A re-investigation of copper coordination in the octa-repeats region of the prion protein

An aqueous solution spectroscopic (Vis and EPR) study of the copper(II) complexes with the Ac-HGGG-NH2 and Ac-PHGGGWGQ-NH2 polypeptides (generically designated as L) suggests square base pyramids ascribable to [Cu(L)H(-2)] complex species, which contain three nitrogen donor atoms, arising from imidazole and peptide groups, in the equatorial plane and for a pseudo-octahedral geometry in the case of [CuLH-3]- and [Cu(L)H-4]2- which have four nitrogen donor atoms in their equatorial plane. The coordination sphere of the copper complex in the [Cu(L)H(-2)] species, which is present at neutral pH values, is completed by two oxygen donor atoms. ESI-MS spectra ascertained that water molecules are not present in the coordination equatorial plane of this latter species, in comparison with other copper(II) complexes with ligands bearing nitrogen and oxygen donor atoms and surely having equatorial water molecules. This indicates the coordination of a carbonyl oxygen atom in the equatorial plane has to be invoked. However, no direct proof about the involvement of a carbonyl group oxygen donor atom apically linked to copper was obtained, due to the flexibility of these structures at room temperature. Additionally, the low A(ll) value leads one to consider another oxygen atom of a carbonyl group being involved in the apical bond to copper in a fast exchange fashion. This apical interaction, which may also involve a water molecule, is more pronounced in the Cu-Ac-HGGG-NH2 than in the analogous Cu-Ac-PHGGGWGQ-NH2 system, probably because of the presence of tryptophan and proline in the polypeptide sequence.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Addition of p-azido-L-phenylalanine to the genetic code of Escherichia coli

We report the selection of a new orthogonal aminoacyl tRNA synthetase/tRNA pair for the in vivo incorporation of a photocrosslinker, p-azido-l-phenylalanine, into proteins in response to the amber codon, TAG. The amino acid is incorporated in good yield with high fidelity and can be used to crosslink interacting proteins.     

Neutron diffraction structure determination of the high-temperature form of lithium tritantalate,HLiTa3O8

The crystal structure of HLiTa₃O₈ has been reexamined by electron and neutron diffraction techniques. Neutron Weissenberg and electron diffraction photographs show that the space group of the compound isPmmn and notPmma as determined previously by X-ray diffraction techniques. There are eight molecules in the unit cell of lattice parametersa = 16.718(2)A?,b = 7.696(1)A?,c = 8.931(1)A?. These values show that thebaxis of the new cell is doubled with respect to the parameter measured by X-rays. The structural refinement was based on 1074 independent reflections measured on a single crystal with a four-circle neutron diffractometer. The positions of all atoms, including the lithium atoms have been determined. The finalR andwRfactors were 0.036 and 0.035, respectively. The eight lithium cations occupy two sets of4fpositions(x,¼, z)of thePmmn space group. The ordering of four lithium ions over two sets of possible positions (4j) of space groupPmma is responsible for the doubling of theb axis. The other four Li⁺ occupy two sets of positions (2d) of space groupPmma. All lithium ions are surrounded by 12 oxygen atoms arranged as cuboctahedra. The large thermal vibrations found for the lithium atoms and the ionic conductivity of HLiTa₃O₈ at high temperatures are consistent with weak LiO bonding.     

Rapid detection and identification of liquid crystal states by light scattering

Thermotropic mesophases can be detected by the light scattering properties of these phases. This article deals with a rapid scan technique for the detection and characterization of these mesophases by measuring light scattering as a function of temperature. From the number of compounds studied it is apparent that the method allows for a rapid and reasonably precise determination of transition temperatures. In addition, the method is found to be useful in the characterization of mesophases, in particular the nematic phase.