Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne "click reaction".

The copper-catalyzed 1,3-dipolar cycloaddition of an azide to a terminal alkyne (CuAAC) is one of the most popular chemical transformations, with applications ranging from material to life sciences. However, despite many mechanistic studies, direct observation of key components of the catalytic cycle is still missing. Initially, mononuclear species were thought to be the active catalysts, but later on, dinuclear complexes came to the front. We report the isolation of both a previously postulated π,σ-bis(copper) acetylide and a hitherto never-mentioned bis(metallated) triazole complex. We also demonstrate that although mono- and bis-copper complexes promote the CuAAC reaction, the dinuclear species are involved in the kinetically favored pathway

Timescale for equilibration of N/Z gradients in dinuclear systems

Equilibration of N/Z in binary breakup of an excited and transiently deformed projectile-like fragment (PLF*), produced in peripheral collisions of 64Zn + 27Al, 64Zn, 209Bi at E/A = 45 MeV, is examined. The composition of emitted light fragments (3<=Z<=6) changes with the decay angle of the PLF*. The most neutron-rich fragments observed are associated with a small rotation angle. A clear target dependence is observed with the largest initial N/Z correlated with the heavy, neutron-rich target. Using the rotation angle as a clock, we deduce that N/Z equilibration persists for times as long as 3-4 zs (1zs = 1 x 10^-21 s = 300 fm/c). The rate of N/Z equilibration is found to depend on the initial neutron gradient within the PLF*.Comment: 6 pages, 4 figure

\u3cem\u3eArabidopsis thaliana\u3c/em\u3e GLX2-1 Contains a Dinuclear Metal Binding Site, but Is Not a Glyoxalase 2

In an effort to probe the structure and function of a predicted mitochondrial glyoxalase 2, GLX2-1, from Arabidopsis thaliana, GLX2-1 was cloned, overexpressed, purified and characterized using metal analyses, kinetics, and UV–visible, EPR, and 1H-NMR spectroscopies. The purified enzyme was purple and contained substoichiometric amounts of iron and zinc; however, metal-binding studies reveal that GLX2-1 can bind nearly two equivalents of either iron or zinc and that the most stable analogue of GLX2-1 is the iron-containing form. UV–visible spectra of the purified enzyme suggest the presence of Fe(II) in the protein, but the Fe(II) can be oxidized over time or by the addition of metal ions to the protein. EPR spectra revealed the presence of an anti-ferromagnetically-coupled Fe(III)Fe(II) centre and the presence of a protein-bound high-spin Fe(III) centre, perhaps as part of a FeZn centre. No paramagnetically shifted peaks were observed in 1H-NMR spectra of the GLX2-1 analogues, suggesting low amounts of the paramagnetic, anti-ferromagnetically coupled centre. Steady-state kinetic studies with several thiolester substrates indicate that GLX2-1 is not a GLX2. In contrast with all of the other GLX2 proteins characterized, GLX2-1 contains an arginine in place of one of the metal-binding histidine residues at position 246. In order to evaluate further whether Arg246 binds metal, the R246L mutant was prepared. The metal binding results are very similar to those of native GLX2-1, suggesting that a different amino acid is recruited as a metal-binding ligand. These results demonstrate that Arabidopsis GLX2-1 is a novel member of the metallo-β-lactamase superfamily

Characterization of fragment emission in ^{20}Ne (7 - 10 MeV/nucleon) + ^{12}C reactions

The inclusive energy distributions of the complex fragments (3 $\leq$ Z $\leq$ 7) emitted from the bombardment of ^{12}C by ^{20}Ne beams with incident energies between 145 and 200 MeV have been measured in the angular range 10$^{o} \leq \theta_{lab} \leq$ 50^{o}. Damped fragment yields in all the cases have been found to be the characteristic of emission from fully energy equilibrated composites. The binary fragment yields are compared with the standard statistical model predictions. Enhanced yields of entrance channel fragments (5 $\leq$ Z $\leq$ 7) indicate the survival of orbiting-like process in ^{20}Ne + ^{12}C system at these energies.Comment: 18 pages, 13 figure

Formation and structural chemistry of the unusual cyanide-bridged dinuclear species [Ru-2(NN)(2)(CN)(7)](3-)(NN=2,2 '-bipyridine or 1,10-phenanthroline)

Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)(4)](2) (NN = 2,2'-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)(4)](2) salts, in the formation of small amounts of salts of the dinuclear species [Ru-2(NN)(2)(CN)(7)](3). These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)(4)](2) following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H2O)(5.5)][Ru-2(bipy)(2)(CN)(7)] center dot 11H(2)O and [Pr(H2O)(6)][Ru-2(phen)(2)(CN)(7)] center dot 9H(2)O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru(2)Ln(2)(mu-CN)(4) squares and Ru(4)Ln(2)(mu-CN)(6) hexagons, which alternate to form a one-dimensional chain. In [CH6N3](3)[Ru-2(bipy)(2)(CN)(7)] center dot 2H(2)O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru-2(NN)(2)(CN)(7)](3) anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4'-Bu-t(2)-2,2'-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH6N3](2)[Ru((t)Bu(2)bipy)(CN)(4)] center dot 2H(2)O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru-2(phen)(2)(CN)(7)](3) could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)(4)](2) if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru-2(bipy)(2)(CN)(7)](3) (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)(4)](2), with a (MLCT)-M-3 emission at 581 nm

Characterization of the Active Site and Insight into the Binding Mode of the Anti-angiogenesis Agent Fumagillin to the Manganese(II)-Loaded Methionyl Aminopeptidase from \u3cem\u3eEscherichia coli\u3c/em\u3e

EPR spectra were recorded for methionine aminopeptidase from Escherichia coli (EcMetAP-I) samples (~2.5 mM) to which one and two equivalents of Mn(II) were added (the latter is referred to as [MnMn(EcMetAP-I)]). The spectra for each sample were indistinguishable except that the spectrum of [MnMn(EcMetAP-I)] was twice as intense. The EPR spectrum of [MnMn(EcMetAP-I)] exhibited the characteristic six-line g≈2 EPR signal of mononuclear Mn(II) with A av(55Mn)=9.3 mT (93 G) and exhibited Curie-law temperature dependence. This signal is typical of Mn(II) in a ligand sphere comprising oxygen and/or nitrogen atoms. Other features in the spectrum were observed only as the temperature was raised from that of liquid helium. The temperature dependences of these features are consistent with their assignment to excited state transitions in the S=1, 2 ... 5 non-Kramer’s doublets, due to two antiferromagnetically coupled Mn(II) ions with an S=0 ground state. This assignment is supported by the observation of a characteristic 4.5 mT hyperfine pattern, and by the presence of signals in the parallel mode consistent with a non-Kramers’ spin ladder. Upon the addition of the anti-angiogenesis agent fumagillin to [MnMn(EcMetAP-I)], very small changes were observed in the EPR spectrum. MALDI-TOF mass spectrometry indicated that fumagillin was, however, covalently coordinated to EcMetAP-I. Therefore, the inhibitory action of this anti-angiogenesis agent on EcMetAP-I appears to involve covalent binding to a polypeptide component at or near the active site rather than direct binding to the metal ions

Angular anisotropy of the fusion-fission and quasifission fragments

The anisotropy in the angular distribution of the fusion-fission and quasifission fragments for the $^{16}$O+$^{238}$U, $^{19}$F+$^{208}$Pb and $^{32}$S+$^{208}$Pb reactions is studied by analyzing the angular momentum distributions of the dinuclear system and compound nucleus which are formed after capture and complete fusion, respectively. The orientation angles of axial symmetry axes of colliding nuclei to the beam direction are taken into account for the calculation of the variance of the projection of the total spin onto the fission axis. It is shown that the deviation of the experimental angular anisotropy from the statistical model picture is connected with the contribution of the quasifission fragments which is dominant in the $^{32}$S+$^{208}$Pb reaction. Enhancement of anisotropy at low energies in the $^{16}$O+$^{238}$U reaction is connected with quasifission of the dinuclear system having low temperature and effective moment of inertia.Comment: 17 pages 8 figures. Submitted to Euro. Phys. Jour.