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EN
Chemical analysis of different materials at the place where analytes are present (on-site analysis) has several advantages in comparison to analysis of these materials after delivering the samples to laboratory. Mobile devices, possessing expected properties in terms of using energy, mass and volume are needed for such analyses. The obtained results should be comparable to those obtained with the stationary instruments. Mass and ion mobility spectrometers are examples of the instruments fulfilling these requirements. At the beginning, the article describes the developments in combining of mass and ion mobility spectrometers (MS, IMS) with miniature gas chromatographs (GC). Both systems are used for analyses in the field, mainly for determination of environmental pollutions. They are used not only for analysis of typical chemicals present in different environmental compartments (in air, water and soil samples) but also for analysis of explosives, drugs and chemical warfare agents when fast results are needed. Particularly noteworthy is their applications in space exploration on the International Space Station. The selected examples of applications of miniaturised GC-MS and GC-IMS devices are presented in the second part of this mini review.
PL
Praca prezentuje wyniki badań wrażliwości spektrometru mas z nowatorskim układem polaryzacji źródła elektronów, zapewniającym niezależny dobór natężenia prądu emisji elektronowej i napięcia przyśpieszającego elektrony. Dzięki takiemu rozwiązaniu możliwe jest wyznaczenie wrażliwości natężenia prądu jonowego niezależnie względem natężenia prądu emisji elektronowej i napięcia przyśpieszającego elektrony. Badania objęły również pozostałe charakterystyki spektrometru mas oraz wrażliwości natężenia prądu jonowego względem ciśnienia i napięcia przyspieszającego jony. Wyniki potwierdzają zalety nowego rozwiązania w spektrometrze mas.
EN
The sensitivity measurement results of a mass spectrometer (Fig. 1) with an innovative biasing system in an electron source [1] are presented. The biasing system ensures that an accelerating voltage and an electron emission current are independent of each other. Owing to that, the sensitivity of an ion current versus the electron emission current (Fig. 2), and independently versus the electron accelerating voltage (Fig. 3) can be determined. The researches included the determination of the mass spectrometer characteristics and sensitivity of the ion current in function of a pressure (Fig. 4.) and the ion current in function of an ion accelerating voltage (Fig. 5, Fig. 6). The results confirm that new biasing system is highly suitable for the mass spectrometer.
PL
W pracy przedstawiono przegląd rozwiązań stosowanych w próżniomierzach jonizacyjnych i spektrometrach mas wykorzystujących strumień termoelektronów do jonizacji materii w postaci gazowej, w szczególności przykłady konstrukcji źródeł jonów oraz układów polaryzacji ich elektrod. Na podstawie wyników przeprowadzonej analizy zaproponowano nowy sposób detekcji prądu termoemisji elektronowej dla układów stabilizacji natężenia strumienia i energii elektronów.
EN
This paper presents an overview of the vacuum measurement instruments using electron - impact gas ion sources, especially examples of the ion sources and biasing systems. Based on the analysis results a new thermionic emission current detection method to implementation in stabilizer of ionizing beam intensity and electron energy has been proposed.
4
Content available remote From the discovery of radioactivity to the development of the K-Ar dating method
EN
In this paper I try to explain why the potassium-argon dating method was developed much later than other radiometric methods (like U-He and U-Pb), which were established at the beginning of the 20th century. In fact the pioneering paper by Aldrich and Nier (1948) was published 50 years after the discovery of polonium and radium, when nearly all the details concerning potassium isotopes and radioactivity of potassium-40 had been investigated. The role of Marie Curie’s concept of the na-ture of radioactivity in the discovery of the radioactivity of potassium is emphasized.
PL
Omówiono zastosowanie strukturalno-algorytmicznych metod poprawy dokładności ilościowej analizy chemicznej chromatograficznych systemów pomiarowych z detekcją spektrometrem mas. Zaproponowano zwiększenie dokładności wyników przez wyeliminowanie wpływu niepewności w procesie przygotowania próbki. Dla bezpośrednio skalibrowanego spektrometru mas pozwala to oszacować dyspersję i całkowitą niepewność wyniku analizy. Podano przykład liczbowy.
EN
Features of the application of structural-algorithmic methods of increasing the accuracy of the results of quantitative chemical analysis with the use of chromatographic-mass-spectrometric measuring system are considered. Proposed is method of excluding the influence of the uncertainty of the sample preparation stage. It allows for the directly calibrated mass spectrometer to assess the output data dispersion and to determine the overall uncertainty analysis. Formulas for such analysis of uncertainty are presented. As illustration numerical example of uncertainty calculations is included and conclusions are formulated.
PL
Nowatorski system tandemowej spektrometrii mas tandemowej spektrometrii mas (PTM Discovery System), oferuje użytkownikowi możliwość zastosowania dwóch różnych metod fragmentacji MS: CID (ang. – collision induced dissociation) oraz ETD (ang. – electron transfer dissociation), których wyniki doskonale się uzupełniają. Informacje uzyskane przy pomocy obu technik idealnie nadają się do analizy modyfikacji posttranslacyjnych (PTM) białek, np. fosforyzacji. Fragmentacja oparta na metodzie ETD, podobnie jak powszechnie znana metoda CID, pozwala na szybką identyfikację peptydów w połączeniu z technikami rozdziału online.
EN
A novel tandem mass spectrometry instrument (PTM Discovery System) offers the application of two different MS fragmentation techniques (i.e. collision induced dissociation, CID, and electron transfer dissociation, ETD) showing highly complementary fragmentation results. The information obtained from both techniques is ideally suited for the characterization of post translational modification (PTM), such as phosphorylation. ETD based fragmentation shows a similar short duty cycle as common CID, allowing fast peptide identification and characterization in combination with online separation techniques.
EN
This paper presents a powerful analytical technique which uses an inductively coupled plasma (ICP) ionization source and mass spectrometric (MS) detector with a time of flight (TOF) analyzer. The technique has been introduced in 1993 and has attracted rapidly the attention of researchers in the field of atomic spectroscopy as a method that offers substantial improvement of figures of merit of widely used ICP-MS technique with quadrupole filters. A mass spectrum in ICP-TOFMS technique is generated for a packet of ions simultaneously extracted from a continuous ion beam generated in plasma and accelerated to the same kinetic energy (Ek = 0.5 mv2). Setting the ions to the same kinetic energy results in different velocities acquired by the ions of different masses. The separation of the ions of different m/z is accomplished due to different times of their passing a fixed path (field-free region) in the instrument. Extremely low time difference (nanosecond regime) between adjacent masses reflects in quasi-simultaneous detection of all isotopes reaching the detector. The technique offers extremely high speed: spectral frequency 20-30 kHz (i.e. 20000-30000 mass spectra can be accumulated per second), an ability to obtain full elemental analysis for a packet of ions extracted from a continuous ion beam and a significantly better, as compared with quadrupole ICP-MS, precision of the measurements. Analytical performance and applicability of the technique in multi-clemental analysis of various materials have been extensively examined since 1998 when the ICP-TOFMS spectrometers have been commercially available (from LECO, USA („LECO Renaissance") and GBC, Australia („Optimass 8000")). The technique has turned to be particularly suited for detection of fast transient signals generated, e.g. by laser ablation, chromatographic systems, capillary clectrophoresis and FIA. The basic principles, analytical capabilities of the ICP-TOFMS technique and characteristics of the instruments used are discussed in this paper. Analytical applications of the technique are presented.
8
Content available Sulfur isotope effects for the SO2(g)-SO2(aq) system
EN
Sulfur isotope fractionation (34S/32S) factors were determined for the SO2(g)-SO2(aq) system. The influence of temperature on the investigated sulfur isotopes separation between phases was studied as well.
9
Content available Sulfur isotope composition of selected Polish coals
EN
Literature studies show that there are few data on sulfur isotope ratio in available the Polish coals. Elaboration of a method for the separation of sulfur from coal and measurement of sulfur isotope ratio of Polish coals is the scope of this work. The aim of the study was the preparation of coal samples and extraction of the particular form of sulfur. The stable compounds (Ag2S and BaSO4) were converted into sulfur dioxide. Sulfur isotope ratio in the gas phase was determined using a mass spectrometer. Samples were taken from selected Polish coal mines. Hard coal from Upper Silesia Basin, one sample from the Bogdanka coal-mine and one sample of lignite from the Be?chatow coal-mine.
PL
W pracy opisano zastosowanie prostego stabilizatora szeregowego napięcia do kontrolowania temperatury włókna, Tf w termoemisyjnym źródle jonów spektrometru masowego. Napięcie na włóknie, Vf jest mierzone za pomocą pary przewodów dołączonych wewnątrz źródła jonów równolegle do pary przewodów służących do grzania włókna. Pokazano, że wartość Vf jest wprost proporcjonalna do Tf w szerokim zakresie temperatur. Wartość Tf jest kontrolowana jedynie wartością napięcia referencyjnego, Vf które może być wybierane ręcznie z dzielniku napięcia lub za pomocą komputera. Sygnały cyfrowe z komputera są transmitowane optoelektroniczne a następnie w kontrolerze temperatury są przetwarzane na sygnał analogowy. Opisane urządzenie jest stosowane w spektrometrze mas służącym do analizy zawartości potasu metodą rozcieńczenia izotopoweg0.
EN
We describe the use of a simple voltage stabilizer that controls filament temperature, Tf in the ion source of a thermal ionization mass spectrometer (TIMS). The filament voltage, Vf is measured by means of a separate pair of wires connected inside of the ion source in parallel to the wires supplying power. It has been demonstrated that Vf is directly proportional to Tf in a wide range of filament temperature. The Tf value is solely controlled by the reference voltage, Vf which can be manually selected from a voltage divider or by means of a computer. Digital signals from the computer in form of series of pulses are transmitted opto-electronically and subsequently converted to the analog signals. The temperature controller described here is succesfully applied for analysis of potassium concentration by the isotope dilution method.
PL
W pracy zostało przedstawione urządzenie do identyfikacji rodzaju prądu jonowego w spektrometrach z wybieraniem magnetycznym. W spektrometrach tego typu iloraz m/e jest wprost proporcjonalny do kwadratu indukcji magnetycznej. W opisanym urządzeniu sygnał napięciowy będący miarą ilorazu m/e został uzyskany za pomocą dwóch hallotronów umieszczonych w szczelinie elektromagnesu. Wyniki badań eksperymentalnych potwierdzają korzystne właściwości metrologiczne (precyzję) opracowanego urządzenia.
EN
In this paper the device for identification of the ion beams in a magnetically scanned mass spectrometer is considered. For mass spectrometers with magnetic scanning the m/e ratio is directly proportional to the square of the magnetic field strength. In the device described a voltage signal precisely matching the ratio m/e is obtained by means of two Hall probes placed into the gap of the electromagnet. Results of the experimental testing confirm the advantageous metrological properties (precision) of the recently developed device.
EN
The principle of ion cyclotron resonance (ICR) reported in 1930 by Lawrence et al. [9] was firstly applied in mass spectrometry by Hipple, Sommer and Thomas in 1949 [26]. Their instrument has never been commercilized due to several problems with electronics and vacuum. Next instrument constructed by Wobschall et al. In the 1960s [27] had more chamce. It was modified by Llewellyn [28] in cooperation with Baldeschwieler et al. [29] and became a commercial Varian mass spectrometer in the late 1960s. Its drift cell contained three separated regions: ion source, analyser and ion collector. Important modification in ICRMS was proposed by McIver in 1970 [10a, b]. He introduced a one region trapped-ion analyzer cell and pulsed mode of operation. First FT-ICR experiments were carried out by Comisarow and Marshall in 1974 [11]. They also applied a one region trapped-ion analyzer cell. The pulsed mode of operation in the one region cell was combined with Fourier transform techniques in first commercial Nicolet FT-ICR mass spectrometer. From this moment the FT-ICR mass spectrometry has become more attractive and more frequently used by chemists. Since ions may be trapped for extended periods prior to detection in an ICR cell, both, ICR and FT-ICR mass spectrometry have been used to the study of gas-phase ion-molecule reactions [1-6]. First experimental gas-phase data of sufficient precision obtained by ICRMS became available from the 1970s for the proton-transfer reactions [2, 7, 8, 10, 41-43]. Relative acidity (DGA) or basicity (DGB) determinations were based on measurements of the equilibrium constants of proton exchange between two anions (A-1 and A-2) or two bases (B1 and B2) [7, 8, 13a]. These reactions have been studied in order to determine intrinsic gas-phase acidities or basicities of compounds and to establish general gas-phase acidity/basicity scale. Presently there are few thousands gas-phase data compiled in this scale by Lias et al. [50]. The upper limit of the GB scale is separated from the lower limit of the GA scale by ca 150 kJ/mol (Fig. 6), and thus spontaneous neutralization reactions between neutral acids and bases can not yet be observed in the gas phase.
PL
W pracy zaprezentowano możliwości zastosowania spektrometru masowego typu, "mass-reflectron" do badań jednorodności przestrzennej składu chemicznego i domieszkowania stopów metali lekkimi pierwiastkami. Na podstawie wykonanych badań stopów intermetalicznych wykazano użyteczność prezentowanej metody w zakresie analizy jednorodności głównych składników stopowych: Al, Fe, Cr jak również lekkich domieszek: H, C, O.
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