DNA quantification approach by GE-ICP-SFMS and complementary total phosphorus determination by ICP-SFMS
Quantification of DNA is still a great challenge for scientists in many fields. Here, we present the on-line coupling of gel electrophoresis (GE) and inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for quantitative purposes. GE conditions are chosen for optimised separations depending on the target analyte composition in terms of DNA chain length. In particular, agarose concentrations are varied in the range 0.6–2.2%, which corresponds to a separation range of DNA from 100 base pairs (bp) to genomic DNA (approximately 3 Mbp). Separated DNA compounds are directly transported at a flow rate of 100 μL min−1 to a Micromist nebuliser which is followed by ICP-SFMS with 31P de…
On-line coupling of gel electrophoresis and inductively coupled plasma-sector field-mass spectrometry for the determination of dsDNA fragments.
The on-line coupling of gel electrophoresis (GE) and inductively coupled plasma-mass spectrometry (ICPMS) is described for the first time. The new method combines the separation power of GE for large biomolecules and the high sensitivity and elemental selectivity of ICPMS. This coupling has been achieved by means of gels housed in glass tubes (length 2.5-20 cm; i.d. 0.5-5 mm). The gel is fixed by glass frits permeable for the analytes. After the electrophoretic separation at voltages up to 500 V, the analytes are transferred to the nebulizer of the ICPMS by an eluent stream, which is separated from the electrode chamber by a membrane. This filter blocks molecules with molecular masses large…
On-line removal of mass interferences in palladium determination by ICP-MS using modified capillaries coupled to micro-flow nebulizers
This paper describes a novel approach developed for on-line removal of interferences within modified capillaries coupled to micro-flow nebulizers, for palladium determination by inductively coupled plasma mass spectrometry (ICP-MS). A strong cation exchanger [2-(4-chlorosulfophenyl)ethyltrichlorosilane)] was covalently bound to the silica capillary that was coupled to a microconcentric nebulizer (MCN) or to a direct injection nebulizer (DIN). The modified surface of the capillary was able to selectively retain copper and yttrium from aqueous samples at pH 7.5 during the sample introduction step, while Pd was not retained and 105Pd could be determined in the absence of interferent elements. …
Proteinanalytik einmal anders - ICP-MS als Untersuchungsmethode
Wie sind metallhaltige Proteine zusammengesetzt? In welcher Konzentration liegen sie vor? Die Massenspektrometrie mit induktiv gekoppeltem Plasma gibt darauf Antworten, qualitativ und quantitativ.
Determination of phytic acid and its degradation products by ion-pair chromatography (IPC) coupled to inductively coupled plasma-sector field-mass spectrometry (ICP-SF-MS)
We developed a method for the determination of phytic acid (IP6) and its degradation products (IP1-IP5) by ion-pair chromatography coupled to a double focussing inductively coupled plasma-sector field-mass spectrometer (ICP-SF-MS). For the detection of the phosphorus species a mass resolution (m/Δm) of 4000 was needed in order to separate the 31P+ signal from the interfering clusterions. The separation of the six phosphorus species was enabled by a gradient elution using tetrabutylammonium hydroxide (TBA) as ion-pair reagent. Calibration data were reported and a detection limit of 230 ng g−1 for IP6 could be obtained. The method was firstly proved for a hydrolyzate of commercially available…
Lead speciation in rainwater samples by modified fused silica capillaries coupled to a direct injection nebulizer (DIN) for sample introduction in ICP-MS
Lead speciation using modified silica capillaries for the introduction of liquid samples to a direct injection nebulizer of an inductively coupled plasma quadrupole mass spectrometer is described and demonstrated. The fused silica capillaries were coated by covalently bonding a cation exchange active organic molecule to the activated capillary surface. The best results were obtained by introducing a bifunctional reagent in a prior step. In this case, a silane reagent was chosen which acted as a methacrylic acid group for further binding. The influence of the chemical modification of the surface of the sample capillary of the DIN on the selective retention of inorganic lead (Pb2+) and trieth…
Gel Electrophoresis Coupled to Inductively Coupled Plasma−Mass Spectrometry Using Species-Specific Isotope Dilution for Iodide and Iodate Determination in Aerosols
In this paper, we present an online coupling of gel electrophoresis (GE) and inductively coupled plasma-mass spectrometry (ICP-MS) for the determination of iodine species (iodide and iodate) in liquid (seawater) and aerosol samples. For the first time, this approach is applied to the analysis of small molecules, and initial systematic investigations revealed that the migration behavior as well as the detection sensitivity strongly depends on the matrix (e.g., high concentrations of chloride). These effects could consequently affect the accuracy of analytical results, so that they need to be considered for the analysis of real samples. The technique used for quantification is species-specifi…
Plant protein phosphorylation monitored by capillary liquid chromatography–element mass spectrometry
Abstract Many essential cellular functions such as growth rate, motility, and metabolic activity are linked to reversible protein phosphorylation, since they are controlled by signaling cascades based mainly on phosphorylation/dephosphorylation events. Quantification of global or site-specific protein phosphorylation is not straightforward with standard proteomic techniques. The coupling of capillary liquid chromatography (μLC) with ICP-MS (inductively coupled plasma-mass spectrometry) is a method which allows a quantitative screening of protein extracts for their phosphorus and sulfur content, and thus provides access to the protein phosphorylation degree. In extension of a recent pilot st…
Determination of phosphorylation degrees in caseins by on-line gel electrophoresis coupled to ICP-SFMS
The determination of the phosphorylation degree of proteins is essential in many biochemical fields. Besides mass spectrometric techniques elucidating the protein structure, ICP-MS has entered this research area as it provides excellent quantification capabilities. In this work the separation of the proteins has been carried out by gel electrophoresis on-line coupled to an ICP equipped with a double-focusing sector field-MS (ELEMENT 2). Based on the simultaneous detection of 32S+ and 31P+, this work presents an alternative approach to determining the phosphorylation degree of caseins. For the example of α- and β-casein the results obtained were in excellent agreement with the expected value…
A novel approach for analysis of oligonucleotide-cisplatin interactions by continuous elution gel electrophoresis coupled to isotope dilution inductively coupled plasma mass spectrometry and matrix-assisted laser desorption/ionization mass spectrometry.
In this work we present a novel approach for in vitro studies of cisplatin interactions with 8-mer oligonucleotides. The approach is based on the recently developed coupling of continuous elution gel electrophoresis (GE) to an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS) with the aim of monitoring the interaction process between this cytostatic drug and the nucleotides. In contrast to existing methods, the electrophoretic separation conditions used here allow both the determination of the reaction kinetics in more detail as well as the observation of dominant intermediates. Two different nucleotides sequences have been investigated for comparison purposes, one contai…
On-line Chloride Interference Removal for Arsenic Determination in Waste Water and Urine by ICP-MS Using a Modified Capillary
The determination of arsenic in environmental samples like waste waters from industrial effluents and in biological samples like urine is very important due to the toxic nature of some of its species at moderate levels of exposure. The objective of this study was to evaluate the capability of modified anionic capillaries to remove chloride for ICP-MS determination of arsenic, which causes spectral interference due to formation of 40 Ar 35 Cl + . Also high chloride content gives non-spectral interferences. The results indicate that arsenic at a concentration higher than 1 µg L m 1 in a matrix with a chloride content up to 600 mg L m 1 can be accurately determined using a 3-aminopropyltrimeth…
Size characterisation of Au nanoparticles by ICP-MS coupling techniques
In modern nanotechnology the properties of nanoparticles (NPs) in different application fields is mainly dependent on their size and their size distribution. This paper aims to develop a reliable method for the size characterisation of Au NPs. Basing on the combination of two different separation techniques (liquid chromatography and gel electrophoresis), coupled on-line to inductively coupled plasma-mass spectrometry (ICP-MS), we study the separation of Au NP standards. Separations by liquid chromatography show size dependent retention behaviour with good reproducibility (RSD < 1%). The results are compared with complementary methods like dynamic light scattering (DLS) and transmission ele…
Analytical Chemistry. A Modern Approach to Analytical Science, 2nd Edition. Edited by Robert Kellner, Jean-Michel Mermet, Matthias Otto, Miguel Valcárel and H. Michael Widmer.
ElaC Encodes a Novel Binuclear Zinc Phosphodiesterase
ElaC is a widespread gene found in eubacteria, archaebacteria, and mammals with a highly conserved sequence. Two human ElaC variants were recently associated with cancer (Tavtigian, S. V., Simard, J., Teng, D. H., Abtin, V., Baumgard, M., Beck, A., Camp, N. J., Carillo, A. R., Chen, Y., Dayananth, P., Desrochers, M., Dumont, M., Farnham, J. M., Frank, D., Frye, C., Ghaffari, S., Gupte, J. S., Hu, R., Iliev, D., Janecki, T., Kort, E. N., Laity, K. E., Leavitt, A., Leblanc, G., McArthur-Morrison, J., Pederson, A., Penn, B., Peterson, K. T., Reid, J. E., Richards, S., Schroeder, M., Smith, R., Snyder, S. C., Swedlund, B., Swensen, J., Thomas, A., Tranchant, M., Woodland, A. M., Labrie, F., Sko…
Development of a new method for the separation of vanadium species and chloride interference removal using modified silica capillaries-DIN-ICP-MS
Abstract A new on-line method for the separation of vanadium (IV) and vanadium (V) as well as for the removal of ClO+ mass spectral interference on vanadium determination by quadrupole-ICP-MS has been developed. The sample introduction system consists of a modified fused silica capillary coupled to a direct injection nebuliser (DIN), between the solvent delivery system and the ICP. Fused silica capillaries were treated with different anion and cation exchanger reagents and were tested for the retention of Cl− and the separation of vanadium ions at μg l−1 levels. A suitable strong anion exchanger functional group (3-aminopropyltrimethoxy silane) was selected. Chlorine anions were retained in…