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By Robert K. Lindsay, etc.
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Extra info for Applications of Artificial Intelligence for Organic Chemistry: The Dendral Project (McGraw-Hill advanced computer science series)
Spiro-fused ring structures have a node of degree 4, corresponding to the four links that fuse on a single vertex atom. A CATALOG has been developed for most vertex graphs of chemical interest. The CATALOG as of this writing contains several thousand vertex graphs including all trivalent vertex graphs up to 18 nodes, plus some quadrivalent varieties. Higher-order graphs are handled by “tricks” that reduce them to trivalent and quadrivalent graphs. For example, a six-valent node may be considered to be a connection of two quadrivalent nodes: \ / \ 1 -*= -*-*/ \ /\ Some examples of vertex graphs and associated chemical structures are given in Figure 4-2.
Such rearrangements do in fact occur and complicate the picture further. The major value of metastable ions is that the presence of a metastable peak establishes a direct parent-daughter relationship between two ions since metastable ions are not formed in the ionization chamber and are thus not products of rearrangements. When this relationship exists, it is known that the two ions are connected (or overlap) in the parent molecule. A very common rearrangement is called hydrogen tr&sfer. This arrangement occurs when hydrogens migrate from one ion to another resulting in a more stable structure.
This widening has relatively little effect on the intensity of sharp peaks, but relatively greater effect on the wide metastable peaks. This technique is called metastable defocusing. When first noted, these unsharp metastable peaks were looked on as an anomaly of the method, and attempts were made to eliminate them. However, they are now recognized as the source of important information that cannot be obtained from normal spectral peaks. The instrument we have described is in fact designed to enhance the chances for the appearance of metastable ions and provide facilities for their measurement without interference from normal ions.