Chemistry of the amino radical ions,a new chain process of the protonated N-chloramines

δ-Deprotonation of amino radical cation occurs competitively with intramolecular hydrogen abstraction or aromatic amination depending on the acidity of the medium.     

Proton and anion control of framework complexity in copper(II) complex structures derived from 2-(hydroxymethyl)pyridine

Three copper(II) complexes derived from 2-(hydroxymethyl)pyridine (LH) have been synthesised and a comparative X-ray investigation of their respective crystal structures undertaken. In the absence of added base, LH reacts with copper(II) chloride or nitrate to yield the five-coordinate [Cu(LH)₂Cl]Cl and six-coordinate [Cu(LH)₂(NO₃)₂] species. In the chloro complex the coordination geometry is distorted trigonal bipyramidal, with the pyridyl nitrogens occupying the axial position and two hydroxyl oxygens from the bidentate ligands together with a chloro group occupying the equatorial sites. The structure of the nitrate species, published previously, has been reinvestigated at low temperature in order to specify the weak interactions in the crystal; it contains two molecules of bidentate LH bound trans in the equatorial plane while monodentate nitrato ligands occupy the axial sites. In each of these complexes the hydroxyl protons act as hydrogen bond donors, interacting with the non-coordinated chloride anion in [Cu(LH)₂Cl]Cl and the coordinated nitrato groups in [Cu(LH)₂(NO₃)₂] to form bridged, hydrogen-bonded, copper(II)-organic arrays in each case; offset face-to-face π-stacking in the latter produces a two dimensional structure. Further weak CH?Cl, CH?O interactions stabilise both arrangements. The X-ray structure of the complex [Cu(L)₂] · 4H₂O containing the deprotonated ligand is also described. The presence of the latter results in the above hydrogen bonding arrangements being ‘switched off’ and instead a new two-dimensional network involving bridging tetrameric water clusters hydrogen bound to adjacent ligand hydroxo groups to give extended sheets is generated; offset face-to-face π-stacking occurs between sheets to yield a three dimensional array.     

Production of an antiproliferative furanoheliangolide by Lychnophora ericoides cell culture

This work reports for the first time the production a furanoheliangolide (goyazensolide) by plant cell culture. Monitoring of the goyazensolide metabolism revealed that the maximum production occurred during the lag phase of the Lychnophora ericoides callus culture. The antiproliferative activity of obtained goyazensolide was evaluated against seven cancer cell lines using MTT assay. The results revealed a potent cytotoxic activity for the furaheliangolide with IC50 values in the range of 0.06 microg/ml for CEM leukemia cells to 0.75 microg/ml for B16 melanome cells.     

Novel biomimetic iron-catalysts for environmentally benign epoxidations of olefins

A new selective and easily manageable epoxidation method is presented using an inexpensive and efficient FeCl₃·6H₂O and imidazole derivatives as catalysts. Aqueous hydrogen peroxide as an environmentally benign oxidant is utilized. This novel Fe/imidazole system gives moderate to excellent yields toward aromatic mono-, di-, and tri-substituted olefins.     

Anion Controlled Supramolecular Self‐Assembly of Tetraprotonated Tris[2‐(benzylamino)ethyl]amine

The novel supramolecular assembly of composition [{(bz₃tren)H₄}⁴⁺ · (ReO₄)^— · 3(Cl)^—] resulted from the self‐organization of a mixture of tris[2‐(benzylamino)ethyl]amine (bz₃tren), HCl and NH₄ReO₄ at a molar ratio of 1:4.7:1 in methanol. The crystal architecture is characterized by stacks of repeating sandwich‐type building blocks that contain charge‐assisted N—H···O(Re) hydrogen bonds [N···O 2.81‐2.86Å] and weaker C—H···O(Re) interactions [C···O 3.11Å]. The stacks are further linked by N—H···Cl [N···Cl 3.03Å] and weaker C—H···Cl [C···Cl 3.47‐3.74Å] interactions into two‐dimensional layers bordered by the benzyl groups of the [(bz₃tren)H₄]⁴⁺ cations. Edge‐to‐face C—H···π interactions involving the aromatic rings occur within and between the layers. The protonation constants of bz₃tren in methanol were determined by potentiometric titration. The corresponding structures of the ligand in its different protonation states were calculated at the DFT‐level.     

Fluoride Ion Promoted Reactivity of Thiocarbonyl Containing Molecules with Silyl Derivatives: A Novel Access to Allyl Sulfides

Abstract

Fluoride ion induced reaction of allyl- and benzyl-silanes with thiocarbonyls leads, contrary to the corresponding lithium or Grignard reagents, to products of S-functionalization.     

Surface‐activated chemical ionization and cation exchange chromatography for the analysis of enterotoxin A

Surface‐activated chemical ionization (SACI) has been widely used in recent years for the analysis of different compounds (e.g. peptides, street drugs, amino acids). The main benefits of this technology are its high sensitivity and its effectiveness under different chromatographic conditions [i.e. ion exchange chromatography and reversed‐phase (RP) chromatography]. Here we used SACI in conjunction with quadrupole time‐of‐flight mass spectrometry to analyze enterotoxin A, which is produced by Staphylococcus aureus, in milk matrix using both RP and ion exchange chromatographies. SACI had increased sensitivity as compared with electrospray ionization. Moreover, the higher quantitation efficiency of this technique, mainly in terms of limit of detection (0.01 ng/ml), limit of quantitation (0.05 ng/ml), linearity range (0.05–50 ng/ml), matrix effect, accuracy (intraday and interday accuracy errors were 9.2% and 10.3%, respectively) and precision (intraday and interday precision errors were 5.3% and 12.8%, respectively), is shown and discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Remarks on the Paper On Strong Isotopy of Dickson Semifields and Geometric Implications

In the course of publishing our previous paper [1] the editors unfortunately ignored the improved version we had submitted in time. This latest version was prepared in response to the very helpful and thorough critique of the referee. The differences between the two versions of the paper do not affect the actual results but concern the clearness of the exposition. In the following we will not specify all changes we made for the revised version but restrict ourselves to supplement the argumentation.     

Voltage-gated sodium channels in taste bud cells

Background  

Taste bud cells transmit information regarding the contents of food from taste receptors embedded in apical microvilli to gustatory nerve fibers innervating basolateral membranes. In particular, taste cells depolarize, activate voltage-gated sodium channels, and fire action potentials in response to tastants. Initial cell depolarization is attributable to sodium influx through TRPM5 in sweet, bitter, and umami cells and an undetermined cation influx through an ion channel in sour cells expressing PKD2L1, a candidate sour taste receptor. The molecular identity of the voltage-gated sodium channels that sense depolarizing signals and subsequently initiate action potentials coding taste information to gustatory nerve fibers is unknown.