Cyclotron resonance mode

The most common modes of operation for ms/ms systems include daughter scan, parent ion scan, neutral loss scan, and selected reaction monitoring. The mode chosen depends on the information required. Stmctural identification is generally obtained using daughter or parent ion scan. The mass analyzers commonly used in tandem systems include quadmpole, magnetic-sector, electric-sector, time-of-flight, and ion cyclotron resonance. Some instmments add a third analyzer such as the triple quadmpole ms (27). 

To check the identity and purity of the products obtained in the above reactions it is not sufficient to analyze for the sulfur content since a mixture may incidentally have the same S content. Either X-ray diffraction on single crystals or Raman spectra of powder-like or crystalline samples will help to identify the anion(s) present in the product. However, the most convincing information comes from laser desorption Fourier transform ion cyclotron resonance (FTICR) mass spectra in the negative ion mode (LD mass spectra). It has been demonstrated that pure samples of K2S3 and K2S5 show peaks originating from S radical anions which are of the same size as the dianions in the particular sample no fragment ions of this type were observed [28]. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

Laser desorption (LD) Fourier transform ion cyclotron resonance MS (FTICR-MS) in the positive mode was applied for the analysis of... 

Octadecyl sulfate sodium salt (Ci8H37-0-S03 Na+) was examined by laser desorption (LD) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) in the negative mode resulting in [M - H] ions. Little fragmentation was observed under these conditions [28]. 

Laser ablation coupled to ion cyclotron resonance Fourier transform mass spectrometry (in both positive and negative ion modes) can be used to distinguish natural and... 

In thick ( 300 pm) crystals of GaN electronic excitons of shallow dopants have been observed in far infrared absorption at 215 cm 1 [44], Interpreted as the ls-2p transition of a residual shallow donor, its binding energy was calculated to be (35.5 0.5) meV. Further modes at 149 and 242 cm 1 have been observed in mixed phase GaN/GaAs in Raman scattering and have been associated with electronic excitations of shallow donors in cubic and sphalerite GaN, respectively [45] see also [46], Far infared absorption at 23.2 cm 1 in magnetic fields has been used to determine the effective electron mass in GaN, m = 0.20 0.005 m, (corrected for polaron effects) in cyclotron resonance [47]. 

Modes of MS ionization are El, Cl, FAB, PDI, MALDI and ESI and major MS analysers include time-of-llight (TOE) quadmpole ion-trap (QIT) Fourier transform ion cyclotron resonance (FTICR) and orbitrap. 

Fig. 1 Schematic representation of a mass spectrometer depicting its main components and the different modes used. Abbreviations DIP direct insertion probe DEP direct exposure probe GC gas chromatography LC liquid chromatography CE capillary chromatography TEC thin-layer chromatography FEE field-flow fractionation APCI atmospheric pressure ionization El electron impact Cl chemical ionization FAB fast-atom bombardment PD plasma desorption MALDI matrix-assisted laser desorption ionization ED laser desorption TSP thermospray ESI electron spray ionization HSI hypherthermal surface ionization Q quadropole QQQ triple quadropole TOE time-of-fiight FTMS Fourier transform mass spectrometer IT ion trap EM electrom multiplier PM photomultiplier ICR ion cyclotron resonance.

A more general approach that can be employed for all mass analyzers [as time-of-flight (TOF), ion cyclotron resonance (Fourier trans-form-mass spectroscopy, FT-MS), Q-TOF] is based upon measuring the full width half-maximum, as shown in Fig. 2.2. In the same figure, the definition of mass accuracy is also reported. This parameter reflects on the specificity of mass measurements. In fact, on one hand it allows to determine the accurate mass of a selected ion (and, consequently, its elemental composition). On the other hand it allows to operate in accurate mass mode in order to identify species of interest present in complex matrices on the basis of their elemental composition. 

Radical cations of saturated hydrocarbons have strong electronic absorptions in the visible and near-infrared region of the spectrum. The strongly colored nature of alkane radical cations is in striking contrast to neutral alkanes that absorb electronically only in the vacuum UV. The electronic absorption of alkane radical cations has been studied in the solid phase by matrix isolation using y-irradiation [1-3] and in the gas phase by ion cyclotron resonance (ICR) photodissociation in either the steady-state or pulsed mode of operation [4]. Both methods have their specific merits and drawbacks. A major concern in matrix isolation spectroscopy is spectral purity (because of the possible presence of other absorbing species) and... 

Ion cyclotron resonance (ICR) and flowing afterglow experiments can also be used to derive relative affinities. Neutral beam experiments, where a beam of alkali atoms such as Cs is crossed with a beam of molecules such as PCI3 or (012)2 have been used to derive thermochemistry for anions such as PCli" and Cli", but proper analysis of this type of data is difficult. High-resolution negative ion photoelectron spectroscopy (NIPES) experiments can provide otherwise unobtainable information on hypervalent anions, including precise electron affinities and vibrational frequencies.This technique has limited applicability to hypervalent species with more than three atoms because of vibrational congestion from low-frequency modes. 

Fig. 3.8. Positive mode electrospray ionization Fourier-transform ion cyclotron resonance mass spectrum of Suwannee River fulvic acid mixture, (a) Entire spectrum over 225-3000 m/z region (b) and (c) after scale expansion to highlight the 370-450 and 423-426 m/z regions (d) and (e) after further expansion to highlight 0.3 mass windows. Reprinted from Stenson etal. (2002) with permission from the American Chemical Society.

In this contribution, we report on the surface modifications of polymers by a dual frequency electron cyclotron resonance (ECR) plasma and their influence on the formation of the metal-polymer interfaces. The surface modifications are studied with respect to different parameters of the plasma treatment including the influence of an atmospheric contact. The interface of an evaporated metal film with a polymer surface is characterized in terms of the observed growth mode of the film as a function of the polymer surface properties. 

---