Geometries of functional group interactions in enzyme-ligand complexes: Guides for receptor modelling

Summary An approach is described which makes use of X-ray structural data from enzyme-ligand complexes in order to obtain information for application in receptor modelling. The atomic surroundings of five different ligand functional groups were determined for all complex structures recorded in the Brookhaven Protein Data Bank. These atomic surroundings were then superimposed with respect to the atoms of the functional groups of the ligands in order to obtain clouds of neighbouring atoms. General principles were sought to describe the orientiation or favoured position of groups or atoms around those functional groups when bound to a macromolecule. Some simple conclusions and leads for further modelling were thus derived.     

Amalgamation of partitions from multiple segmentation bases: A comparison of non-model-based and model-based methods

The segmentation of customers on multiple bases is a pervasive problem in marketing research. For example, segmentation service providers partition customers using a variety of demographic and psychographic characteristics, as well as an array of consumption attributes such as brand loyalty, switching behavior, and product/service satisfaction. Unfortunately, the partitions obtained from multiple bases are often not in good agreement with one another, making effective segmentation a difficult managerial task. Therefore, the construction of segments using multiple independent bases often results in a need to establish a partition that represents an amalgamation or consensus of the individual partitions. In this paper, we compare three methods for finding a consensus partition. The first two methods are deterministic, do not use a statistical model in the development of the consensus partition, and are representative of methods used in commercial settings, whereas the third method is based on finite mixture modeling. In a large-scale simulation experiment the finite mixture model yielded better average recovery of holdout (validation) partitions than its non-model-based competitors. This result calls for important changes in the current practice of segmentation service providers that group customers for a variety of managerial goals related to the design and marketing of products and services.     

Use of stable isotopes as surrogates for radionuclides for security studies

During the past decade, interest has increased in qualifying and quantifying the threat posed to the public by the illegal use of radionuclides. In order to take investigations beyond the laboratory bench into more realistic scenarios, environmental and safety considerations dictate that these studies be performed on stable and benign surrogates. This paper discusses some of these studies, specifically the use of cerium dioxide for actinide ceramics and calcium and natural strontium ceramics for those based on ⁹⁰Sr.     

Analyse von Bleilegirungen

Ohne Zusammenfassung     

Ma?analytische Bestimmung des Quecksilbers

Ohne Zusammenfassung     

Nachweis und Bestimmung der Halogene

Ohne Zusammenfassung     

ChemInform Abstract: A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

Binary palladium fluorides from PdF to PdF₆ are investigated by matrix‐isolation methods using thermal evaporation and laser ablation to generate Pd atoms for reaction with F₂‐doped Ar and Ne matrices as well as neat F₂ matrices.     

Gas-phase fragmentation characteristics of benzyl-aminated lysyl-containing tryptic peptides

The fragmentation characteristics of peptides derivatized at the side-chain ε-amino group of lysyl residues via reductive amination with benzaldehyde have been examined using collision-induced dissociation (CID) tandem mass spectrometry. The resulting MS/MS spectra exhibit peaks representing product ions formed from two independent fragmentation pathways. One pathway results in backbone fragmentation and commonly observed sequence ion peaks. The other pathway corresponds to the unsymmetrical, heterolytic cleavage of the C_ζ-N_ε bond that links the benzyl derivative to the side-chain lysyl residue. This results in the elimination of the derivative as a benzylic or tropylium carbocation and a (n − l)⁺-charged peptide product (where n is the precursor ion charge state). The frequency of occurrence of the elimination pathway increases with increasing charge of the precursor ion. For the benzylmodified tryptic peptides analyzed in this study, peaks representing products from both of these pathways are observed in the MS/MS spectra of doubly-charged precursor ions, but the carbocation elimination pathway occurs almost exclusively for triply-charged precursor ions. The experimental evidence presented herein, combined with molecular orbital calculations, suggests that the elimination pathway is a charge-directed reaction contingent upon protonation of the secondary ε-amino group of the benzyl-derivatized lysyl side chain. If the secondary ε-amine is protonated, the elimination of the carbocation is observed. If the precursor is not protonated at the secondary ε-amine, backbone fragmentation persists. The application of appropriately substituted benzyl analogs may allow for selective control over the relative abundance of product ions generated from the two pathways.