Applications are presented that link RDF technologies to methods from statistics and cheminformatics. Calculated molecular descriptors can also.
Python for molecular modeling. Python Molecular Viewer (PMV) http://mgltools.scripps.edu. Chemistry toolkits and utilities. Molecular Descriptors: LINK. Modular Chemical Descriptor Language (MCDL): Stereochemical modules . In the majority of cases it is a four- coordinated atom (such as a carbon atom), but there is a substantial number of stereoisomers having chiral centers with three substituents. Notable examples include chiral sulfoxides. The priorities of the substituents attached to a chiral center are the MCDL priorities (based on ASCII codes) of the attached fragments and terminal atoms, if any (see below). Once these are known, a Fischer projection of the configuration at the chiral atom is drawn. A Fischer projection is a planar representation of a molecule that preserves information about chirality. With the chiral atom at its center, a horizontal line represents two bonds bending forward toward the viewer, and a vertical line represents two bonds bending back away from the viewer. In the projection, the highest MCDL priority substituent on the chiral atom is placed at the top and the second highest at the bottom. The other two substituents appear at the left and right and are positioned to preserve the configuration of the chiral atom. Once oriented in this way, the atom stereochemistry is specified in the MCDL linear descriptor as . The MCDL composition and connectivity modules for both of these are C; CHH; 2. CHHH; CO; 2. OH. The chiral atom is fragment 1 in the descriptor. Its substituents and their priorities are CHH (2), CHHH (3), CO (5), and OH (6). Three- dimensional representations of this compound's enantiomers are shown in Figure 2 with the priorities of the substituents indicated. Figure 1. Structural formula of 2- hydroxy- 2- methylbutanoic acid. Figure 2. Three- dimensional representations of 2- hydroxy- 2- methylbutanoic acid's enantiomers with the MCDL priorities of the substituents on the chiral atom indicated. The two structures are redrawn as Fischer projection formulas in Figure 3. The four substituents have been placed on the projection so the fragment having the highest priority is at the top and the next highest at the bottom. Thus, the stereochemistry for the left structure is specified in the MCDL as . The MCDL composition module of lactic acid is CH; CHHH; CO; 2. OH, and the chiral carbon is part of the first fragment. The attached fragments and their MCDL priorities are CHHH (2), CO (3), and OH (4). The fourth substituent on the chiral carbon, H, is actually part of fragment 1, but it must be considered on its own in order to specify the stereochemistry in the linear descriptor. To handle this situation, a new rule is added to the MCDL: Structural fragments have higher priorities than terminal atoms (numbers have lower ASCII codes than letters). Thus, of the four substituents attached to the chiral atom in lactic acid, the terminal atom H has the lowest priority. Orienting the R configuration as the Fischer projection in Figure 4 gives the MCDL descriptor . While treatment of structures with multiple chiral centers in the MCDL is straightforward in many cases, the presence of multiple chiral centers in certain quasi- symmetrical structures may lead to complications due to the fact that the unique part of the MCDL linear descriptor is generated without consideration of stereochemistry. As a result, constitutionally, but not stereochemically, equivalent chiral centers may receive arbitrarily selected fragment numbers. Figure 5 shows the 3- dimensional structure of meso- tartaric acid having two constitutionally identical, but stereochemically different, chiral centers (opposite configurations). Because of the topological symmetry of the molecule, two MCDL numbering schemes are possible. The MCDL stereochemistry descriptor for this numbering scheme is . Since 5 is a higher priority than H, this difference allows us to choose . As a general rule, for quasi- symmetrical structures where multiple equivalent numbering schemes are possible, all must be explored for selection of the canonical (the lowest ASCII code sequence) stereochemistry descriptor. An alternative approach entails the use of hash variables for constitutionally equivalent stereogenic fragments (see Generation of atomic MCDL stereodescriptors from structure diagrams section below). Three- substituent chiral centers. The MCDL can also specify chirality of atomic centers with only three substituents in those cases where the fourth substituent position is occupied by an electron pair. In this case, the electron pair is treated as a . The priority of the electron pair is defined in the MCDL as 0 (zero), giving it, maybe surprisingly, higher priority than structural fragments and terminal atoms. For example, the chirality descriptors of ethyl(fluoromethyl)sulfoxide (CFHH; CHH; CHHH; SO. Vls. 3d - Chemistry toolkits and utilities. Chemistry toolkits & utilities.
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