Expedient method for the transmetalation of Zn(II)-centered salphen complexes

Various mono- and bis-ZnII complexes derived from salphen ligands have been conveniently transmetalated with a number of transition metal (TM) acetates (M=Ni, Pd, Mn) in THF to afford their respective TM-salphen counterparts in excellent isolated yields (80-100%). This new transmetalation procedure allows in situ switching between supramolecular and catalytic functions of the metallosalphen complex.     

Quantitation of 17beta-nandrolone metabolites in boar and horse urine by gas chromatography-mass spectrometry

A method to quantify metabolites of 17beta-nandrolone (17betaN) in boar and horse urine has been optimized and validated. Metabolites excreted in free form were extracted at pH 9.5 with tert-butylmethylether. The aqueous phases were applied to Sep Pak C18 cartridges and conjugated steroids were eluted with methanol. After evaporation to dryness, either enzymatic hydrolysis with beta-glucuronidase from Escherichia coli or solvolysis with a mixture of ethylacetate:methanol:concentrated sulphuric acid were applied to the extract. Deconjugated steroids were then extracted at alkaline pH with tert-butylmethylether. The dried organic extracts were derivatized with MSTFA:NH4I:2-mercaptoethanol to obtain the TMS derivatives, and were subjected to analysis by gas chromatography mass spectrometry (GC/MS). The procedure was validated in boar and horse urine for the following metabolites: norandrosterone, noretiocholanolone, norepiandrosterone, 5beta-estran-3alpha, 17beta-diol, 5alpha-estran-3beta, 17beta-diol, 5alpha-estran-3beta, 17alpha-diol, 17alpha-nandrolone, 17betaN, 5(10)-estrene-3alpha, 17alpha-diol, 17alpha-estradiol and 17beta-estradiol in the different metabolic fractions. Extraction recoveries were higher than 90% for all analytes in the free fraction, and better than 80% in the glucuronide and sulphate fractions, except for 17alpha-estradiol in the glucuronide fraction (74%), and 5alpha-estran-3beta, 17alpha-diol and 17betaN in the sulphate fraction (close to 70%). Limits of quantitation ranged from 0.05 to 2.1 ng mL(-1) in the free fraction, from 0.3 to 1.7 ng mL(-1) in the glucuronide fraction, and from 0.2 to 2.6 ng mL(-1) in the sulphate fraction. Intra- and inter-assay values for precision, measured as relative standard deviation, and accuracy, measured as relative standard error, were below 15% for most of the analytes and below 25%, for the rest of analytes. The method was applied to the analysis of urine samples collected after administration of 17betaN laureate to boars and horses, and its suitability for the quantitation of the metabolites in the three fractions has been demonstrated.     

Preparation and structure of three solvatomorphs of the polymer [Co(dbm)2(4ptz)]n: spin canting depending on the supramolecular organization

The syntheses and X-ray structures of three isomeric 1D coordination polymers are reported. The complex [Co(dbm)2(MeOH)2] (1) was used as a precursor in these reactions. The preparation and structure of 1 is also presented; this mononuclear complex is in the cis configuration because this allows the formation of a network of intermolecular hydrogen bonds in the solid state. Reaction of 1 with 2,4,6-tris-(4-pyridyl)-1,3,5-triazine (4ptz) yields the polymers [Co(dbm)2(4ptz)]n.nTHF (2a), [Co(dbm)2(4ptz)]n.0.75nTHF.0.5nEt2O (2b), and [Co(dbm)2(4ptz)]n.3nDMF (2c) in the form of zigzag chains, instead of the expected honeycomb architectures. This is because of the establishment of extended pi-pi stacking throughout these solids, which could not have occurred otherwise. Compounds 2a, 2b, and 2c are solvatomorphs, and formation of either one of them depends on the exact conditions of crystallization, which lead to significant differences in the supramolecular organization of the chains. Bulk magnetic measurements on 2a reveal weak antiferromagnetic exchange within the chains and small ordering throughout the solid that results in the manifestation of the phenomenon of spin canting, whereas for 2c the different supramolecular organization causes the antiferromagnetic exchange not to result in spin canting.     

Combined theoretical and experimental analysis of the bonding in the heterobimetallic cubane-type Mo(3)NiS(4) and Mo(3)CuS(4) core clusters

X-ray structural data for the cubane-type clusters [Mo3CuS4(dmpe)3Cl4](+) and Mo3NiS4(dmpe)3Cl4 (dmpe = 1,2-bis(dimethylphosphino)ethane) with 16 metal electrons have been compared with optimized structural parameters calculated using "ab initio" methodologies. Compound Mo3NiS4(dmpe)3Cl4 crystallizes in the cubic noncentrosymmetric space group P213 with a Mo-Ni distance of 2.647 Angstrom, that is 0.2 Angstrom shorter than the Mo-Cu bond length in the isoelectronic copper cluster. The best agreement between theory and experiments has been obtained using the B3P86 method. In order to validate the B3P86 results, accurate infrared and Raman spectra have been acquired and the vibrational modes associated to the cubane-type Mo3M'S4 (M' = Cu or Ni) unit have been assigned theoretically. The electronic changes taking place when incorporating the M' into the Mo3S4 unit have been analyzed from a theoretical and experimental perspective. The bond dissociation energies between M'-Cl and Mo3S4 fragments show that formation of [Mo3CuS4(dmpe)3Cl4](+) is 135 kcal/mol energetically less favorable than the Ni incorporation. The more robust nature of the Mo3NiS4 fragment has been confirmed by mass spectrometry. The X-ray photoelectron spectroscopy (XPS) spectra of the trimetallic and tetrametallic complexes have been measured and the obtained binding energies compared with the computed electronic populations based on topological approaches of the electron localization function (ELF). The energies and shapes of the Cu 2p and Ni 2p lines indicate formal oxidation states of Cu(I) and Ni(II). However, the reductive addition of nickel into [Mo3S4(dmpe)3Cl3](+) causes a small decrease in the Mo 3d binding energies. This fact prevents an unambiguous assignment of an oxidation state in a conventional way, a circumstance that has been analyzed through the covariance of the electronic populations associated to the C(M') core and V(Mo3Ni) and V(S(2)') valence basins where Mo3NiS4 is a particularly electronically delocalized chemical entity.     

Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface

For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.     

Characterizing turbulence in globally coupled maps with stochastic finite automata

We describe a method to discriminate between ordered and turbulent behavior in a general class of collective systems known as Globally Coupled Maps (GCM). Our method is able to discover an unknown small ordered region inside the turbulent phase of GCM parameter space. The computational nature of the method is the main novelty of our approach; it is another example of how measures based on computational notions of structure may provide new information in the study of dynamical systems.