometry of the lithium adducts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Tetraacylglycerol (an acylglycerol estolide) contains an acyl chain attached to the hydroxyl group of another acyl chain attached to the glycerol backbone. Lequerolic acid (Ls, OH1420:111) is the main fatty acid in lequerella oil and can be used in industry. We have used electrospray ionization mass...

  12. Generation of naphthoquinone radical anions by electrospray ionization: solution, gas-phase, and computational chemistry studies.

    PubMed

    Vessecchi, Ricardo; Naal, Zeki; Lopes, José N C; Galembeck, Sérgio E; Lopes, Norberto P

    2011-06-01

    Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(•-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q+15](-) was described as being a reaction between the solvent system and the radical anion, Q(•-). The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses. PMID:21561138

  13. Examination and Manipulation of Protein Surface Charge in Solution with Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Gross, Deborah S.; Van Ryswyk, Hal

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for examining the charge of proteins in solution. The charge can be manipulated through choice of solvent and pH. Furthermore, solution-accessible, protonated lysine side chains can be specifically tagged with 18-crown-6 ether to form noncovalent adducts. Chemical derivatization…

  14. An electrodynamic ion funnel for electrospray ionization source based time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bhushan, K. G.; Rao, K. C.; Sule, U.; Reddy, P.; Rodrigues, S. M.; Gaikwad, D. T.; Mukundhan, R.; Gupta, S. K.

    2016-04-01

    An electrodynamic ion funnel has been developed for improving the sensitivity of electrospray ionization sources widely used in the mass spectrometric study of proteins and other biological macromolecules. The ion funnel consists of 52 electrodes and works under the combined influence of RF and DC voltages in the pressure range of 0.1 to 5 mbar. A novel feature of this ion funnel is the specific shape of the exit electrode that improves transmission of lower mass ions by reducing the depth of effective trapping potentials. In this paper, we report on the optimization of the ion funnel design using ion trajectory simulation software SIMION 8.0 especially in the mass range 500–5000 amu, followed by experimental observations of the ion transmission from the electrospray interface. It is seen that the electrospray-ion funnel combination greatly enhances the transmission when compared with an electrospray-skimmer interface. Ion currents > 1 nA could be obtained at the exit of the ion funnel for dilute Streptomycin Sulphate (~ 1500 amu) solution with the ion funnel operating in the 500–900 kHz frequency range, amplitude of 70 Vp‑p, under a DC gradient of about 20 Volts/cm at a background pressure of 0.3 mbar. Details of the construction of the ion funnel along with the experimental results are presented.

  15. Enhanced Raman scattering from aromatic dithiols electrosprayed into plasmonic nanojunctions.

    PubMed

    El-Khoury, Patrick Z; Johnson, Grant E; Novikova, Irina V; Gong, Yu; Joly, Alan G; Evans, James E; Zamkov, Mikhail; Laskin, Julia; Hess, Wayne P

    2015-01-01

    We describe surface enhanced Raman spectroscopy (SERS) experiments in which molecular coverage is systematically varied from 3.8 × 10(5) to 3.8 × 10(2) to 0.38 molecules per μm(2) using electrospray deposition of ethanolic 4,4'-dimercaptostilbene (DMS) solutions. The plasmonic SERS substrate used herein consists of a well-characterized 2-dimensional (2D) array of silver nanospheres (see El-Khoury et al., J. Chem. Phys., 2014, 141, 214308), previously shown to feature uniform topography and plasmonic response, as well as intense SERS activity. When compared to their ensemble averaged analogues, the spatially and temporally averaged spectra of a single molecule exhibit several unique features including: (i) distinct relative intensities of the observable Raman-active vibrational states, (ii) more pronounced SERS backgrounds, and (iii) broader Raman lines indicative of faster vibrational dephasing. The first observation may be understood on the basis of an intuitive physical picture in which the removal of averaging over multiple molecules exposes the tensorial nature of Raman scattering. When an oriented single molecule gives rise to the recorded SERS spectra, the relative orientation of the molecule with respect to vector components of the local electric field determines the relative intensities of the observable vibrational states. Using a single molecule SERS framework, described herein, we derive a unique molecular orientation in which a single DMS molecule is isolated at a nanojunction formed between two silver nanospheres in the 2D array. The DMS molecule is found lying nearly flat with respect to the metal. The derived orientation of a single molecule at a plasmonic nanojunction is consistent with observations (ii) and (iii). In particular, a careful inspection of the temporal spectral variations along the recorded single molecule SERS time sequences reveals that the time-averaged SERS backgrounds arise from individual molecular events, marked by broadened

  16. Enhanced Raman scattering from aromatic dithiols electrosprayed into plasmonic nanojunctions.

    PubMed

    El-Khoury, Patrick Z; Johnson, Grant E; Novikova, Irina V; Gong, Yu; Joly, Alan G; Evans, James E; Zamkov, Mikhail; Laskin, Julia; Hess, Wayne P

    2015-01-01

    We describe surface enhanced Raman spectroscopy (SERS) experiments in which molecular coverage is systematically varied from 3.8 × 10(5) to 3.8 × 10(2) to 0.38 molecules per μm(2) using electrospray deposition of ethanolic 4,4'-dimercaptostilbene (DMS) solutions. The plasmonic SERS substrate used herein consists of a well-characterized 2-dimensional (2D) array of silver nanospheres (see El-Khoury et al., J. Chem. Phys., 2014, 141, 214308), previously shown to feature uniform topography and plasmonic response, as well as intense SERS activity. When compared to their ensemble averaged analogues, the spatially and temporally averaged spectra of a single molecule exhibit several unique features including: (i) distinct relative intensities of the observable Raman-active vibrational states, (ii) more pronounced SERS backgrounds, and (iii) broader Raman lines indicative of faster vibrational dephasing. The first observation may be understood on the basis of an intuitive physical picture in which the removal of averaging over multiple molecules exposes the tensorial nature of Raman scattering. When an oriented single molecule gives rise to the recorded SERS spectra, the relative orientation of the molecule with respect to vector components of the local electric field determines the relative intensities of the observable vibrational states. Using a single molecule SERS framework, described herein, we derive a unique molecular orientation in which a single DMS molecule is isolated at a nanojunction formed between two silver nanospheres in the 2D array. The DMS molecule is found lying nearly flat with respect to the metal. The derived orientation of a single molecule at a plasmonic nanojunction is consistent with observations (ii) and (iii). In particular, a careful inspection of the temporal spectral variations along the recorded single molecule SERS time sequences reveals that the time-averaged SERS backgrounds arise from individual molecular events, marked by broadened

  17. Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

    SciTech Connect

    Shukla, Anil; Bogdanov, Bogdan

    2015-02-14

    Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

  18. Leaf Anatomy and Photochemical Behaviour of Solanum lycopersicum L. Plants from Seeds Irradiated with Low-LET Ionising Radiation

    PubMed Central

    De Micco, V.; Paradiso, R.; Aronne, G.; De Pascale, S.; Quarto, M.; Arena, C.

    2014-01-01

    Plants can be exposed to ionising radiation not only in Space but also on Earth, due to specific technological applications or after nuclear disasters. The response of plants to ionising radiation depends on radiation quality/quantity and/or plant characteristics. In this paper, we analyse some growth traits, leaf anatomy, and ecophysiological features of plants of Solanum lycopersicum L. “Microtom” grown from seeds irradiated with increasing doses of X-rays (0.3, 10, 20, 50, and 100 Gy). Both juvenile and compound leaves from plants developed from irradiated and control seeds were analysed through light and epifluorescence microscopy. Digital image analysis allowed quantifying anatomical parameters to detect the occurrence of signs of structural damage. Fluorescence parameters and total photosynthetic pigment content were analysed to evaluate the functioning of the photosynthetic machinery. Radiation did not affect percentage and rate of seed germination. Plants from irradiated seeds accomplished the crop cycle and showed a more compact habitus. Dose-depended tendencies of variations occurred in phenolic content, while other leaf anatomical parameters did not show distinct trends after irradiation. The sporadic perturbations of leaf structure, observed during the vegetative phase, after high levels of radiation were not so severe as to induce any significant alterations in photosynthetic efficiency. PMID:24883400

  19. Capillary zone electrophoresis of basic analytes in methanol as non-aqueous solvent mobility and ionisation constant.

    PubMed

    Porras, S P; Riekkola, M L; Kenndler, E

    2001-01-01

    The electrophoretically relevant properties of monoacidic 21 bases (including common drugs) containing aliphatic or aromatic amino groups were determined in methanol as solvent. These properties are the actual mobilities (that of the fully ionised weak bases), and their pKa values. Actual mobilities were measured in acidic methanolic solutions containing perchloric acid. The ionisation constants of the amines were derived from the dependence of the ionic mobilities on the pH of the background electrolyte solution. The pH scale in methanol was established from acids with known conventional pK*a values in this solvent used as buffers, avoiding thus further adjustment with a pH sensitive electrode that might bias the scale. Actual mobilities in methanol were found larger than in water, and do not correlate well with the solvent's viscosity. The pK*a values of the cation acids, HB-, the corresponding form of the base, B, are higher in methanol, whereas a less pronounced shift was found than for neutral acids of type HA. The mean increase (compared to pure aqueous solution) for aliphatic ammonium type analytes is 1.8, for substituted anilinium 1.1, and for aromatic ammonium from pyridinium type 0.5 units. The interpretation of this shift was undertaken with the concept of the medium effect on the particles involved in the acid-base equilibrium: the proton, the molecular base, B, and the cation HB+. PMID:11206793

  20. Internet-based ICRP resource for healthcare providers on the risks and benefits of medical imaging that uses ionising radiation.

    PubMed

    Demeter, S; Applegate, K E; Perez, M

    2016-06-01

    The purpose of the International Commission on Radiological Protection (ICRP) Committee 3 Working Party was to update the 2001 web-based module 'Radiation and your patient: a guide for medical practitioners' from ICRP. The key elements of this task were: to clearly identify the target audience (such as healthcare providers with an emphasis on primary care); to review other reputable sources of information; and to succinctly publish the contribution made by ICRP to the various topics. A 'question-and-answer' format addressing practical topics was adopted. These topics included benefits and risks of imaging using ionising radiation in common medical situations, as well as pertaining to specific populations such as pregnant, breast-feeding, and paediatric patients. In general, the benefits of medical imaging and related procedures far outweigh the potential risks associated with ionising radiation exposure. However, it is still important to ensure that the examinations are clinically justified, that the procedure is optimised to deliver the lowest dose commensurate with the medical purpose, and that consideration is given to diagnostic reference levels for particular classes of examinations.

  1. Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

    PubMed Central

    Rudd, David; Benkendorff, Kirsten; Voelcker, Nicolas H.

    2015-01-01

    Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS) methods namely nanostructure-assisted laser desorption ionisation (NALDI) and desorption ionisation on porous silicon (DIOS) surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples. PMID:25786067

  2. Optimized conditions for hydrocarbon group type analysis of base oils by thin-layer chromatography-flame ionisation detection.

    PubMed

    Kamiński, Marian; Gudebska, Joanna; Górecki, Tadeusz; Kartanowicz, Rafał

    2003-04-01

    The results of research on the optimization of the thin-layer chromatography-flame ionisation detection for the determination of group composition of natural base oils, including separation of the aromatics into subgroups, are presented. Neutral base oils obtained in several steps of refining from vacuum distillation petroleum fractions are the most difficult to analyze by hydrocarbon group type analysis (HGTA) because of the high content of aliphatic fragments in their molecules. Factors affecting the accuracy and precision of the results were identified. The paper presents the analytical procedure, including two different calibration methods, as well as the results of studies on the reproducibility of HGTA of typical base oils of different viscosity classes under the optimized conditions. The same conditions were found suitable for HGTA of other high-boiling petroleum fractions by TLC with flame ionisation detection. The paper also introduces a new procedure for reproducible determination of polar fractions in base oils utilizing solid-phase extraction columns, and presents a corrected procedure for the determination of saturated compounds and aromatics (mono-, bi- and polycyclic) in base oils by column liquid chromatography.

  3. Trefoil factor 3 (TFF3) enhances the oncogenic characteristics of prostate carcinoma cells and reduces sensitivity to ionising radiation.

    PubMed

    Perera, Omesha; Evans, Angharad; Pertziger, Mikhail; MacDonald, Christa; Chen, Helen; Liu, Dong-Xu; Lobie, Peter E; Perry, Jo K

    2015-05-28

    Trefoil factor 3 (TFF3) is a secreted protein which functions in mucosal repair of the gastrointestinal tract. This is achieved through the combined stimulation of cell migration and prevention of apoptosis and anoikis, thus facilitating repair. Deregulated TFF3 expression at the gene and protein level is implicated in numerous cancers. In prostate cancer TFF3 has previously been reported as a potential biomarker, overexpressed in a subset of primary and metastatic cases. Here we investigated the effect of increased TFF3 expression on prostate cancer cell behaviour. Oncomine analysis demonstrated that TFF3 mRNA expression was upregulated in prostate cancer compared to normal tissue. Forced-expression models were established in the prostate cancer cell lines, DU145 and PC3, by stable transfection of an expression vector containing the TFF3 cDNA. Forced expression of TFF3 significantly increased total cell number and cell viability, cell proliferation and cell survival. In addition, TFF3 enhanced anchorage independent growth, 3-dimensional colony formation, wound healing and cell migration compared to control transfected cell lines. We also observed reduced sensitivity to ionising radiation in stably transfected cell lines. In dose response experiments, forced expression of TFF3 significantly enhanced the regrowth of PC3 cells following ionising radiation compared with control transfected cells. In addition, TFF3 enhanced clonogenic survival of DU145 and PC3 cells. These studies indicate that targeting TFF3 for the treatment of prostate cancer warrants further investigation.

  4. Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

    NASA Astrophysics Data System (ADS)

    Le Breton, M.; Bacak, A.; Muller, J. B. A.; O'Shea, S. J.; Xiao, P.; Ashfold, M. N. R.; Cooke, M. C.; Batt, R.; Shallcross, D. E.; Oram, D. E.; Forster, G.; Bauguitte, S. J.-B.; Percival, C. J.

    2013-09-01

    A chemical ionisation mass spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I- reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume-defining techniques employing CO and CH3CN measurements. The 6-sigma technique produced the highest R2 values for correlations with CO. A normalised excess mixing ratio (NEMR) of 3.68 ± 0.149 pptv ppbv-1 was calculated, which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work, the emission total for HCN from BB was 0.92 Tg (N) yr-1.

  5. Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

    NASA Astrophysics Data System (ADS)

    Le Breton, M.; Bacak, A.; Muller, J. B. A.; O'Shea, S. J.; Xiao, P.; Ashfold, M. N. R.; Cooke, M. C.; Batt, R.; Shallcross, D. E.; Oram, D. E.; Forster, G.; Bauguitte, S. J.-B.; Percival, C. J.

    2013-02-01

    A Chemical Ionisation Mass Spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I- reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume defining techniques employing CO and CH3CN measurements. The 6 sigma technique produced the highest R2 values for correlations with CO. A Normalised Excess Mixing Ratio (NEMR) of 3.76 ± 0.022 pptv ppbv-1 was calculated which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work the emission total for HCN from BB was 0.92 Tg (N) yr-1.

  6. Optimisation of the quantitative determination of chlormequat by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Horak, J; Werther, W; Schmid, E R

    2001-01-01

    The plant growth regulator chlormequat, an involatile quaternary ammonium salt, has been quantified by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). Restrictions for quantitative MALDI-TOFMS analysis, such as irreproducible crystallisation and unsatisfactory laser stability, have been overcome by the application of two synthesised isotopically labelled standards and the optimisation of the measurement protocol. Data acquisition at constant laser power was compared to data acquisition at approximately constant ion abundance of the relevant ions (analyte and internal standards). Data acquisition at constant ion abundance performed better and enabled a high number of consecutive firings to the same sample deposition area. Furthermore an increased sample-to-sample repeatability and a high reproducibility over several weeks without re-calibration have been attained by this method. Linearity over three orders of magnitude (0.05 to 30 ng/microL chlormequat), with a correlation coefficient of 0.9997, was achieved using [13C3]-chlormequat as internal standard. Limit of detection and limit of determination were determined to be in the low pg/microL range for pure standard solutions. Thin-layer chromatography was applied for the removal of high amounts of choline, which is often present in plant tissue extracts and can adversely affect the ionisation and detection of chlormequat by MALDI-TOFMS. The use of two internal standards ([13C3]- and [2H9]-chlormequat) enabled direct quantification and simultaneous control of the recovery. PMID:11223954

  7. Study on the influence of the B4C layer thickness on the neutron flux and energy distribution shape in multi-electrode ionisation chamber.

    PubMed

    Tymińska, K; Maciak, M; Ośko, J; Tulik, P; Zielczyński, M; Gryziński, M A

    2014-10-01

    A model of a multi-electrode ionisation chamber, with polypropylene electrodes coated with a thin layer of B4C was created within Monte Carlo N-Particle Transport Code (MCNPX) and Fluktuierende Kaskade (FLUKA) codes. The influence of the layer thickness on neutron absorption in B4C and on the neutron spectra in the consecutive intra-electrode gas volumes has been studied using the MCNPX and FLUKA codes. The results will be used for designing the new type of the ionisation chamber.

  8. Study on the influence of the B4C layer thickness on the neutron flux and energy distribution shape in multi-electrode ionisation chamber.

    PubMed

    Tymińska, K; Maciak, M; Ośko, J; Tulik, P; Zielczyński, M; Gryziński, M A

    2014-10-01

    A model of a multi-electrode ionisation chamber, with polypropylene electrodes coated with a thin layer of B4C was created within Monte Carlo N-Particle Transport Code (MCNPX) and Fluktuierende Kaskade (FLUKA) codes. The influence of the layer thickness on neutron absorption in B4C and on the neutron spectra in the consecutive intra-electrode gas volumes has been studied using the MCNPX and FLUKA codes. The results will be used for designing the new type of the ionisation chamber. PMID:24729596

  9. Quantifying Protein-Fatty Acid Interactions Using Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Lan; Kitova, Elena N.; Klassen, John S.

    2011-02-01

    The application of the direct electrospray ionization mass spectrometry (ESI-MS) assay to quantify interactions between bovine β-lactoglobulin (Lg) and a series of fatty acids (FA), CH3(CH2)xCOOH, where x = 6 (caprylic acid, CpA), 8 (capric acid, CA), 10 (lauric acid, LA), 12 (myristic acid, MA), 14 (palmitic acid, PA) and 16 (stearic acid, SA), is described. Control ESI-MS binding measurements performed on the Lg-PA interaction revealed that both the protonated and deprotonated gas phase ions of the (Lg + PA) complex are prone to dissociate in the ion source, which leads to artificially small association constants ( K a ). The addition of imidazole, a stabilizing solution additive, at high concentration (10 mM) increased the relative abundance of (Lg + PA) complex measured by ESI-MS in both positive and negative ion modes. The K a value measured in negative ion mode and using sampling conditions that minimize in-source dissociation is in good agreement with a value determined using a competitive fluorescence assay. The K a values measured by ESI-MS for the Lg interactions with MA and SA are also consistent with values expected based on the fluorescence measurements. However, the K a values measured using optimal sampling conditions in positive ion mode are significantly lower than those measured in negative ion mode for all of the FAs investigated. It is concluded that the protonated gaseous ions of the (Lg + FA) complexes are kinetically less stable than the deprotonated ions. In-source dissociation was significant for the complexes of Lg with the shorter FAs (CpA, CA, and LA) in both modes and, in the case of CpA, no binding could be detected by ESI-MS. The affinities of Lg for CpA, CA, and LA determined using the reference ligand ESI-MS assay, a method for quantifying labile protein-ligand complexes that are prone to in-source dissociation, were found to be in good agreement with reported values.

  10. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    PubMed

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories. PMID:26168975

  11. An approach toward quantification of organic compounds in complex environmental samples using high-resolution electrospray ionization mass spectrometry

    SciTech Connect

    Nguyen, Tran B.; Nizkorodov, Sergey; Laskin, Alexander; Laskin, Julia

    2013-01-07

    Quantitative analysis of individual compounds in complex mixtures using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) is complicated by differences in the ionization efficiencies of analyte molecules in the mixture, resulting in signal suppression during ionization. However, the ability to obtain concentration estimates of compounds in an environmental sample is important for data interpretation and comparison. We introduce an approach for estimating mass concentrations of analytes observed in a multicomponent mixture by HR-ESI-MS, without prior separation. The approach relies on a calibration of the instrument using appropriate standards added to the mixture of studied analytes. An illustration of how the proposed calibration can be applied in practice is provided for aqueous extracts of isoprene photooxidation organic aerosol, with multifunctional organic acids standards. We show that the observed ion sensitivities in ESI-MS are positively correlated with the “adjusted mass,” defined as a product of the molecular mass and the H/C ratio in the molecule (adjusted mass = H/C x molecular mass). The correlation of the observed ESI sensitivity with adjusted mass is justified by considering trends of the physical and chemical properties of organic compounds that affect ionization in the positive ion mode, i.e., gas-phase basicity, polarizability, and molecular size.

  12. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    PubMed

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories.

  13. In situ analysis of Titan's tholins by Laser 2 steps Desorption Ionisation

    NASA Astrophysics Data System (ADS)

    Benilan, Y.; Carrasco, N.; Cernogora, G.; Gazeau, M.; Mahjoub, A.; Szopa, C.; Schwell, M.

    2013-12-01

    The main objective of the whole project developed in collaboration (LISA/LATMOS) is to provide a better understanding of the chemical composition of Titan aerosols laboratory analogs, called tholins, and thereby of their formation pathways. The tholins are produced in the PAMPRE reactor (French acronyme for Aerosols Microgravity Production by Reactives Plasmas) developed at LATMOS. These tholins are generated in levitation (wall effects are thus limited) in a low pressure radiofrequency plasma. Up to now, the determination of the physical and chemical properties of these tholins was achieved after their collection and ex-situ analysis by several methods. Their bulk composition was then determined but their insoluble part is still unknown. Other studies were performed after the transfer of the soluble part of the aerosols to different analytical instruments. Therefore, possible artifacts could have influenced the results. We present the SMARD (a French acronym for Mass Spectrometry of Aerosols by InfraRed Laser Desorption) program. A challenging issue of our work is to perform the soluble and unsoluble parts of PAMPRE tholins' analysis in real time and in situ. The coupling of the PAMPRE reactor to a unique instrument (Single Particle Laser Ablation Mass Spectrometry) developed at LISA should allow determining in real time and in situ the characteristics (chemical composition together with granulometry) of the nanometric aerosols. The later are introduced in the analytical instrument using an aerodynamic lens device. Their detection and aerodynamic diameter are determined using two continuous diode lasers operating at λ = 403 nm. Then, the L2DI (Laser 2 steps Desorption Ionisation) technique is used in order to access to the chemical composition of individual particles: they are vaporized using a 10 μm CO2 pulsed laser and the gas produced is then ionized by a 248 nm KrF Excimer laser. Finally, the molecular ions are analyzed by a 1 m linear time-of-flight mass

  14. Low-molecular weight protein profiling of genetically modified maize using fast liquid chromatography electrospray ionization and time-of-flight mass spectrometry.

    PubMed

    Koc, Anna; Cañuelo, Ana; Garcia-Reyes, Juan F; Molina-Diaz, Antonio; Trojanowicz, Marek

    2012-06-01

    In this work, the use of liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC-TOFMS) has been evaluated for the profiling of relatively low-molecular weight protein species in both genetically modified (GM) and non-GM maize. The proposed approach consisted of a straightforward sample fractionation with different water and ethanol-based buffer solutions followed by separation and detection of the protein species using liquid chromatography with a small particle size (1.8 μm) C(18) column and electrospray-time-of-flight mass spectrometry detection in the positive ionization mode. The fractionation of maize reference material containing different content of transgenic material (from 0 to 5% GM) led to five different fractions (albumins, globulins, zeins, zein-like glutelins, and glutelins), all of them containing different protein species (from 2 to 52 different species in each fraction). Some relevant differences in the quantity and types of protein species were observed in the different fractions of the reference material (with different GM contents) tested, thus revealing the potential use of the proposed approach for fast protein profiling and to detect tentative GMO markers in maize.

  15. Trace analysis of trimethoprim and sulfonamide, macrolide, quinolone, and tetracycline antibiotics in chlorinated drinking water using liquid chromatography electrospray tandem mass spectrometry

    USGS Publications Warehouse

    Ye, Z.; Weinberg, H.S.; Meyer, M.T.

    2007-01-01

    A multirun analytical method has been developed and validated for trace determination of 24 antibiotics including 7 sulfonamides, 3 macrolides, 7 quinolones, 6 tetracyclines, and trimethoprim in chlorine-disinfected drinking water using a single solid-phase extraction method coupled to liquid chromatography with positive electrospray tandem mass spectrometry detection. The analytes were extracted by a hydrophilic-lipophilic balanced resin and eluted with acidified methanol (0.1% formic acid), resulting in analyte recoveries generally above 90%. The limits of quantitation were mostly below 10 ng/L in drinking water. Since the concentrated sample matrix typically caused ion suppression during electrospray ionization, the method of standard addition was used for quantitation. Chlorine residuals in drinking water can react with some antibiotics, but ascorbic acid was found to be an effective chlorine quenching agent without affecting the analysis and stability of the antibiotics in water. A preliminary occurrence study using this method revealed the presence of some antibiotics in drinking waters, including sulfamethoxazole (3.0-3.4 ng/L), macrolides (1.4-4.9 ng/L), and quinolones (1.2-4.0 ng/L). ?? 2007 American Chemical Society.

  16. Low-molecular weight protein profiling of genetically modified maize using fast liquid chromatography electrospray ionization and time-of-flight mass spectrometry.

    PubMed

    Koc, Anna; Cañuelo, Ana; Garcia-Reyes, Juan F; Molina-Diaz, Antonio; Trojanowicz, Marek

    2012-06-01

    In this work, the use of liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC-TOFMS) has been evaluated for the profiling of relatively low-molecular weight protein species in both genetically modified (GM) and non-GM maize. The proposed approach consisted of a straightforward sample fractionation with different water and ethanol-based buffer solutions followed by separation and detection of the protein species using liquid chromatography with a small particle size (1.8 μm) C(18) column and electrospray-time-of-flight mass spectrometry detection in the positive ionization mode. The fractionation of maize reference material containing different content of transgenic material (from 0 to 5% GM) led to five different fractions (albumins, globulins, zeins, zein-like glutelins, and glutelins), all of them containing different protein species (from 2 to 52 different species in each fraction). Some relevant differences in the quantity and types of protein species were observed in the different fractions of the reference material (with different GM contents) tested, thus revealing the potential use of the proposed approach for fast protein profiling and to detect tentative GMO markers in maize. PMID:22740254

  17. Ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry coupled with hierarchical cluster analysis to evaluate Wikstroemia indica (L.) C. A. Mey. from different geographical regions.

    PubMed

    Wei, Lan; Wang, Xiaobo; Mu, Shanxue; Sun, Lixin; Yu, Zhiguo

    2015-06-01

    A sensitive, rapid and simple ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry method was developed to determine seven constituents (umbelliferone, apigenin, triumbelletin, daphnoretin, arctigenin, genkwanin and emodin) in Wikstroemia indica (L.) C. A. Mey. The chromatographic analysis was performed on an ACQUITY UPLC® BEH C18 column (2.1 × 50 mm, 1.7 μm) by gradient elution with the mobile phase of 0.05% formic acid aqueous solution (A) and acetonitrile (B). Multiple reaction monitoring mode with positive and negative electrospray ionization interface was carried out to detect the components. This method was validated in terms of specificity, linearity, accuracy, precision and stability. Excellent linear behavior was observed over the certain concentration ranges with the correlation coefficient values higher than 0.999. The intraday and innerday precisions were within 2.0%. The recoveries of seven analytes were 99.4-101.1% with relative standard deviation less than 1.2%. The 18 Wikstroemia indica samples from different origins were classified by hierarchical clustering analysis according to the contents of seven components. The results demonstrated that the developed method could successfully be used to quantify simultaneously of seven components in Wikstroemia indica and could be a helpful tool for the detection and confirmation of the quality of traditional Chinese medicines.

  18. Determination of cnidilin and its two metabolites in rat plasma by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry.

    PubMed

    Zhu, Hong; Liu, Pengwei; Shi, Xiaowei; Xu, Huijun; Ren, Yanping; Wang, Qiao; Zhang, Lantong

    2013-01-01

    Simple, fast, and sensitive HPLC coupled with an electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) method for the simultaneous determination of cnidilin and its two metabolites, 3",8-methoxy-isoimperatorin (M1) and 5"-hydroxyl-8-methoxy-isoimperatorin (M2), in rat plasma has been developed. Pimpinellin was used as the internal standard and the total analysis time was 7 min. Methanol was the only reagent during the process of sample handling used as a protein precipitant. The analytes were separated on a reversed-phase C18 column with gradient elution consisting of 0.5% aqueous formic acid and methanol (containing 0.5% formic acid) in the multiple-reaction monitoring mode. Cnidilin, M1, M2, and the internal standard could be well ionized under positive electrospray ionization conditions. Full validation of the method (linearity, precision, accuracy, limit of detection, and limit of quantification) was carried out and the method was successfully employed in a metabolism study of cnidilin administered to rats at a dose of 24 mg/kg. The pharmacokinetic parameters of cnidilin determined after orally administrating the single coumarin to the rat were obtained and the mass fragmentation pathways for analysis are proposed in this article. PMID:23188706

  19. Ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry coupled with hierarchical cluster analysis to evaluate Wikstroemia indica (L.) C. A. Mey. from different geographical regions.

    PubMed

    Wei, Lan; Wang, Xiaobo; Mu, Shanxue; Sun, Lixin; Yu, Zhiguo

    2015-06-01

    A sensitive, rapid and simple ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry method was developed to determine seven constituents (umbelliferone, apigenin, triumbelletin, daphnoretin, arctigenin, genkwanin and emodin) in Wikstroemia indica (L.) C. A. Mey. The chromatographic analysis was performed on an ACQUITY UPLC® BEH C18 column (2.1 × 50 mm, 1.7 μm) by gradient elution with the mobile phase of 0.05% formic acid aqueous solution (A) and acetonitrile (B). Multiple reaction monitoring mode with positive and negative electrospray ionization interface was carried out to detect the components. This method was validated in terms of specificity, linearity, accuracy, precision and stability. Excellent linear behavior was observed over the certain concentration ranges with the correlation coefficient values higher than 0.999. The intraday and innerday precisions were within 2.0%. The recoveries of seven analytes were 99.4-101.1% with relative standard deviation less than 1.2%. The 18 Wikstroemia indica samples from different origins were classified by hierarchical clustering analysis according to the contents of seven components. The results demonstrated that the developed method could successfully be used to quantify simultaneously of seven components in Wikstroemia indica and could be a helpful tool for the detection and confirmation of the quality of traditional Chinese medicines. PMID:25866087

  20. On-Tissue Derivatization via Electrospray Deposition for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging of Endogenous Fatty Acids in Rat Brain Tissues

    PubMed Central

    2016-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is used for the multiplex detection and characterization of diverse analytes over a wide mass range directly from tissues. However, analyte coverage with MALDI MSI is typically limited to the more abundant compounds, which have m/z values that are distinct from MALDI matrix-related ions. On-tissue analyte derivatization addresses these issues by selectively tagging functional groups specific to a class of analytes, while simultaneously changing their molecular masses and improving their desorption and ionization efficiency. We evaluated electrospray deposition of liquid-phase derivatization agents as a means of on-tissue analyte derivatization using 2-picolylamine; we were able to detect a range of endogenous fatty acids with MALDI MSI. When compared with airbrush application, electrospray led to a 3-fold improvement in detection limits and decreased analyte delocalization. Six fatty acids were detected and visualized from rat cerebrum tissue using a MALDI MSI instrument operating in positive mode. MALDI MSI of the hippocampal area allowed targeted fatty acid analysis of the dentate gyrus granule cell layer and the CA1 pyramidal layer with a 20-μm pixel width, without degrading the localization of other lipids during liquid-phase analyte derivatization. PMID:27181709

  1. Cloud-point extraction is compatible with liquid chromatography coupled to electrospray ionization mass spectrometry for the determination of bisoprolol in human plasma.

    PubMed

    Giebułtowicz, Joanna; Kojro, Grzegorz; Buś-Kwaśnik, Katarzyna; Rudzki, Piotr J; Marszałek, Ryszard; Leś, Andrzej; Wroczyński, Piotr

    2015-12-01

    Cloud-point extraction (CPE) draws increasing interest in a number of analytical fields including bioanalysis, but combining CPE and LC-MS with electrospray ionization (ESI) in the determination of drugs in biological fluids such as plasma, serum or blood has not been reported so far. Bisoprolol was determined in human plasma by CPE using Trition X-114 as a surfactant and metoprolol as the internal standard. NaOH concentration, temperature and Trition X-114 concentration were optimized. All analyses were performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). All validation experiments met international acceptance criteria and no significant matrix effect was observed. The compatibility of CPE and LC-ESI-MS/MS was confirmed using clinical plasma samples and appropriate statistical tests. The determination of bisoprolol concentration in human plasma in the range 1.0-70ngmL(-1) by the CPE method leads to the results which are equivalent to those obtained by the widely used liquid-liquid extraction method. The results revealed that a structural analogue may be an appropriate internal standard when CPE is used as the extraction technique. CPE offers significant practical advantages over the classical extraction methods, including a positive impact on the environment, therefore its wider application in future pharmacokinetic studies is justifiable.

  2. Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

    SciTech Connect

    Bateman, Adam P.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

    2012-07-02

    The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found between the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.

  3. On-Tissue Derivatization via Electrospray Deposition for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging of Endogenous Fatty Acids in Rat Brain Tissues.

    PubMed

    Wu, Qian; Comi, Troy J; Li, Bin; Rubakhin, Stanislav S; Sweedler, Jonathan V

    2016-06-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is used for the multiplex detection and characterization of diverse analytes over a wide mass range directly from tissues. However, analyte coverage with MALDI MSI is typically limited to the more abundant compounds, which have m/z values that are distinct from MALDI matrix-related ions. On-tissue analyte derivatization addresses these issues by selectively tagging functional groups specific to a class of analytes, while simultaneously changing their molecular masses and improving their desorption and ionization efficiency. We evaluated electrospray deposition of liquid-phase derivatization agents as a means of on-tissue analyte derivatization using 2-picolylamine; we were able to detect a range of endogenous fatty acids with MALDI MSI. When compared with airbrush application, electrospray led to a 3-fold improvement in detection limits and decreased analyte delocalization. Six fatty acids were detected and visualized from rat cerebrum tissue using a MALDI MSI instrument operating in positive mode. MALDI MSI of the hippocampal area allowed targeted fatty acid analysis of the dentate gyrus granule cell layer and the CA1 pyramidal layer with a 20-μm pixel width, without degrading the localization of other lipids during liquid-phase analyte derivatization.

  4. Nursing Positions

    MedlinePlus

    ... Story" 5 Things to Know About Zika & Pregnancy Nursing Positions KidsHealth > For Parents > Nursing Positions Print A ... and actually needs to feed. Getting Comfortable With Breastfeeding Nursing can be one of the most challenging ...

  5. Charge reduced electrospray size spectrometry of mega- and gigadalton complexes: whole viruses and virus fragments.

    PubMed

    Hogan, Christopher J; Kettleson, Eric M; Ramaswami, Bala; Chen, Da-Ren; Biswas, Pratim

    2006-02-01

    The ability to analyze and identify large macromolecular complexes whose molecular weight is beyond the analyzable range of mass spectrometry is of great interest. The size of such complexes makes them suitable for analysis via mobility size spectrometry. In this work, charge reduced electrospray size spectrometry was used for the analysis of bacteriophage viruses with total molecular masses ranging from 3.6 MDa up to the gigadalton range. The electrospray source used was operated in "cone jet" mode with a mean droplet diameter of 170.56 nm. Bacteriophage MS2 was found to have a mobility diameter of 24.13 +/- 0.06 nm and remain highly viable after the electrospray process. Larger bacteriophages T2 and T4 have lengths greater than the diameter of the electrospray jet and droplets; thus, they could not be completely enclosed and were found to fragment at the virus capsid head-tail noncovalent interface during either the jet formation or jet breakup process. No viable T2 or T4 virions were detectable after being electrosprayed. While the exact mechanism of fragmentation could not be determined, it is proposed here that macromolecular fragmentation at noncovalent interfaces occurs due to mechanically and electrically induced stresses during jet formation and jet breakup. Bacteriophage T4 capsid heads were found to be statistically significantly larger than bacteriophage T2 capsid heads, with a mean peak diameter of 88.32 +/- 1.02 nm for T4 and 87.03 +/- 0.18 nm for T2. While capsid head fragments were detectable, tail and tail-fiber fragments could not be detected by size spectrometric analysis. This is attributed to the fact that the contractile tails of bacteriophage T2 and T4 virions mechanically deform to a varying degree while confined within the smaller jet and droplets. Further evidence of contractile tail deformation during the electrospray process was found by measuring the size spectrum of bacteriophage lambda, which has a noncontractile tail. Bacteriophage

  6. Positive Psychology

    ERIC Educational Resources Information Center

    Peterson, Christopher

    2009-01-01

    Positive psychology is a deliberate correction to the focus of psychology on problems. Positive psychology does not deny the difficulties that people may experience but does suggest that sole attention to disorder leads to an incomplete view of the human condition. Positive psychologists concern themselves with four major topics: (1) positive…

  7. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    SciTech Connect

    Lentz, Nicholas B.

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

  8. Detection of saccharides by reactive desorption electrospray ionization (DESI) using modified phenylboronic acids

    NASA Astrophysics Data System (ADS)

    Zhang, Yun; Chen, Hao

    2010-01-01

    We have reported previously a method for the detection of sugars via in-situ derivatization with phenylboronic acid PhB(OH)2 using reactive desorption electrospray ionization (DESI, Chen et al., Chem. Commun. (2006) 597-599). The present study describes an improved method that employs modified phenylboronic acids including 3-nitrophenylboronic acid and N-methyl-4-pyridineboronic acid iodide. In contrast to using PhB(OH)2, enhanced sensitivity of using 3-nitrophenylboronic acid was observed due to the stabilization of the resulting boronate ester anion by the electron-withdrawing nitro group and the limit of detections (LODs) for glucose in water using 3-nitrophenylbornic acid and phenylboronic acid were determined to be 0.11 mM and 0.40 mM, respectively. In the case of N-methyl-4-pyridineboronic acid iodide, the corresponding LOD is 6.9 [mu]M and the higher sensitivity obtained is attributed to the efficient ionization of both the reactive DESI reagent and reaction product since the precursor acid with a quaternary ammonium group is pre-charged. In this case, additional important features are found: (i) unlike using phenylboronic acid or 3-nitrophenylbornic acid, the experiment, performed in the positive ion mode, is applicable to neutral and acidic saccharide solutions, facilitating the analysis of biological fluids without the need to adjust pH; (ii) simply by changing the spray solvent from water to acetonitrile, the method can be used for direct glucose analyses of both urine and serum samples via online desalting, due to the low solubility of salts of these biofluids in the sprayed organic solvent; (iii) in comparison with other sugar derivatizing reagents such as the Girard's reagent T, the N-methyl-4-pyridineboronic acid iodide shows higher reactivity in the reactive DESI; and (iv) the ions of saccharide DESI reaction products undergo extensive ring or glycosidic bond cleavage upon CID, a feature that might be useful in the structure elucidation of

  9. Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

    PubMed

    Warren, Alexander D; Conway, Ulric; Arthur, Christopher J; Gates, Paul J

    2016-07-01

    The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd.

  10. Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

    PubMed

    Warren, Alexander D; Conway, Ulric; Arthur, Christopher J; Gates, Paul J

    2016-07-01

    The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27434807

  11. Impact of molecular weight on the formation of electrosprayed chitosan microcapsules as delivery vehicles for bioactive compounds.

    PubMed

    Gómez-Mascaraque, Laura G; Sanchez, Gloria; López-Rubio, Amparo

    2016-10-01

    The molecular weight of chitosan is one of its most determinant characteristics, which affects its processability and its performance as a biomaterial. However, information about the effect of this parameter on the formation of electrosprayed chitosan microcapsules is scarce. In this work, the impact of chitosan molecular weight on its electrosprayability was studied and correlated with its effect on the viscosity, surface tension and electrical conductivity of solutions. A Discriminant Function Analysis revealed that the morphology of the electrosprayed chitosan materials could be correctly predicted using these three parameters for almost 85% of the samples. The suitability of using electrosprayed chitosan capsules as carriers for bioactive agents was also assessed by loading them with a model active compound, (-)-epigallocatechin gallate (EGCG). This encapsulation, with an estimated efficiency of around 80% in terms of preserved antioxidant activity, showed the potential to prolong the antiviral activity of EGCG against murine norovirus via gradual bioactive release combined with its protection against degradation in simulated physiological conditions.

  12. In-Situ Organic Compound Analysis of the Meteorite Surface by Desorption Electrospray Ionization Coupled with an Orbitrap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Naraoka, H.; Hashiguchi, M.

    2016-08-01

    It-situ analysis of organic compounds on the meteorite surface was performed by desorption electrospray ionization coupled with high resolution mass spectrometry. Indigenous peaks of meteorite origin were discriminated from the background.

  13. Positional plagiocephaly

    PubMed Central

    Cummings, Carl

    2011-01-01

    Cranial asymmetry occurring as a result of forces that deform skull shape in the supine position is known as deformational plagiocephaly. The risk of plagiocephaly may be modified by positioning the baby on alternate days with the head to the right or the left side, and by increasing time spent in the prone position during awake periods. When deformational plagiocephaly is already present, physiotherapy (including positioning equivalent to the preventive positioning, and exercises as needed for torticollis and positional preference) has been shown to be superior to counselling about preventive positioning only. Helmet therapy (moulding therapy) to reduce skull asymmetry has some drawbacks: it is expensive, significantly inconvenient due to the long hours of use per day and associated with skin complications. There is evidence that helmet therapy may increase the initial rate of improvement of asymmetry, but there is no evidence that it improves the final outcome for patients with moderate or severe plagiocephaly. PMID:23024590

  14. Polarisation dependences of harmonic generation in the plasma produced in the ionisation of excited-state hydrogen-like atoms

    SciTech Connect

    Silin, Viktor P; Silin, Pavel V

    2005-02-28

    An analytic theory of harmonic generation in the plasma produced from the gas of hydrogen-like atoms in excited states is considered for relatively intense radiation. The consideration of l-degeneracy of the electrons in these excited states allowed deriving the dependence of generation efficiency on the principal quantum number. In the context of the Bethe model of gas ionisation, we revealed the threshold nonlinear dependence of the maximum generation efficiency on the degree of circular polarisation of the pump field for its given intensity. Analytic calculations were performed for the fifth and seventh harmonics. The results of these calculations allowed generalising to the case of excited atoms the previously obtained results for the third harmonic in the plasma arising from hydrogen-like atoms in the ground state. (nonlinear optical phenomena)

  15. Excitation of low-frequency residual currents at combination frequencies of an ionising two-colour laser pulse

    NASA Astrophysics Data System (ADS)

    Vvedenskii, N. V.; Kostin, V. A.; Laryushin, I. D.; Silaev, A. A.

    2016-05-01

    We have studied the processes of excitation of low-frequency residual currents in a plasma produced through ionisation of gases by two-colour laser pulses in laser-plasma schemes for THz generation. We have developed an analytical approach that allows one to find residual currents in the case when one of the components of a two-colour pulse is weak enough. The derived analytical expressions show that the effective generation of the residual current (and hence the effective THz generation) is possible if the ratio of the frequencies in the two-colour laser pulse is close to a rational fraction with a not very big odd sum of the numerator and denominator. The results of numerical calculations (including those based on the solution of the three-dimensional time-dependent Schrödinger equation) agree well with the analytical results.

  16. Application of thoron interference as a tool for simultaneous measurement of radon and thoron with a pulse ionisation chamber.

    PubMed

    Tripathi, R M; Sumesh, C G; Vinod Kumar, A; Puranik, V D

    2013-07-01

    Pulse ionisation chamber (PIC)-based monitors measuring radioactive gas radon ((222)Rn) without energy discrimination will have interference due to thoron ((220)Rn) present in the atmosphere. A technique has been developed to use this property of interference for simultaneous measurement of radon and thoron gas. These monitors work on the principle of counting of gross alphas emitted from radon and its progeny. A theoretical model has been developed for the variation of thoron sensitivity with respect to the flow rate of gas through the monitor. The thoron sensitivity of the monitor is found to vary with the flow rate of gas through the monitor. Using this sensitivity, the sampling procedure has been developed and verified for simultaneous measurement of radon and thoron. The PIC-measured radon and thoron concentration using this procedure agrees well with those measured by using standard radon and thoron discriminating monitor.

  17. Surface analysis using a new plasma assisted desorption/ionisation source for mass spectrometry in ambient air

    NASA Astrophysics Data System (ADS)

    Bowfield, A.; Barrett, D. A.; Alexander, M. R.; Ortori, C. A.; Rutten, F. M.; Salter, T. L.; Gilmore, I. S.; Bradley, J. W.

    2012-06-01

    The authors report on a modified micro-plasma assisted desorption/ionisation (PADI) device which creates plasma through the breakdown of ambient air rather than utilising an independent noble gas flow. This new micro-PADI device is used as an ion source for ambient mass spectrometry to analyse species released from the surfaces of polytetrafluoroethylene, and generic ibuprofen and paracetamol tablets through remote activation of the surface by the plasma. The mass spectra from these surfaces compare favourably to those produced by a PADI device constructed using an earlier design and confirm that the new ion source is an effective device which can be used to achieve ambient mass spectrometry with improved spatial resolution.

  18. Role of the resistivity of insulating field emitters on the energy of field-ionised and field-evaporated atoms.

    PubMed

    Arnoldi, L; Silaeva, E P; Vurpillot, F; Deconihout, B; Cadel, E; Blum, I; Vella, A

    2015-12-01

    In order to improve the accuracy of laser atom probe analyses, it is important to understand all the physical processes induced by the combination of the high electrical field and the femtosecond laser beam during field evaporation. New information can be accessed from the energy of evaporated surface atoms or field-ionised atoms of an imaging gas. In order to study the ions energy, we combine La-APT and FIM analyses in a new experimental setup equipped with electrostatic lenses. We report measurements for semiconductors and oxides and we study the influence of the illumination conditions (laser power and wavelength), the evaporation rate, the sample geometry and the tip preparation processes. The results are discussed taking into account the resistive properties of non-metallic samples and the photo-stimulated conductivity. This work clarifies the role of the laser and DC field in the energy deficit of field evaporated ions. PMID:25484362

  19. Matrix-assisted laser desorption/ionisation mass spectrometry imaging and its development for plant protein imaging

    PubMed Central

    2011-01-01

    Matrix-Assisted Laser Desorption/Ionisation (MALDI) mass spectrometry imaging (MSI) uses the power of high mass resolution time of flight (ToF) mass spectrometry coupled to the raster of lasers shots across the cut surface of tissues to provide new insights into the spatial distribution of biomolecules within biological tissues. The history of this technique in animals and plants is considered and the potential for analysis of proteins by this technique in plants is discussed. Protein biomarker identification from MALDI-MSI is a challenge and a number of different approaches to address this bottleneck are discussed. The technical considerations needed for MALDI-MSI are reviewed and these are presented alongside examples from our own work and a protocol for MALDI-MSI of proteins in plant samples. PMID:21726462

  20. Detection of drugs in lifted cyanoacrylate-developed latent fingermarks using two laser desorption/ionisation mass spectrometric methods.

    PubMed

    Sundar, Latha; Rowell, Frederick

    2014-02-01

    This paper describes a method for lifting cyanoacrylate (CNA)-developed latent fingermarks from a glass surface and the detection of five drugs in lifted marks from fingers that had been in contact with the drugs, using Surface Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (SALDI-TOF-MS) or Matrix Assisted Laser Desorption Ionisation TOF-MS (MALDI-TOF-MS). Two drugs of abuse (cocaine and methadone) and three therapeutic drugs (aspirin, paracetamol and caffeine) were used as contact residues. Latent fingermarks spiked with the drugs were subjected to CNA fuming followed by dusting with ARRO SupraNano™ MS black magnetic powder (SALDI-TOF-MS) or 2,5-dihydroxybenzoic acid (DHB) (MALDI-TOF-MS). The dusted mark was then exposed to solvent vapour before lifting with a commercial fingerprint lifting tape following established procedures. The presence of the drugs was then confirmed by direct analysis on the tape without further processing using SALDI- or MALDI-TOF-MS. The black magnetic fingerprint powder provided visual enhancement of the CNA-fingermark while no visual enhancement was observed for marks dusted with DHB powder. Similar [M + H](+) peaks for all the drug analytes were observed for both methods along with some sodium and potassium adducts for SALDI-MS and some major fragment ions but the SALDI signals were generally more intense. Simple exposure to acetone vapour of the CNA-developed marks enabled their effective transfer onto the tape which was crucial for subsequent MS detection of the analytes.