Discriminant example

In addition to nanoaperture arrays, structured af>ertures could provide higher fluorescence rate enhancement than single apertures, while still enabling efficient signal-to-background discrimination. Examples include the bull s eye structures (56, 23), nanopockets (68) or combined slit and aperture (69). 

The geometrical measurements previously extracted help the making decision system to decide for example whether the defect is linear or not. This defect discrimination into two categories is considered as a first attempt for defect classification. To this end, we define a linearity ratio (Ri) Rl =Length / width. If Rl is equal or near to "1", the defect is volumic, otherwise it is a linear defect. 

The chirality code of a molecule is based on atomic properties and on the 3D structure. Examples of atomic properties arc partial atomic charges and polarizabilities, which are easily accessible by fast empirical methods contained in the PETRA package. Other atomic properties, calculated by other methods, can in principle be used. It is convenient, however, if the chosen atomic property discriminates as much as possible between non-equivalent atoms. 3D molecular structures are easily generated by the GORINA software package (see Section 2.13), but other sources of 3D structures can be used as well. 

The selectivity of an electrophile, measured by the extent to which it discriminated either between benzene and toluene, or between the meta- and ara-positions in toluene, was considered to be related to its reactivity. Thus, powerful electrophiles, of which the species operating in Friedel-Crafts alkylation reactions were considered to be examples, would be less able to distinguish between compounds and positions than a weakly electrophilic reagent. The ultimate electrophilic species would be entirely insensitive to the differences between compounds and positions, and would bring about reaction in the statistical ratio of the various sites for substitution available to it. The idea has gained wide acceptance that the electrophiles operative in reactions which have low selectivity factors Sf) or reaction constants (p+), are intrinsically more reactive than the effective electrophiles in reactions which have higher values of these parameters. However, there are several aspects of this supposed relationship which merit discussion. 

Reaction of an achiral reagent with a molecule exhibiting enantiotopic faces will produce equal quantities of enantiomers, and a racemic mixture will result. The achiral reagent sodium borodeuteride, for example, will produce racemic l-deM/eno-ethanol. Chiral reagent can discriminate between the prochiral faces, and the reaction will be enantioselective. Enzymatic reduction of acetaldehyde- -[Pg.106]

We will use it here in order to derive an analytical form for a crystal profile with a rough interface as an exphcit example. An order parameter

crystalline phase with 0 > 0 and the gaseous (or hquid) one with 0 < 0. 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

The similarity recognition hypothesis presented here would be applicable to the specific and precise discrimination in chemical and biological systems. It is hoped that this review will serve to stimulate further work on the physicochemical origin of the shape-similarity effect on specific molecular recognition, for example, work on weak interactions specific for the three-dimensional shape of interacting groups. 

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