Dimension Concepts and Reduced Dimensions in Toxicological QShAR Databases as Tools for Data Quality Assessment

The dimensions of databases can be defined based on a variety of concepts, ranging from the standard tools of principal component analysis to context-biased approaches. The effective dimensions of databases, in particular the effective dimensions involving continua such as electron density data, provide a set of important tools for database comparisons and for the evaluation of some aspects of database quality. The problems associated with database comparisons and database mergers, such as those occurring in the process of database unification in the actual merger of two pharmaceutical companies, provide challenging tasks and opportunities for data science. Some of the tools for effective dimension reduction and dimension expansion are reviewed in the context of database quality control and conditions for database compatibility are presented. A common misconception affecting data sampling techniques for data quality evaluation is discussed and methods for circumventing the associated sampling errors are described.     

Influence of Metal,Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study

The nature of intermolecular interactions governing supramolecular polymerizations is very important for controlling their cooperativity. In order to address this problem, supramolecular columns made of Pt^II and Pd^II complexes of oligo(phenylene ethynylene)‐based pyridine (OPE) and tetrazolylpyridine ligands (TEP) were investigated through the dispersion‐corrected PM6 method. Aromatic, CH–π, M–Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of Pt^II led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor for controlling cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger preformed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons.     

Stereoselective syntheses of pinane-based 1,3-diamines and their application as chiral ligands in the enantioselective addition of diethylzinc to benzaldehyde

A library of 1,3-difunctionalized pinane derivatives was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The key intermediate β-lactam 2 was prepared regio- and stereoselectively from (?)-apopinene 1. The treatment of 2 with di-tert-butyl dicarbonate afforded N-Boc β-lactam 3, while acid-catalyzed ring opening of 2 resulted in amino acid 4. Nucleophilic ring opening of 3 with dimethylamine, followed by deprotection and benzylation, furnished β-amino amides 5, 8, and 11, which were transformed in two steps into the corresponding N-tosyldiamines 7, 10, and 13, respectively. Since the use of other amines, such as diethylamine, to study the influence of dialkyl substitution was unsuccessful, an alternative synthetic route was applied. Amidation of tosylated β-amino acid 14 furnished amides 15–25. Reduction of 15, 16, 19, 20, and 24 resulted in N-tosyl diamines 26–30. The β-amino amides and N-tosylated diamines were used as chiral ligands in the enantioselective alkylation of benzaldehyde with diethylzinc, resulting in (R)- and (S)-1-phenyl-1-propanol. The (R)-enantiomer was predominant except when 17, 22, 23, and 25 were used as ligands, in which case the opposite stereochemistry was observed. The best ee values (up to 83%) were obtained when 17, 20, 23, and 25 were used as catalysts.     

Prompt gamma neutron activation analysis (PGAA): recent developments and applications

Journal of Radioanalytical and Nuclear Chemistry - Prompt gamma neutron activation analysis has become an important part of the analytical toolkit, practiced at several research reactors worldwide....     

Characterizations of higher-order convexity properties with respect to Chebyshev systems

In this paper various notions of convexity of real functions with respect to Chebyshev systems defined over arbitrary subsets of the real line are introduced. As an auxiliary notion, a concept of a relevant divided difference and also a related lower Dinghas type derivative are also defined. The main results of the paper offer various characterizations of the convexity notions in terms of the nonnegativity of a generalized divided difference and the corresponding lower Dinghas type derivative.     

Novel Method for the High-Yielding Synthesis of Steroidal Hydroxamic acid Derivatives

Steroidal 17-hydroxamic acid derivatives were synthesized in high yields in palladium-catalysed carbonylation reaction of 17-iodo-androst-16-ene derivatives under mild reaction conditions.     

Increasing the dynamic range for the analysis of boron in PGAA

Prompt gamma activation analysis (PGAA) is especially sensitive for elements with high neutron-capture cross sections, like boron, which can be detected down to a level of ng/g. However, if it is a major component, the high count rate from its signal will distort the spectra, making the evaluation difficult. A lead attenuator was introduced in front of the HPGe-detector to reduce low-energy gamma radiation and specifically the boron gamma rays reaching the detector, whose thickness was found to be optimal at 10 mm. Detection efficiencies with and without the lead attenuator were compared, and it was shown that the dynamic range of the PGAA technique was significantly increased. The method was verified with the analyses of stoichiometric compounds: TiB₂, NiB, PVC, Alborex, and Alborite.