Instrumental Configurations

In Dynamic Secondary Ion Ma s Spectrometry (SIMS), a focused ion beam is used to sputter material from a specific location on a solid surface in the form of neutral and ionized atoms and molecules. The ions are then accelerated into a mass spectrometer and separated according to their mass-to-charge ratios. Several kinds of mass spectrometers and instrument configurations are used, depending upon the type of materials analyzed and the desired results. 

Each type of mass spectrometer has its associated advantages and disadvantages. Quadrupole-based systems offer a fairly simple ion optics design that provides a certain degree of flexibility with respect to instrument configuration. For example, quadrupole mass filters are often found in hybrid systems, that is, coupled with another surface analytical method, such as electron spectroscopy for chemical analysis or scanning Auger spectroscopy. 

Figure 9 Spectrum of ZnSe using the two-laser (PAI) instrumental configuration.

Ensure that the actual instrument configuration conforms to what is written under Experimental supplier, models, modifications, consumables (HPLC or GC columns, gaskets, etc.), and software for the main instrument, peripherals (injectors, integrators, computers, printers, plotters, etc.), and ancillary equipment (vortexer, dispensers, balances, centrifuges, filters, tubing, etc.). 

Sample solution instability or incomplete extraction/separation would show up if several aliquots from the same sample work-up were put in a series of vials that would be run in sequence that would cover at least the duration of the longest sequence that could be accommodated on the autosample/instrument configuration. For example, if an individual chromatogram is acquired for 5.5 minutes, postrun reequilibration and injection take another 2.75 minutes, and 10 repeat injections are performed for each sample vial in the autosampler, then at least 15 60/(5.5 -I- 2.75)/10 = 11 vials would have to be prepared for a 5 P.M. to 8 A.M. (=15 hour) overnight run. If there is any appreciable trend, then the method will have to be modified or the allowable standing time limited. 

In the case of carbamate insecticides, both ESI and APCI can be used. However, in this study, the sensitivity of APCI was 3-5-fold less than that of ESI. In this case, the Z-spray configuration was used with APCI, which gives a lower efficiency of ions reaching the mass analyzer than is achieved with other instrumental configurations. 

Once the selectivity is optimized, a system optimization can be performed to Improve resolution or to minimize the separation time. Unlike selectivity optimization, system cqptimization is usually highly predictable, since only kinetic parameters are generally considered (see section 1.7). Typical experimental variables include column length, particle size, flow rate, instrument configuration, sample injection size, etc. Hany of these parameters can be. Interrelated mathematically and, therefore, computer simulation and e]q>ert systems have been successful in providing a structured approach to this problem (480,482,491-493). 

Various tandem MS instrument configurations have been developed, e.g. sector instruments, such as CBCE, CBCECB or CECBCE, and hybrid instruments, e.g. BCECQQ (B = magnetic sector analyser, E = electrostatic analyser, C = collision cell, Q = quadrupole mass spectrometer), all with specific performance. Sector mass spectrometers have been reviewed [168],... 

The quadrupole mass filter is the most abundant mass analyser today and RF-only multipoles are used as transmission devices/collision regions in various instrumental configurations. The mass filter is used extensively as a stand-alone mass analyser and as an analyser in multistage mass spectrometers. 

Instrument configuration Types of solvents that are available for running HPLC, sampling accessories on hand for IR, detectors available for GC, and the sensitivity toward particular analytes of each detector and instrument... 

Andreae discusses each of these steps in detail [712]. A typical instrumental configuration to accomplish these steps is shown in Fig. 5.19 for the borohy-dride reduction/flame photometric detection system for tin speciation analysis. 

No tandem MS experiment can be successful if the precursor ions fail to fragment (at the right time and place). The ion activation step is crucial to the experiment and ultimately defines what types of products result. Hence, the ion activation method that is appropriate for a specific application depends on the MS instrument configuration as well as on the analyzed compounds and the structural information that is wanted. Various, more or less complementary, ion activation methods have been developed during the history of tandem MS. Below we give brief descriptions of several of these approaches. A more detailed description of peptide fragmentation mles and nomenclature is provided in Chapter 2. An excellent review of ion activation methods for tandem mass spectrometry is written by Sleno and Volmer, see Reference 12, and for a more detailed review on slow heating methods in tandem MS, see Reference 13. 

Fig. 11.16. Representation of three tandem mass spectrometry (MS/MS) scan modes illustrated for a triple quadrupole instrument configuration. The top panel shows the attributes of the popular and prevalent product ion CID experiment. The first mass filter is held at a constant m/z value transmitting only ions of a single mlz value into the collision region. Conversion of a portion of translational energy into internal energy in the collision event results in excitation of the mass-selected ions, followed by unimolecular dissociation. The spectrum of product ions is recorded by scanning the second mass filter (commonly referred to as Q3 ). The center panel illustrates the precursor ion CID experiment. Ions of all mlz values are transmitted sequentially into the collision region as the first analyzer (Ql) is scanned. Only dissociation processes that generate product ions of a specific mlz ratio are transmitted by Q3 to the detector. The lower panel shows the constant neutral loss CID experiment. Both mass analyzers are scanned simultaneously, at the same rate, and at a constant mlz offset. The mlz offset is selected on the basis of known neutral elimination products (e.g., H20, NH3, CH3COOH, etc.) that may be particularly diagnostic of one or more compound classes that may be present in a sample mixture. The utility of the two compound class-specific scans (precursor ion and neutral loss) is illustrated in Fig. 11.17.

It is important that we know at what Reynolds number our instrumental configurations give turbulent flow and work below this figure or we will think that shear thickening is occurring A figure of Re < 3000 to 10,000 is usually satisfactory for cone and plates or capillary viscometers, but values as low as 300 may be the maximum for some cup and bob units. 

In the last twenty years, many of the developed and validated high performance liquid chromatography methods with conventional diode array or fluorescence detectors (DAD, FLD) were improved and substituted by new hyphenation with mass spectrometric instrumentation and/or NMR, especially for the analyses of raw materials derived from Natural sources. The main goal of this coupling is achieved by improvement of selectivity and sensitivity of new instrumental configurations [7], Furthermore, with these configurations it is possible to obtain, in only one analysis, the complete chemical structure elucidation, identification and quantification of targeted compounds. 

These instrumental configuration can be successfully applied in Food chemistry analyses, especially related to the determination of novel Nutraceutics [22], and on recombinant monoclonal antibodies [23],... 

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