Ligation of water to magnesium chelates of biological importance

Water binding to several Mg(2+) chelates, ethylenediamine, ethylenediamine-N,N’-diacetate, porphyrin, chlorophyll a and bacteriochlorophyll a, to form five- and six-coordinate complexes is studied by means of density functional theory. The results obtained for magnesium chelates are compared with the properties of the respective aqua complexes and the influence of the permittivity of environment on the ligand binding energies is discussed. Although the most common coordination number of Mg(2+) is six, in the tetrapyrrolic chelates it is reduced to five because the accommodation of the sixth water ligand results in no gain in energy. This is in line with the experimental observations made for coordination of chlorophylls in vivo. The binding between Mg(2+) and water is mostly of electrostatic nature, which is supported by the finding that its energy is correlated both with the electron density of the chelator and with electrostatic potential determined at the ligand binding site. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00894-012-1459-3) contains supplementary material, which is available to authorized users

The role of crystallography in drug design

Structure and function are intimately related. Nowhere is this more important than the area of bioactive molecules. It has been shown that the enantioselectivity of an enzyme is directly related to its chirality. X-ray crystallography is the only method for determining the “absolute” configuration of a molecule and is the most comprehensive technique available to determine the structure of any molecule at atomic resolution. Results from crystallographic studies provide unambiguous, accurate, and reliable 3-dimensional structural parameters, which are prerequisites for rational drug design and structure-based functional studies

Effects of one valence proton on seniority and angular momentum of neutrons in neutron-rich(51)( 122-)(131)Sb isotopes

Background: Levels fulfilling the seniority scheme and relevant isomers are commonly observed features in semimagic nuclei; for example, in Sn isotopes (Z=50). Seniority isomers in Sn, with dominantly pure neutron configurations, directly probe the underlying neutron-neutron (νν) interaction. Furthermore, an addition of a valence proton particle or hole, through neutron-proton (νπ) interaction, affects the neutron seniority as well as the angular momentum. Purpose: Benchmark the reproducibility of the experimental observables, like the excitation energies (EX) and the reduced electric-quadrupole transition probabilities [B(E2)], with the results obtained from shell-model interactions for neutron-rich Sn and Sb isotopes with N<82. Study the sensitivity of the aforementioned experimental observables to the model interaction components. Furthermore, explore from a microscopic point of view the structural similarity between the isomers in Sn and Sb, and thus the importance of the valence proton. Methods: The neutron-rich Sb122–131 isotopes were produced as fission fragments in the reaction Be9(U238, f) with 6.2 MeV/u beam energy. A unique setup, consisting of AGATA, VAMOS++, and EXOGAM detectors, was used which enabled the prompt-delayed γ-ray spectroscopy of fission fragments in the time range of 100 ns to 200μs. Results: New isomers and prompt and delayed transitions were established in the even-A Sb122–130 isotopes. In the odd-A Sb123–131 isotopes, new prompt and delayed γ-ray transitions were identified, in addition to the confirmation of the previously known isomers. The half-lives of the isomeric states and the B(E2) transition probabilities of the observed transitions depopulating these isomers were extracted. Conclusions: The experimental data was compared with the theoretical results obtained in the framework of large-scale shell-model (LSSM) calculations in a restricted model space. Modifications of several components of the shell-model interaction were introduced to obtain a consistent agreement with the excitation energies and the B(E2) transition probabilities in neutron-rich Sn and Sb isotopes. The isomeric configurations in Sn and Sb were found to be relatively pure. Furthermore, the calculations revealed that the presence of a single valence proton, mainly in the g7/2 orbital in Sb isotopes, leads to significant mixing (due to the νπ interaction) of (i) the neutron seniorities (υν) and (ii) the neutron angular momentum (Iν). The above features have a weak impact on the excitation energies, but have an important impact on the B(E2) transition probabilities. In addition, a constancy of the relative excitation energies irrespective of neutron seniority and neutron number in Sn and Sb was observed.The neutron-rich $^{122-131}$Sb isotopes were produced as fission fragments in the reaction $^{9}$Be($^{238}$U,~f) with 6.2 MeV/u beam energy. An unique setup, consisting of AGATA, VAMOS++ and EXOGAM detectors, was used which enabled the prompt-delayed gamma-ray ($\gamma$) spectroscopy of fission fragments in the time range of 100 ns - 200 $\mu$s. New isomers, prompt and delayed transitions were established in the even-A $^{122-130}$Sb isotopes. In the odd-A $^{123-131}$Sb isotopes, new prompt and delayed $\gamma$-ray transitions were identified, in addition to the confirmation of the previously known isomers. The half-lives of the isomeric states and the $B(E2)$ transition probabilities of the observed transitions depopulating these isomers were extracted. The experimental data was compared with the theoretical results obtained in the framework of Large-Scale Shell-Model (LSSM) calculations in a restricted model space. Modifications of several components of the shell model interaction were introduced to obtain a consistent agreement with the excitation energies and the $B(E2)$ transition probabilities in neutron-rich Sn and Sb isotopes. The isomeric configurations in Sn and Sb were found to be relatively pure. Further, the calculations revealed that the presence of a single valence proton, mainly in the $g_{7/2}$ orbital in Sb isotopes, leads to significant mixing (due to the $\nu\pi$ interaction) of: (i) the neutron seniorities ($\upsilon_{\nu}$) and (ii) the neutron angular momentum ($I_{\nu}$). The above features have a weak impact on the excitation energies, but have an important impact on the $B(E2)$ transition probabilities. In addition, a constancy of the relative excitation energies irrespective of neutron seniority and neutron number in Sn and Sb was observed

Global properties of K hindrance probed by the ? decay of the warm rotating W-174 nucleus

The K hindrance to the gamma decay is studied in the warm rotating W-174 nucleus, focusing on the weakening of the selection rules of the K quantum number with increasing excitation energy. W-174 was populated by the fusion reaction of Ti-50 (at 217 MeV) on a Te-128 target, and its gamma decay was detected by the AGATA Demonstrator array coupled to a BaF2 multiplicity filter at Laboratori Nazionali di Legnaro of INFN. A fluctuation analysis of gamma coincidence matrices gives a similar number of low-K and high-K discrete excited bands. The results are compared to simulations of the gamma-decay flow based on a microscopic cranked shell model at finite temperature in which the K mixing is governed by the interplay of Coriolis force with the residual interaction. Agreement between simulations and experiment is obtained only by hindering the E1 decay between low-K and high-K bands by an amount compatible with that determined by spectroscopic studies of K isomers in the same mass region, with a similar trend with excitation energy. The work indicates that K mixing due to temperature effects may play a leading role for the entire body of discrete excited bands, which probes the onset region of K weakening.The K hindrance to the gamma decay is studied in the warm rotating W-174 nucleus, focusing on the weakening of the selection rules of the K quantum number with increasing excitation energy. W-174 was populated by the fusion reaction of Ti-50 (at 217 MeV) on a Te-128 target, and its gamma decay was detected by the AGATA Demonstrator array coupled to a BaF2 multiplicity filter at Laboratori Nazionali di Legnaro of INFN. A fluctuation analysis of gamma coincidence matrices gives a similar number of low-K and high-K discrete excited bands. The results are compared to simulations of the gamma-decay flow based on a microscopic cranked shell model at finite temperature in which the K mixing is governed by the interplay of Coriolis force with the residual interaction. Agreement between simulations and experiment is obtained only by hindering the E1 decay between low-K and high-K bands by an amount compatible with that determined by spectroscopic studies of K isomers in the same mass region, with a similar trend with excitation energy. The work indicates that K mixing due to temperature effects may play a leading role for the entire body of discrete excited bands, which probes the onset region of K weakening

Identification of high-spin proton configurations in 136Ba and 137Ba

The high-spin structures of 136 Ba and 137 Ba are investigated after multinucleon-transfer (MNT) and fusion-evaporation reactions. 136 Ba is populated in a 136 Xe + 238 U MNT reaction employing the high-resolution Advanced GAmma Tracking Array (AGATA) coupled to the magnetic spectrometer PRISMA at the Laboratori Nazionali di Legnaro, Italy, and in two 9Be + 130 Te fusion-evaporation reactions using the High-efficiency Observatory for γ -Ray Unique Spectroscopy (HORUS) at the FN tandem accelerator of the University of Cologne, Germany. Furthermore, both isotopes are populated in an elusive reaction channel in the 11 B + 130 Te fusion-evaporation reaction utilizing the HORUS γ -ray array. The level scheme above the Jπ = 10 + isomer in 136 Ba is revised and extended up to an excitation energy of approximately 5.5 MeV. From the results of angular-correlation measurements, the Ex=3707 - and Ex=4920 -keV states are identified as the bandheads of positive- and negative-parity cascades. While the high-spin regimes of both 132 Te and 134 Xe are characterized by high-energy 12 + → 10 + transitions, the 136 Ba E 2 ground-state band is interrupted by negative-parity states only a few hundred keV above the Jπ = 10 + isomer. Furthermore, spins are established for several hitherto unassigned high-spin states in 137 Ba . The new results close a gap along the high-spin structure of N<82 Ba isotopes. Experimental results are compared to large-scale shell-model calculations employing the GCN50:82, Realistic SM, PQM130, and SN100PN interactions. The calculations suggest that the bandheads of the positive-parity bands in both isotopes are predominantly of proton character