Calculation of crystal optical properties from molecular electron density

We have recently developed a method to obtain distributed atomic polarizabilities adopting a partitioning of the molecular electron density (for example, the Quantum Theory of Atoms in Molecules, [1]), calculated with or without an applied electric field. The procedure [2] allows to obtained atomic polarizability tensors, which are perfectly exportable, because quite representative of an atom in a given functional group. Among the many applications of this idea, the calculation of crystal susceptibility is easily available, either from a rough estimation (the polarizability of the isolated molecule is used) or from a more precise estimation (the polarizability of a molecule embedded in a cluster representing the first coordination sphere is used). Lorentz factor is applied to include the long range effect of packing, which is enhancing the molecular polarizability. Simple properties like linear refractive index or the gyration tensor can be calculated at relatively low costs and with good precision. This approach is particularly useful within the field of crystal engineering of organic/organometallic materials, because it would allow a relatively easy prediction of a property as a function of the packing, thus allowing "reverse crystal engineering". Examples of some amino acid crystals and salts of amino acids [3] will be illustrated, together with other crystallographic or non-crystallographic applications. For example, the induction and dispersion energies of intermolecular interactions could be calculated with superior precision (allowing anisotropic van der Waals interactions). This could allow revision of some commonly misunderstood intermolecular interactions, like the halogen bonding (see for example the recent remarks by Stone or Gilli [4]). Moreover, the chemical reactivity of coordination complexes could be reinvestigated, by coupling the conventional analysis of the electrostatic potential (useful only in the circumstances of hard nucleophilic/electrophilic interaction) with the distributed atomic polarizability. The enhanced reactivity of coordinated organic ligands would be better appreciated. [1] R. F. W. Bader, Atoms in Molecules: A Quantum Theory. Oxford Univ. Press, 1990. [2] A. Krawczuk-Pantula, D. Pérez, K. Stadnicka, P. Macchi, Trans. Amer. Cryst. Ass. 2011, 1-25 [3] A. S. Chimpri1, M. Gryl, L. H.R. Dos Santos1, A. Krawczuk, P. Macchi Crystal Growth & Design, in the press. [4] a) A. J. Stone, J. Am. Chem. Soc. 2013, 135, 7005−7009; b) V. Bertolasi, P. Gilli, G. Gilli Crystal Growth & Design, 2013, 12, 4758-4770.

Dein Gott ist ein Esel. Griechische und römische Tierkarikaturen als Spiegel antiker Wertvorstellungen

Die Doktorarbeit “Dein Gott ist ein Esel. Griechische und römische Tierkarikaturen als Spiegel antiker Wertvorstellungen” hat sowohl die lange und intensive Beziehung zwischen Mensch und Tier als auch das antike Humorverständnis zum Thema. Trotz seiner verschiedenen Rollen als Helfer und Freund blieb (und bleibt) das Tier der Stereotyp des ‚Anderen’, das Gegenbild, das alle Menschen teilen. Das Lachen und damit die Karikatur wiederum helfen uns, zu reflektieren und Distanz zu den Dingen und vielleicht zu uns selbst zu gewinnen. Tierkarikaturen sind deshalb besonders geeignet, ein Spiegel menschlicher Fehler und Schwächen zu sein. In der Regel handelt es sich bei den antiken Tierkarikaturen um Bilder von Menschen, die tiergestaltig ‚verzerrt’ sind, zum Beispiel ein Lehrer mit dem Äusseren eines Esels. Solche Darstellungen sind ab dem 6. Jh. v. Chr. zu finden und werden in hellenistischer und römischer Zeit häufiger, wo der Fokus der Arbeit liegt. Meist sind es Terrakotta- oder Bronzefiguren, die verschiedenen gesellschaftlichen Bereichen zugeordnet werden können wie Religion, Politik, Freizeit usw. Unter Berücksichtigung des spezifischen kulturellen und funktionalen Kontextes jedes Stückes sowie zeitgenössischen schriftlichen Quellen wird die Bedeutung dieser Karikaturen erarbeitet.

Current role of enzyme analysis for urea cycle disorders

Urea cycle disorders (UCD) are due to defects of any of its six enzymes or two transporters. The definitive diagnosis of defects of the three mitochondrial enzymes, N-acetylglutamate synthase (NAGS), carbamylphosphate synthetase I (CPS1) and ornithine transcarbamylase (OTC) depends on either molecular mutation analysis or measurement of enzyme activity, whereas the diagnosis of deficiencies of the three cytosolic enzymes argininosuccinate synthetase (ASS), argininosuccinate lyase (ASL) and arginase I (ARG1) is usually straightforward, based on marker metabolites. Enzyme assays for all UCD have been used since their first description, for disease confirmation and in some instances even for prenatal diagnosis. The genetic bases of the UCD have only been unraveled from the 1980s; the last gene cloned being the NAGS gene in 2002. In this review we discuss the enzymatic assays for all urea cycle enzymes from a historical perspective, their potential and drawbacks, and the current role of enzymatic analysis in UCD in general.