Use of calculated quantum chemical properties as surrogates for solvatochromic parameters in structure-activity relationships

Cramer, Christopher J.; Famini, George R.; Lowrey, Alfred H.

doi:10.1021/ar00035a006

Cited by 90 publications

(60 citation statements)

References 86 publications

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“…If the rays are truncated when the electron density has fallen to the 0.002-erau 3 level, their endpoints define the molecular VDW surface. 33 Within our electronic modeling paradigm, atomic surface properties are determined on this 0.002-erau 3 isosurface.…”

Section: Tae Librarymentioning

confidence: 99%

“…These terms are further defined in Table I 3 oxygens, sp 2 oxygens, sulfurs, fluorines, and chlorines. Several clustering methods were used on each data set to ascertain the most useful method for the given data.…”

Section: Tae Definition and Identificationmentioning

confidence: 99%

“…Separate descriptions of electrostatic interactions, van der Waals forces, charge transfer interactions, polarizability, and hydrophobic effects are desirable, but such clear dimensions are not often possible given the kind of molecular information available in a typical QSAR or QSPR study. One approach to this problem has been to use property indices computed from atomic connectivity patterns of molecules, or from spectral 3 and experimental 4 data taken from a training set of molecules, but clean separation of each type of interaction into a set of additive linear models can be elusive in the real world. A well-utilized alternative approach uses molecular connectivity information to construct topological property indices and substructure keys.…”

Section: Introductionmentioning

confidence: 99%

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QSPR analysis of HPLC column capacity factors for a set of high-energy materials using electronic van der waals surface property descriptors computed by transferable atom equivalent method

Breneman

Rhem

1997

J. Comput. Chem.

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The new transferable atom equivalent (TAE) method for rapid molecular electron density reconstruction was used to compute a set of molecular surface property descriptors. These descriptors were then used to construct HPLC column capacity factor PLS models for a series of high‐energy materials. The new TAE‐derived surface property indices are also available from ab initio or semiempirical wave functions, but the speed and accuracy of TAE reconstruction make it the method of choice for obtaining these indices. The new QSPR indices are based upon the extrema, distributions, and surface integrals of the electronic kinetic energy density, the Politzer average local ionization potential (pip), and the electrostatic potential, as well as the rates at which these properties change normal to the 0.002‐e/au3 molecular surface. The distribution of the properties were recorded as surface histograms. While property extrema and surface integral averages proved to be descriptive, the most useful new indices were found to correspond to histogram bin data computed for K and G surface kinetic energy densities. All‐subsets‐regression modeling showed that when mixtures of traditional connectivity indices, theoretical linear solvation energy relations (TLSERs), and generalized interaction properties functions (GIPFs) were included with the new indices in the variable sets, the new indices were consistently involved in the best 2% of the capacity factor models. Peak retention time data from two different columns were examined (a Hypersil “CPS” cyanoalkylated column and a standard reverse‐phase Hypersil “ODS” column) using a phosphate buffer mobile phase at pH 3.0. The result were compared to an earlier TLSER correlation analysis of the same data by Lowrey and Famini. The TAE‐generated surface property descriptors were shown to provide superior PLS models for both sets of columns and conditions. © 1997 by John Wiley & Sons, Inc.

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Section: Tae Librarymentioning

confidence: 99%

Section: Tae Definition and Identificationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

QSPR analysis of HPLC column capacity factors for a set of high-energy materials using electronic van der waals surface property descriptors computed by transferable atom equivalent method

Breneman

Rhem

1997

J. Comput. Chem.

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“…These techniques have produced good correlations for these interactions in a large number of compounds [11]. The LSER methodology and the related ideas of quantitative structureactivity relationships [12] are widely used in life sciences, and related fields of biology, chemistry and physics, to understand complex interactions associated with molecular structure and properties [10]. This paper analyzes HPLC characteristic capacity factors for common energetic materials and related molecules, using the computationally based theoretical linear solvation energy relationships (TLSER) [13].…”

Section: Introductionmentioning

confidence: 99%

“…TLSER descriptors have been shown to give good correlations between calculated quantities and experimental observations. These descriptors also provide good physical interpretations for a wide variety of properties including HPLC retention indices and absorption indices for some ylides [17], activities of local anesthetics related to the molecular transform [ 18], and dopamine receptor activities for hydrated derivatives of cocaine [12]. Ford and Livingstone pointed out the advantages of computationally derived descriptors for LSER [19].…”

Section: Introductionmentioning

confidence: 99%

Using theoretical descriptors in quantitative structure-activity relationships: HPLC capacity factors for energetic materials

Lowrey

Famini

1995

Struct Chem

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The widespread application of computational techniques to studies in biology and chemistry has led to a quest for important characteristic properties that may be directly derived from these methods. The theoretical linear solvation energy relationships (TLSER) have successfully replaced empirical parameters, such as in the linear solvation energy relationships (LSER) of Kamlet and Taft, with theoretical descriptors that are consistently derived for a wide variety of chemical and biological properties and for a large range of molecules. These descriptors are small in number, well-defined in theoretical terms, and provide a systematic basis for computational studies of complex phenomena. Energetic materials are a class of molecules whose explosive characteristics have been previously studied by empirical methods. The forensic and environmental sciences have prompted the conduct of detailed high performance liquid chromatography (HPLC) studies for identifying of trace quantities of commonly used explosives. The TLSER methodology provides good correlations between the calculated quantities and the experimentally determined HPLC capacity factors. This provides a reasonable interpretation of retention times in terms of molecular volume and quantities associated with acidity and basicity.

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Using theoretical descriptors to model solvent effects in the isomerization ofcis-stilbene

McGill

Rice

Baronavski

et al. 1996

Int. J. Quantum Chem.

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mExperimental observations of the photoinduced excited-state lifetime of cis-stilbene have shown a distinct dependence on solvation processes. The rate of decay, dominated by a cis-trans isomerization, is more rapid in polar solvents than in nonpolar solvents. Linear solvation energy relationship (LSER) techniques show that this can be explained in terms of polarity and polarizability parameters for the solvent. Theoretical linear solvation energy relationship (TLSER) analysis shows that this can be explained in terms of solvent polarizability and electrostatic basicity. New TLSER descriptors based on calculated solvent bond diplole parameters are also successful in describing this solvent dependence. Solvent-dependent dipole moments are calculated for an approximate stilbene transition-state geometry using the polarizable continuum model (PCM), which suggests the usefulness of a more detailed study of this photoisomerization process using current solvation theory and computational techniques. 0

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Use of calculated quantum chemical properties as surrogates for solvatochromic parameters in structure-activity relationships

Cited by 90 publications

References 86 publications

QSPR analysis of HPLC column capacity factors for a set of high-energy materials using electronic van der waals surface property descriptors computed by transferable atom equivalent method

QSPR analysis of HPLC column capacity factors for a set of high-energy materials using electronic van der waals surface property descriptors computed by transferable atom equivalent method

Using theoretical descriptors in quantitative structure-activity relationships: HPLC capacity factors for energetic materials

Using theoretical descriptors to model solvent effects in the isomerization ofcis-stilbene

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