Mass Spectral Search System MSSS

Heller, S. R., and Milne, G. W. EPA/NIH Mass Spectral Search System (MSSS), A Division of CIS. Washington, DC U.S. Government Printing Office. An interactive computer searching system containing the spectra of over 32,000 compounds. These can be searched on the basis of peak intensities as well as by Biemann and probability matching techniques. 

The spray paint can was inverted and a small amount of product was dispensed into a 20 mL glass headspace vial. The vial was immediately sealed and was incubated at 80°C for approximately 30 min. After this isothermal hold, a 0.5-mL portion of the headspace was injected into the GC/MS system. The GC-MS total ion chromatogram of the paint solvent mixture headspace is shown in Figure 15. Numerous solvent peaks were detected and identified via mass spectral library searching. The retention times, approximate percentages, and tentative identifications are shown in Table 8 for the solvent peaks. These peak identifications are considered tentative, as they are based solely on the library search. The mass spectral library search is often unable to differentiate with a high degree of confidence between positional isomers of branched aliphatic hydrocarbons or cycloaliphatic hydrocarbons. Therefore, the peak identifications in Table 8 may not be correct in all cases as to the exact isomer present (e.g., 1,2,3-cyclohexane versus 1,2,4-cyclohexane). However, the class of compound (cyclic versus branched versus linear aliphatic) and the total number of carbon atoms in the molecule should be correct for the majority of peaks. 

Figure 5.9. Spectral search at Spectral Database Systems (SDBS). The infrared (IR), nuclear magnetic resonance H-NMR and 13C-NMR), electron spin resonance (ESR), and mass (MS) spectra of organic compounds and common biochemical compounds can be viewed/retrieved from SDBS.

Mass spectral quality is an important consideration in performing a successful GC-MS analysis. The quality of the mass spectra depends on (1) the concentration of the constituents in the sample solution, (2) the GC operating conditions used to resolve the peaks, and (3) excessive pressure fluctuation in the MS unit of the GC-MS system leading to distortion of the mass spectrum, especially an El mass spectrum, as reflected in the relative abundance of the ion peaks. The implication of (3) is that distortions of this type could lead to misinterpretation of the spectrum even though a library search is performed. 

The MST/EPA/NIH Mass Spectral Library 1998 database ( www.nist.gov/ srd/analv.htm) is the product of a muftiyear, comprehensive evaluation and expansion of the world s most widely used mass spectral reference library, and is sold in ASCII or Windows versions. It contains 108,000 compounds with electron ionization spectra, chemical structures, and molecular weights. It is available with the NIST MS Search Program for GC/MS deconvolution, MS interpretation, and chemical substructure analysis. The NIST chemistry WebBopk ( http //webbook.nist.gov) is a. free online system that contains the mass spectra of over 12,000 compounds (this Standard Reference Data Program also has IR and UV-Vis spectra). 

It is not trivial to define or select substructures that should be considered for this purpose. For the STIRS system, considerable effort has gone into the search for substructures that can be successfully classified by the implemented spectral similarity search. The Mass-Lib system uses a predefined set of 180 binary molecular descriptors to characterize the similarity of structures. In most investigations a more or less arbitrary set of substructures, functional groups or more general structural properties (compound classes) has been considered. Self-adapting methods that automatically analyse the molecular structures in the hitlist (for instance by searching for frequent and large substructures) have not been used up to now in MS. 

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