An efficient method for computing the QTAIM topology of a scalar field: The electron density case

An efficient method for computing the quantum theory of atoms in molecules (QTAIM) topology of the electron density (or other scalar field) is presented. A modified Newton–Raphson algorithm was implemented for finding the critical points (CP) of the electron density. Bond paths were constructed with the second‐order Runge–Kutta method. Vectorization of the present algorithm makes it to scale linearly with the system size. The parallel efficiency decreases with the number of processors (from 70% to 50%) with an average of 54%. The accuracy and performance of the method are demonstrated by computing the QTAIM topology of the electron density of a series of representative molecules. Our results show that our algorithm might allow to apply QTAIM analysis to large systems (carbon nanotubes, polymers, fullerenes) considered unreachable until now. © 2012 Wiley Periodicals, Inc.     

A single microcystin in a toxic Microcystis bloom from the river Río de la Plata (Argentina)

Microcystis is one of the most common bloom-forming cyanobacteria genera in diverse ecosystems. More than 80% of its strains are toxic, mainly due to their ability to produce metabolites known as microcystins (MC). Here we report on a M. aeruginosa bloom that appeared in the summer of 2001 at a site of the Río de la Plata, within the city of Buenos Aires. The symptoms in mice indicated that the bloom was hepatotoxic. LC-PDA analysis revealed a similar high concentration (0.9–1?mg?g^–1?d w) of just one MC in the bloom biomass during the 3-month study period. During this period most of the MC (ca. 98 %) was found intracellularly, and the content remained almost the same. The molecular mass of the bloom MC was 1036?Da, as deduced from LC-ESI-MS data. Fragment ion analysis by LC-IT-MS-MS allowed identifying 6 out of the 7 amino acids, as well as their position in the molecule. The molecular mass of the unidentified amino acid residue was 155?Da. According to the data obtained, the MC under study was MC-XR, X representing the unidentified amino acid. This is the first report both on the characterisation of MCs in an urban site of the Río de la Plata waters, and on an Argentinean bloom exhibiting only one MC variant.     

Melamine trisulfonic acid-catalyzed N-formylation of amines under solvent-free conditions

A highly convenient method for N-formylation of amines via treatment by formic acid in the presence of melamine trisulfonic acid as a catalyst has been developed. This method showed improvements over previous reports in terms of yield, reaction time and chemoselectivity.     

中德化学启蒙教材有机内容比较

就化学启蒙教育阶段有机化学教学内容,将德国的《今日化学SⅠ》、国内的沪教版、人教版、鲁教版4套教材,从知识内容的选取、组织呈现等角度进行了比较,并在实验设计、作业设计、拓展学习3方面向教材编写和教学实践提出了建议。     

Multiple Keys for a Single Lock: The Unusual Structural Plasticity of the Nucleotidyltransferase (4′)/Kanamycin Complex

The most common mode of bacterial resistance to aminoglycoside antibiotics is the enzyme‐catalysed chemical modification of the drug. Over the last two decades, significant efforts in medicinal chemistry have been focused on the design of non‐ inactivable antibiotics. Unfortunately, this strategy has met with limited success on account of the remarkably wide substrate specificity of aminoglycoside‐modifying enzymes. To understand the mechanisms behind substrate promiscuity, we have performed a comprehensive experimental and theoretical analysis of the molecular‐recognition processes that lead to antibiotic inactivation by Staphylococcus aureus nucleotidyltransferase 4′(ANT(4′)), a clinically relevant protein. According to our results, the ability of this enzyme to inactivate structurally diverse polycationic molecules relies on three specific features of the catalytic region. First, the dominant role of electrostatics in aminoglycoside recognition, in combination with the significant extension of the enzyme anionic regions, confers to the protein/antibiotic complex a highly dynamic character. The motion deduced for the bound antibiotic seem to be essential for the enzyme action and probably provide a mechanism to explore alternative drug inactivation modes. Second, the nucleotide recognition is exclusively mediated by the inorganic fragment. In fact, even inorganic triphosphate can be employed as a substrate. Third, ANT(4′) seems to be equipped with a duplicated basic catalyst that is able to promote drug inactivation through different reactive geometries. This particular combination of features explains the enzyme versatility and renders the design of non‐inactivable derivatives a challenging task.