Flow Injection Analysis Mass Spectrometry Research Articles

Efficient derivatization-free monitoring of glycosyltransferase reactions via flow injection analysis-mass spectrometry for rapid sugar analytics.

The widespread application of enzymes in industrial chemical synthesis requires efficient process control to maintain high yields and purity. Flow injection analysis-electrospray ionization-mass spectrometry (FIA-ESI-MS) offers a promising solution for real-time monitoring of these enzymatic processes, particularly when handling challenging compounds like sugars and glycans, which are difficult to quickly analyze using liquid chromatography-mass spectrometry due to their physical properties or the requirement for a derivatization step beforehand. This study compares the performance of FIA-MS with traditional hydrophilic interaction liquidchromatography (HILIC)-ultra high-performance liquid chromatography (UHPLC)-mass spectrometry (MS) setups for the monitoring of the enzymatic synthesis of N-acetyllactosamine (LacNAc) using beta-1,4-galactosyltransferase. Our results show that FIA-MS, without prior chromatographic separation or derivatization, can quickly generate accurate mass spectrometric data within minutes, contrasting with the lengthy separations required by LC-MS methods. The rapid data acquisition of FIA-MS enables effective real-time monitoring and adjustment of the enzymatic reactions. Furthermore, by eliminating the derivatization step, this method offers the possibility of being directly coupled to a continuously operated reactor, thus providing a rapid on-line methodology for glycan synthesis as well.

Relationship of Acylcarnitines to Myocardial Ischemic Remodeling and Clinical Manifestations in Chronic Heart Failure.

Progressive myocardial remodeling (MR) in chronic heart failure (CHF) leads to aggravation of systolic dysfunction (SD) and clinical manifestations. Identification of metabolomic markers of these processes may help in the search for new therapeutic approaches aimed at achieving reversibility of MR and improving prognosis in patients with CHF. To determine the relationship between plasma acylcarnitine (ACs) levels, MR parameters and clinical characteristics, in patients with CHF of ischemic etiology (n = 79) and patients with coronary heart disease CHD (n = 19) targeted analysis of 30 ACs was performed by flow injection analysis mass spectrometry. Significant differences between cohorts were found for the levels of 11 ACs. Significant positive correlations (r > 0.3) between the medium- and long-chain ACs (MCACs and LCACs) and symptoms (CHF NYHA functional class (FC); r = 0.31-0.39; p < 0.05); negative correlation (r = -0.31-0.34; p < 0.05) between C5-OH and FC was revealed. Positive correlations of MCACs and LCACs (r = 0.31-0.48; p < 0.05) with the left atrium size and volume, the right atrium volume, right ventricle, and the inferior vena cava sizes, as well as the pulmonary artery systolic pressure level were shown. A negative correlation between C18:1 and left ventricular ejection fraction (r = -0.31; p < 0.05) was found. However, a decrease in levels compared to referent values of ACs with medium and long chain lengths was 50% of the CHF-CHD cohort. Carnitine deficiency was found in 6% and acylcarnitine deficiency in 3% of all patients with chronic heart disease. ACs may be used in assessing the severity of the clinical manifestations and MR. ACs are an important locus to study in terms of altered metabolic pathways in patients with CHF of ischemic etiology and SD. Further larger prospective trials are warranted and needed to determine the potential benefits to treat patients with CV diseases with aberrate AC levels.

High-Throughput Flow Injection Analysis-Mass Spectrometry (FIA-MS) Fingerprinting for the Authentication of Tea Application to the Detection of Teas Adulterated with Chicory.

Tea is a broadly consumed beverage worldwide that is susceptible to fraudulent practices, including its adulteration with other plants such as chicory extracts. In the present work, a non-targeted high-throughput flow injection analysis-mass spectrometry (FIA-MS) fingerprinting methodology was employed to characterize and classify different varieties of tea (black, green, red, oolong, and white) and chicory extracts by principal component analysis (PCA) and partial least squares–discriminant analysis (PLS-DA). Detection and quantitation of frauds in black and green tea extracts adulterated with chicory were also evaluated as proofs of concept using partial least squares (PLS) regression. Overall, PLS-DA showed that FIA-MS fingerprints in both negative and positive ionization modes were excellent sample chemical descriptors to discriminate tea samples from chicory independently of the tea product variety as well as to classify and discriminate among some of the analyzed tea groups. The classification rate was 100% in all the paired cases—i.e., each tea product variety versus chicory—by PLS-DA calibration and prediction models showing their capability to assess tea authentication. The results obtained for chicory adulteration detection and quantitation using PLS were satisfactory in the two adulteration cases evaluated (green and black teas adulterated with chicory), with calibration, cross-validation, and prediction errors below 5.8%, 8.5%, and 16.4%, respectively. Thus, the non-targeted FIA-MS fingerprinting methodology demonstrated to be a high-throughput, cost-effective, simple, and reliable approach to assess tea authentication issues.

Creatine and creatinine quantification in olympic athletes: dried blood spot analysis pilot study.

Capillary dried blood spot (DBS) samples facilitate field-based collection without venipuncture. This pilot study aims to evaluate the viability of creatine (Cr) and creatinine (Crt) quantification using fresh capillary serum (CrS/CrtS) and DBS samples (CrDBS/CrtDBS), using Flow Injection Analysis Mass Spectrometry (FIA – MS). Nine Olympic Athletes provided a capillary blood sample to assess CrS/CrtS and CrDBS/CrtDBS quantified by FIA – MS. No difference between CrtS (mean ± SD: 813.6 ± 102.4 μmol/L) and CrtDBS (812.4 ± 108.1 μmol/L) was observed with acceptable variance [SEM 88.7; CV 10.7%; ICC 0.57 (CI 95% 0.06 – 0.84)] and agreement [very strong (Spearman: r = 0.77; p < 0.01) or strong (Pearson: r = 0.56; p = 0.04); Bland Altman: lower (-193) and upper (+196) limits of agreement]. CrS (mean ± SD: 691.8 ± 165.2 μmol/L) was significantly different to CrDBS (2911 ± 571.4 μmol/L) with unacceptable variance [SEM 171.6; CV 27%; ICC 0.002 (CI 95% -0.02 – 0.07)] and ‘weak’ agreement [Spearman: r = 0.21, p = 0.47 and Pearson: r = 0.06, p = 0.84; Bland Altman lower (-3367) and upper (-1072) limits of agreement]. Crt quantification is viable using both CrtS and CrtDBS (but not for Cr and CrS/CrDBS), with the DBS tissue handling technique offering several methodological and practice facing advantages. Future work should expand upon the sample size, explore sport/discipline relevant analytes across a full competitive season, including key training, recovery and performance blocks of their periodized performance plan.

Urinary Metabolomic Profile of Neonates Born to Women with Gestational Diabetes Mellitus.

Gestational diabetes mellitus (GDM) is one of the most frequent pregnancy complications with potential adverse outcomes for mothers and newborns. Its effects on the newborn appear during the neonatal period or early childhood. Therefore, an early diagnosis is crucial to prevent the development of chronic diseases later in adult life. In this study, the urinary metabolome of babies born to GDM mothers was characterized. In total, 144 neonatal and maternal (second and third trimesters of pregnancy) urinary samples were analyzed using targeted metabolomics, combining liquid chromatographic mass spectrometry (LC-MS/MS) and flow injection analysis mass spectrometry (FIA-MS/MS) techniques. We provide here the neonatal urinary concentration values of 101 metabolites for 26 newborns born to GDM mothers and 22 newborns born to healthy mothers. The univariate analysis of these metabolites revealed statistical differences in 11 metabolites. Multivariate analyses revealed a differential metabolic profile in newborns of GDM mothers characterized by dysregulation of acylcarnitines, amino acids, and polyamine metabolism. Levels of hexadecenoylcarnitine (C16:1) and spermine were also higher in newborns of GDM mothers. The maternal urinary metabolome revealed significant differences in butyric, isobutyric, and uric acid in the second and third trimesters of pregnancy. These metabolic alterations point to the impact of GDM in the neonatal period.

Novel Fast Chromatography-Tandem Mass Spectrometric Quantitative Approach for the Determination of Plant-Extracted Phytosterols and Tocopherols.

Phytosterols and tocopherols are commonly used in food and pharmaceutical industries for their health benefits. Current analysis methods rely on conventional liquid chromatography, using an analytical column, which can be tedious and time consuming. However, simple, and fast analytical methods can facilitate their qualitative and quantitative analysis. In this study, a fast chromatography-tandem mass spectrometric (FC-MS/MS) method was developed and validated for the quantitative analysis of phytosterols and tocopherols. Omitting chromatography by employing flow injection analysis—mass spectrometry (FIA-MS) failed in the quantification of target analytes due to analyte-to-analyte interferences from phytosterols. These interferences arise from their ambiguous MS fingerprints that would lead to false identification and inaccurate quantification. Therefore, a C18 guard column with a 1.9 µm particle size was employed for FC-MS/MS under isocratic elution using acetonitrile/methanol (99:1 v/v) at a flow rate of 600 µL/min. Analyte-to-analyte interferences were identified and eliminated. The false peaks could then be easily identified due to chromatographic separation. In addition, two internal standards were evaluated, namely cholestanol and deuterated cholesterol. Both internal standards contributed to the observed analyte-to-analyte interferences; however, adequate shift in the retention time for deuterated cholesterol eliminated its interferences and allowed for an accurate quantification. The method is fast (1.3 min) compared to published methods and can distinguish false peaks observed in FIA-MS. Seven analytes were quantified simultaneously, namely brassicasterol, campesterol, stigmasterol, β-sitosterol, α-tocopherol, δ-tocopherol, and γ-tocopherol. The method was successfully applied in the quantitative analysis of phytosterols and tocopherols present in the unsaponifiable matter of canola oil deodorizer distillate (CODD). β-sitosterol and γ-tocopherol were the most abundant phytosterols and tocopherols, respectively.

A high-throughput, ultrafast, and online three-phase electro-extraction method for analysis of trace level pharmaceuticals

Sample preparation is often reported as the main bottleneck of analytical processes. To meet the requirements of both high-throughput and high sensitivity, improved sample-preparation methods capable of fast analyte preconcentration are urgently needed. To this end, a new three-phase electroextraction (EE) method is presented that allows for ultrafast electroextraction hyphenated to flow-injection analysis mass spectrometry (FIA-MS). Four model compounds, i.e., propranolol, amitriptyline, bupivacaine, and oxeladin, were used to optimize and evaluate the method. Within only 30 s extraction time, enrichment factors (EF) of 105–569 and extraction recoveries (ER) of 10.2%–55.7% were achieved for these analytes, with limits of detection (LODs) ranging from 0.36 to 3.21 ng mL−1, good linear response function (R2 > 0.99), low relative standard deviation (0.6%–17.8%) and acceptable accuracy (73–112%). Finally, the optimized three-phase EE method was successfully applied to human urine and plasma samples. Our three-phase electroextraction method is simple to construct and offers ultrafast, online extraction of trace amounts of analytes from biological samples, and therefore has great potential for high-throughput analysis.

An untargeted evaluation of food contact materials by flow injection analysis-mass spectrometry (FIA-MS) combined with independent components analysis (ICA)

Food contact materials (FCMs), especially plastics, are known to be a potential source of contaminants in food. In fact, various groups of additives are used to protect the integrity of the material during processing and life time. However, these intentionally added substances (IAS) could also lead to degradation products called non-intentionally added substances (NIAS), due to reactions occurring in the polymeric material. Complex mixtures of components may therefore be generated within the material, creating a source of potential migrating substances towards food in contact. In this context, an innovative analytical approach is proposed in order to assess IAS and NIAS in plastic FCMs for a fast screening of their composition. For this purpose, solvent extracts of polyethylene (PE) pellets, containers and films were analyzed by flow injection analysis-mass spectrometry (FIA-MS). This direct approach offers the ability to perform a large number of analyses in a short time. Mass spectral fingerprints were then treated by a multivariate data analysis technique called independent components analysis (ICA) in order to overcome the complexity of such data and to highlight hidden information related to IAS and NIAS molecules. ICA applied on mass spectral fingerprints of PE extracts highlighted group discriminations related to different m/z values which were putatively assigned to IAS and also to NIAS. In order to confirm these putative annotations, a hybrid LTQ-Orbitrap was used for high resolution mass spectrometry analysis. Moreover, MS/MS experiments were performed on some discriminant ions to improve their putative identification. The proposed methodology combining FIA-MS fingerprints and ICA proved its efficiency in identifying IAS and NIAS in plastic FCMs and its capability to discriminate different PE samples, in a relatively fast approach compared to classical analytical techniques. This approach may help the FCMs classification for compounders in the selection of the starting substances in plastic formulation and for plastic converters in the control of manufacturing processes as well as for the monitoring of final products.

Emerging flow injection mass spectrometry methods for high-throughput quantitative analysis.

Where does flow injection analysis mass spectrometry (FIA-MS) stand relative to ambient mass spectrometry (MS) and chromatography-MS? Improvements in FIA-MS methods have resulted in fast-expanding uses of this technique. Key advantages of FIA-MS over chromatography-MS are fast analysis (typical run time <60 s) and method simplicity, and FIA-MS offers high-throughput without compromising sensitivity, precision and accuracy as much as ambient MS techniques. Consequently, FIA-MS is increasingly becoming recognized as a suitable technique for applications where quantitative screening of chemicals needs to be performed rapidly and reliably. The FIA-MS methods discussed herein have demonstrated quantitation of diverse analytes, including pharmaceuticals, pesticides, environmental contaminants, and endogenous compounds, at levels ranging from parts-per-billion (ppb) to parts-per-million (ppm) in very complex matrices (such as blood, urine, and a variety of foods of plant and animal origin), allowing successful applications of the technique in clinical diagnostics, metabolomics, environmental sciences, toxicology, and detection of adulterated/counterfeited goods. The recent boom in applications of FIA-MS for high-throughput quantitative analysis has been driven in part by (1) the continuous improvements in sensitivity and selectivity of MS instrumentation, (2) the introduction of novel sample preparation procedures compatible with standalone mass spectrometric analysis such as salting out assisted liquid-liquid extraction (SALLE) with volatile solutes and NH4(+) QuEChERS, and (3) the need to improve efficiency of laboratories to satisfy increasing analytical demand while lowering operational cost. The advantages and drawbacks of quantitative analysis by FIA-MS are discussed in comparison to chromatography-MS and ambient MS (e.g., DESI, LAESI, DART). Generally, FIA-MS sits 'in the middle' between ambient MS and chromatography-MS, offering a balance between analytical capability and sample analysis throughput suitable for broad applications in life sciences, agricultural chemistry, consumer safety, and beyond.

Renewable sorbent material for solid phase extraction with direct coupling of sequential injection analysis-bead injection to liquid chromatography-electrospray ionization tandem mass spectrometry

The use of small scale renewable sorbent material for automated solid phase extraction of multi-residue pharmaceuticals in environmental samples exploiting the sequential injection analysis-bead injection with direct coupling to liquid chromatography-electrospray ionization tandem mass spectrometry (SIA-BI-μSPE-LC-ESI-MS/MS) is presented to determine beta-blockers, namely atenolol, sotalol, pindolol, acebutolol, timolol, metoprolol, labetalol, carazolol, propranolol and betaxolol. These compounds yielded the same product ions, therefore were affected in terms of quantification when flow injection analysis-mass spectrometry (FIA-MS) was used. Thus, analytes and matrix present in the sample travel together into the ionization source which can seriously affect the ionization efficiency and analyte signals due to monitoring over a short time period. Graphical abstract A two-dimensional analysis involving a time dimension (retention time) and an m/z dimension (fragmentation ion) is promising for the various sample types. Using the developed method, absolute recoveries percentages of 10 mL of sample loading volume were >91% for all β-blockers with enrichment factor of 62-74, limits of detection of 0.005-0.07 μg L(-1), limits of quantification of 0.01-0.23 μg L(-1), enrichment factor of 62-72 and repeatability within range 7-12%. This developed method is suggested to be used as quantitative screening technique for drugs of abuse or persistent contamination using different kinds of sorbent materials and complex matrix such as biological fluid sample as well.

Rapid, quantitative analysis of 3′- and 6′-sialyllactose in milk by flow-injection analysis–mass spectrometry: Screening of milks for naturally elevated sialyllactose concentration

Non-protein-bound oligosaccharides are important bioactive components of cow milk, with potential human-health benefits such as stimulation of the growth of beneficial gut bacteria and defense against pathogens. In bovine milk, the majority of oligosaccharides are sialylated; 3′-sialyllactose (3′-N-acetylneuraminyl-d-lactose; 3′-SL) is the predominant sialylated oligosaccharide, followed by 6′-sialyllactose (6′-N-acetylneuraminyl-d-lactose; 6′-SL). Both 3′-SL and 6′-SL have antimicrobial activity. As bovine milk products such as infant formula can be an important component of the human diet, and the concentrations of 3′-SL and 6′-SL are lower in bovine milk compared with human milk, we aimed to identify cows that naturally produce higher concentrations of sialyllactose in their milk. Milk from such cows could be used to produce foods with an increased sialyllactose content, potentially providing increased health benefits. We speculated that cows overexpressing 3′-SL and 6′-SL would exist at low frequency in the population and, to allow their efficient identification, we developed a novel assay for 3′-SL and 6′-SL utilizing flow-injection analysis-mass spectrometry, which could be used for high-throughput analysis of milk samples. We then determined 3′-SL and 6′-SL concentrations in milk samples from 15,507 cows from Friesian, Jersey, and Friesian-Jersey crossbred animals. We found 329 cows with concentrations of 3′-SL or 6′-SL >2-fold higher than the mean, 26 cows with concentrations of 3′-SL or 6′-SL >3-fold higher than the mean, and 1 cow with concentrations of 3′-SL >4-fold higher than the mean. Although these outliers were observed across the 3 groups of cows, breed had a strong effect on mean 3′-SL and 6′-SL concentrations.

Pulsed Laser Deposition of Polymers Doped with Fluorescent Probes. Application to Environmental Sensors

Pulsed laser deposition (PLD) has been used to obtain thin films of poly(methyl methacrylate) and polystyrene doped with fluorescent probes, amino aromatic compounds S5 and S6, that could be used to sense the presence of contaminating environmental agents. These dopants both in solution and inserted in polymeric films are sensitive to changes in pH, viscosity and polarity, increasing their fluorescence emission and/or modifying the position of their emission band. Films deposits on quartz substrates, obtained by irradiating targets with a Ti:Sapphire laser (800 nm, 120 fs pulse) were analyzed by optical and Environmental Scanning Electron Microscopy, Fluorescence Microscopy, Laser-Induced Fluorescence, Micro Raman Spectroscopy and Flow Injection Analysis-Mass Spectrometry. The transfer of the polymer and the probe to the substrate is observed to be strongly dependent on the optical absorption coefficient of the polymeric component of the target at the irradiation wavelength.

Systematic examination of the signal area precision of a single quadrupole enhanced low mass option (ELMO) TSQ™ mass spectrometer

To examine the precision of the signal area response of an enhanced low mass option (ELMO) MSQmass spectrometer, operated in the negative electrospray ionization (ESI) mode, extended tests were performed, using flow injection analysis mass spectrometry (FIA-MS). Analytes were nitrate, nitrite, malonic acid, and D,L-mandelic acid. Composition and concentration of injected samples, application of an ASRS anion suppressor and of the cone wash unit, methanol addition to the FIA flow medium, and the voltage bias of the hexapole transfer lens were test variables. Individual test cycles comprised up to 90 injections, processed within 20 h. With a few exceptions the signal response tended to decline over time leading to a loss of more than 80% of the initial signal area in extreme cases. A hexapole radio-frequency (RF) voltage bias of -0.3 V led to an overall low detector response and to high losses of sensitivity over time. Other correlations between the insufficient signal reproducibility and FIA-MS operating conditions could not be established. The test scheme gave hints how to localize the cause of the mass spectrometer malfunction. The repetition of the test scheme after remedying the detected electronic default demonstrated that relative standard deviations less than 5% can be achieved for a sequence of 30 injections if methanol is added to the FIA flow medium and if a suppressor is used. Based on these findings a recommendation is formulated to supplement current test schemes for instrument performance verification by a detector response precision criterion.

Pulsed laser deposition of polymers doped with fluorescent molecular sensors

Pulsed laser deposition (PLD) has been used to obtain thin films of poly(methyl-methacrylate), PMMA, and polystyrene, PS, doped with fluorescent probes based in the amino aromatic compounds S6, DMA-2,4, Dans and Acrid-acryl. These compounds, both in solution and inserted in polymeric films, show solvatochromic emission band shifts upon changes of pH, polarity and viscosity in their micro-environment and, prepared in thin films, could prove advantageous for use as sensors of the presence of contaminating environmental agents. Deposits, obtained by irradiating targets consisting in films of doped PMMA and PS with a Ti:sapphire laser (800 nm, 120 fs pulse), were analyzed by optical and environmental scanning electron microscopy, fluorescence microscopy, laser-induced fluorescence, micro-Raman spectroscopy and flow injection analysis-mass spectrometry. Results show the effective transfer of the polymer and the probe to the substrate and the high dependence on film structure on the polymer used in the targets. Irradiation with a KrF laser (248 nm, 20 ns) of Dans-doped targets only produced deposits when using PMMA for target preparation. Results are discussed in terms of the participation of multiphoton processes in the fs IR irradiation, the influence of the linear absorption coefficient of the targets and of the different contributions of thermal and chemical effects in the IR femtosecond and UV nanosecond domains.

FIA/MS analysis of temporally ozonated benzo[ a]pyrene and pyrene and their reaction products: Inhibition of gap junction-mediated intercellular communication

In this study, the polycyclic aromatic hydrocarbons, benzo[ a]pyrene (BaP) and pyrene, were subjected to temporal ozonation. The products from ozonation of 5 mg l −1 BaP and 5 mg l −1 pyrene, for varying time intervals (0, 1, 2, 3, 4, 5, 6, 8, 10, 20, and 30 min) were tested for their effects on gap junction-mediated intercellular communication (GJIC) in Clone 9 rat liver cells. Additionally, the ozonation products were also analyzed by flow injection analysis/mass spectrometry (FIA/MS) and the results were compared with the toxicity observed in the GJIC assay. Treatment of the Clone 9 cells with 5 mg l −1 of ozonated BaP products resulted in a decrease in GJIC that was inversely proportional to the length of ozonation. The products from 1 min of ozonation resulted in a 92% decrease in the rate of GJIC, but with >5 min ozonation, the products did not suppress GJIC. In contrast, pyrene (0.5 mg l −1) required >10 min of ozonation to alleviate its effects on GJIC. FIA/MS, using atmospheric pressure chemical ionization (APCI), demonstrated products with higher molecular weights (MW) than their corresponding parent compounds, BaP (MW 252) and pyrene (MW 202). Ozonation of pyrene formed significantly fewer products than BaP. More importantly, pyrene ozonation products were constant from 1 to 10 min, while BaP ozonation products seemed to vary between time intervals. With the longer ozonation times (20 and 30 min), BaP and pyrene formed similar products ( m/z peaks 157, 111, and 96). The suppression of GJIC by ozonated products seemed to correlate with oxidation of the aromatic ring framework. Further oxidation (longer ozonation times) to lower MW products correlated with restoration of normal GJIC.

A flow injection analysis/mass spectrometry method for the quantification of polyethylene glycol 300 in drug formulations

A direct flow injection analysis/mass spectrometry (FIA/MS) method was developed for the quantification of polyethylene glycol. The method was used for the evaluation of distribution uniformity and mixing homogeneity of polyethylene glycol 300 (PEG 300) as a component in drug formulation mixtures. In the method, five of the most intense ions of the PEG 300 oligomer were chosen for selected ion monitoring (SIM) by mass spectrometry. Standard calibration curves were established, using either single channel SIM or the summed intensity of all five SIM channels plotting against the standard concentrations. Both calibration approaches produced comparable results on quantification. The feasibility of the method was demonstrated using both atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). The method provided fast and sensitive quantification of PEG 300 without tedious chromatographic separation or sample preparation. The method has been successfully adopted for the evaluation of the mixing process in drug formulations.

Flow injection analysis mass spectrometry, a tool to investigate the problems in the quantitative analysis of hypericin using reversed‐phase high‐performance liquid chromatography

Rapid Communications in Mass SpectrometryVolume 18, Issue 1 p. 131-132 Letter to the Editor Flow injection analysis mass spectrometry, a tool to investigate the problems in the quantitative analysis of hypericin using reversed-phase high-performance liquid chromatography Anna Piovan, Anna Piovan Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this authorRaffaella Filippini, Corresponding Author Raffaella Filippini raffaella.filippini@unipd.it Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalyMail Stop: University of Padua, Department of Biology, Via U. Bassi, 58/B 35131 Padova, Italy.Search for more papers by this authorAnna Borsarini, Anna Borsarini Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this authorRosy Caniato, Rosy Caniato Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this author Anna Piovan, Anna Piovan Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this authorRaffaella Filippini, Corresponding Author Raffaella Filippini raffaella.filippini@unipd.it Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalyMail Stop: University of Padua, Department of Biology, Via U. Bassi, 58/B 35131 Padova, Italy.Search for more papers by this authorAnna Borsarini, Anna Borsarini Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this authorRosy Caniato, Rosy Caniato Department of Biology, University of Padua, Via U. Bassi, 58/B 35131 Padova, ItalySearch for more papers by this author First published: 11 December 2003 https://doi.org/10.1002/rcm.1277Citations: 10Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article.Citing Literature Volume18, Issue115 January 2004Pages 131-132 RelatedInformation

Rapid isolation of biomarkers for compound specific radiocarbon dating using high-performance liquid chromatography and flow injection analysis-atmospheric pressure chemical ionisation mass spectrometry.

Repeated semi-preparative normal-phase HPLC was performed to isolate selected biomarkers from sediment extracts for radiocarbon analysis. Flow injection analysis-mass spectrometry was used for rapid analysis of collected fractions to evaluate the separation procedure, taking only 1 min per fraction. In this way 100-1000 microg of glycerol dialkyl glycerol tetraethers, sterol fractions and chlorophyll-derived phytol were isolated from typically 100 g of marine sediment, i.e., in sufficient quantities for radiocarbon analysis, without significant carbon isotopic fractionation or contamination.

The analytical characterisation of sub-minute measurement duty cycles in flow injection analysis mass spectrometry, by their carry-over

A high-throughput flow injection analysis mass spectrometry system was developed in-house for the purity estimation of multiple parallel combinatorial chemistry syntheses. A Visual Basic application called RackViewer allows a fast and easy on-screen inspection of these estimates at dispersed laboratory workbenches via the corporate computer network. Due to the increasing numbers of samples to be measured, there is an constant incentive to reduce the measurement duty cycle in order to develop faster throughput rates. Consequently, one threat to the accuracy of these purity estimates is surreptitious inter-sample carry-over. By analogy with the computer screen colour rendering of the purity estimates, carry-over was automatically calculated, then colour depicted within RackViewer. In an earlier report, this carry-over visualisation tool facilitated a stepwise reduction in the measurement duty cycle to 70 s, while maintaining median inter-sample carry-over at levels well below 1%. However, a limiting factor in further optimisation was the physical speed of the autosampler’s sampling head. A recent increase in this speed by the autosampler’s manufacturer allowed a second attempt at achieving well characterised sub-minute measurement duty cycles. Six injection variations involving different syringe and loop wash combinations were examined for their characteristic inter-sample carry-over, using over four hundred samples drawn equally from five diverse combinatorial chemistries. One emerged as the best, with a median inter-sample carry-over of 0.01% and a measurement duty cycle of 44 s.

Discovery of Quasi-Molecular Ions in Electrospray Spectra by Automated Searching for Simultaneous Adduct Mass Differences

Our high-throughput flow injection analysis mass spectrometry (FIA-MS) system using electrospray ionization steers the majority of ion current into quasi molecular ion and adduct m/z positions. One advantage of this dawned on us, i.e., that adducted electrospray spectra are amenable to automated quasi molecular ion discovery by searching for the simultaneous occurrence of adduct mass differences. Therefore, an adduct scanning algorithm was developed, given a graphical user interface, and then incorporated into a Visual Basic application originally developed for reporting of high-throughput FIA-MS results.