Crystal Structure of Staphylococcus aureus Metallopeptidase (Sapep) Reveals Large Domain Motions between the Manganese-bound and Apo-states

Proteases belonging to the M20 family are characterized by diverse substrate specificity and participate in several metabolic pathways. The Staphylococcus aureus metallopeptidase, Sapep, is a member of the aminoacylase-I/M20 protein family. This protein is a Mn2+-dependent dipeptidase. The crystal structure of this protein in the Mn2+-bound form and in the open, metal-free state suggests that large interdomain movements could potentially regulate the activity of this enzyme. We note that the extended inactive conformation is stabilized by a disulfide bond in the vicinity of the active site. Although these cysteines, Cys(155) and Cys(178), are not active site residues, the reduced form of this enzyme is substantially more active as a dipeptidase. These findings acquire further relevance given a recent observation that this enzyme is only active in methicillin-resistant S. aureus. The structural and biochemical features of this enzyme provide a template for the design of novel methicillin-resistant S. aureus-specific therapeutics.

Synthesis, crystal structures and magnetic behavior of two 3D coordination polymers using N-(4/3-arboxyphenyl)iminodiacetic acids as bridging ligands

Research on structure and magnetic properties of polynuclear metal complexes to understand the structural and chemical factors governing the electronic exchange coupling mediated by multi-atom bridging ligands is of growing interest. Hydrothermal treatment of Ni(NO3)(2)center dot 6H(2)O with N-(4-carboxyphenyl)iminodiacetic acid N-4(H(3)CPIDA)] at 150 degrees C yielded a 3D coordination polymer of general formula Ni-3{N-4( CPIDA)}(2)(H2O)(3)]center dot 6H(2)O (1). An analogous network of general formula Co-3{N-3(CPIDA)}(2)(H2O)(3)]center dot 3H(2)O (2) was synthesized using N-(3-carboxyphenyl) iminodiacetic acid N-3(H(3)CPIDA)] in combination with Co(NO3)(2)center dot 6H(2)O under identical reaction condition. Both the complexes contain trinuclear secondary building unit, and crystallized in monoclinic system with space groups C2/c (1) and P2(1)/c (2), respectively. Variable temperature magnetic characterization of these complexes in the temperature range of 2-300 K indicated the presence of overall ferromagnetic and antiferromagnetic behavior for 1 and 2, respectively. Density functional theory calculations (B3LYP functional) were performed for further insight on the trinuclear units to provide a qualitative theoretical interpretation on the overall magnetic behavior of the complexes 1 and 2. (C) 2010 Elsevier B.V. All rights reserved.

Conformations of synthetic alamethicin fragments. Evidence for 310 helical folding from 270-MHz hydrogen-1 nuclear magnetic resonance and circular dichroism studies

IH NMR studies at 270 MHz on the synthetic alamethicin fragments Z-Aib-Pro-Aib-Ala-Aib-Ala-OMe (1-6), Boc-Gln-Aib-Val-Aib-Gly-Leu-Aib-OMe (7-1 3), Boc-Leu-Aib-Pro-Val-Aib-OMe (1 2-16), and Boc-Gly-Leu- Aib-Pro-Val-Aib-OMe (1 1-16) have been carried out in CDC13 and (CD3)2S0. The intramolecularly hydrogen bonded amide hydrogens in these peptides have been delineated by using solvent titration experiments and temperature coefficientsof NH chemical shifts in (CD3)+30. All the peptides adopt highly folded structures, characterized by intramolecular 4 - 1 hydrogen bonds. The 1-6 fragment adopts a 310 helical conformation with four hydrogen bonds, in agreement with earlier studies (Rao, Ch. P., Nagaraj, R., Rao, C. N. R., & Balaram, P. (1980) Biochemistry 19, 425-4311. The 7-13

Magnetic fabrics indicating Late Quaternary seismicity in the Himalayan foothills

The anisotropy of magnetic susceptibility (AMS) study was performed on soft sediment samples from a trenched fault zone across the Himalayan frontal thrust (HFT), western Himalaya. AMS orientation of K-min axes in the trench sediments is consistent with lateral shortening revealed by geometry of deformed regional structures and recent earthquakes. Well-defined vertical magnetic foliation parallel to the flexure cleavage in which a vertical magnetic lineation is developed, high anisotropy, and triaxial ellipsoids suggest large overprinting of earth-quake- related fabrics. The AMS data suggest a gradual variation from layer parallel shortening (LPS) at a distance from the fault trace to a simple shear fabric close to the fault trace. An abrupt change in the shortening direction (K-min) from NE-SW to E-W suggests a juxtaposition of pre-existing layer parallel shortening fabric, and bending-related flexure associated with an earthquake. Hence the orientation pattern of magnetic susceptibility axes helps in identifying co-seismic structures in Late Holocene surface sediments.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups mu-O and mu-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu-II complex Cu(pmadH(2))(2)(NO3)](NO3) (1) was obtained upon treatment of Cu(NO3)(2)center dot 3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu-II-complex Cu-4(pmad)(2)(pmadH)(2)(NO3)](NO3)(H2O) (2). One of the Cu-II centers is in a square pyramidal environment while the other three are in a square planar geometry. Reaction of the same ligand with an equimolar mixture of both Cu(NO3)(2)center dot 3H(2)O and NiCl2 center dot 6H(2)O yielded a tetranuclear heterometallic (Cu2Ni2II)-Ni-II complex Cu2Ni2(pmad)(2)(pmadH)(2)Cl-2]center dot H2O (3) containing both square planar (Ni-II) and square pyramidal (Cu-II) metal centers. Complexes 1-3 represent the first examples of polynuclear metal complexes of 2-pyrimidineamidoxime. The analysis of variable temperature magnetic susceptibility data of 2 reveals that both ferromagnetic and antiferromagnetic interactions exist in this complex (J(1) = +10.7 cm(-1) and J(2) = -2.7 cm(-1) with g = 2.1) leading to a resultant ferromagnetic behavior. Complex 3 shows expected antiferromagnetic interaction between two Cu-II centers through -N-O- bridging pathway with J(1) = -3.4 cm(-1) and g = 2.08. DFT calculations have been used to corroborate the magnetic results.

Electric and magnetic polarizabilities of hexagonal Ln(2)CuTiO(6)(Ln = Y, Dy, Ho, Er, and Yb)

We investigated the rare-earth transition-metal oxide series, Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb), crystallizing in the hexagonal structure with noncentrosymmetric P6(3)cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln = Y, exhibit a low-temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses, and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected cooperative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant among different members of this series are shown to arise from changes in relative contributions from soft polar modes.

Hyperfine effects in the nuclear magnetic resonance of paramagnetic molecules

Paramagnetic, or open-shell, systems are often encountered in the context of metalloproteins, and they are also an essential part of molecular magnets. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for chemical structure elucidation, but for paramagnetic molecules it is substantially more complicated than in the diamagnetic case. Before the present work, the theory of NMR of paramagnetic molecules was limited to spin-1/2 systems and it did not include relativistic corrections to the hyperfine effects. It also was not systematically expandable. --- The theory was first expanded by including hyperfine contributions up to the fourth power in the fine structure constant α. It was then reformulated and its scope widened to allow any spin state in any spatial symmetry. This involved including zero-field splitting effects. In both stages the theory was implemented into a separate analysis program. The different levels of theory were tested by demonstrative density functional calculations on molecules selected to showcase the relative strength of new NMR shielding terms. The theory was also tested in a joint experimental and computational effort to confirm assignment of 11 B signals. The new terms were found to be significant and comparable with the terms in the earlier levels of theory. The leading-order magnetic-field dependence of shielding in paramagnetic systems was formulated. The theory is now systematically expandable, allowing for higher-order field dependence and relativistic contributions. The prevailing experimental view of pseudocontact shift was found to be significantly incomplete, as it only includes specific geometric dependence, which is not present in most of the new terms introduced here. The computational uncertainty in density functional calculations of the Fermi contact hyperfine constant and zero-field splitting tensor sets a limit for quantitative prediction of paramagnetic shielding for now.

Trajectories of charged particles in the static Ernst space-time

The authors study the trajectories of charged particles in Ernst's space-time representing a static black hole immersed in a magnetic field. They find bound orbits always exist for realistic magnetic field strengths. A similar investigation is carried out for the case of Melvin's magnetic universe and for a corresponding test field superposed on a flat space-time.

Flow And Heat-Transfer Over An Upstream Moving Wall With A Magnetic-Field And A Parallel Free Stream

The flow and heat transfer over an upstream moving non-isothermal wall with a parallel free stream have been considered. The magnetic field has been applied in the free stream parallel to the wall and the effect of induced magnetic field has been included in the analysis. The boundary layer equations governing the steady incompressible electrically conducting fluid flow have been solved numerically using a shooting method. This problem is interesting because a solution exists only when the ratio of the wall velocity does not exceed a certain critical value and this critical value depends on the magnetic field and magnetic Prandtl number. Also dual solutions exist for a certain range of wall velocity.

Optical and magnetic properties of the exact PPP states of biphenyl

The low-lying singlets and triplets of biphenyl are obtained exactly within the PPP model using the diagrammatic valence bond method. The energy gaps within the singlet manifold as well as the lowest singlet-triplet gap are found to be in good agreement with experimental results. The two weak absorptions between 4·1 and 4·2 eV reported experimentally are attributed to the two states lying below the optical gap that become weakly allowed on breaking electron-hole and inversion symmetries. The observed blue shift of the spectral lines, attributed to a change in dihedral angle, on going from crystalline to solution to vapour phase is also well reproduced within the PPP model. The bond orders show that the ground singlet state is benzenoidal while the dipole excited state as well as the lowest triplet state are quinonoidal and planar. Comparison with the experimental spin densities and the fine structure constants D and E in the triplet state point to slightly weaker correlations than assumed by the PPP model. The introduction of a 1-8 bond to mimic poly(paraphenylene)s gives an optical gap that is in good agreement with experiment.

Comment on “Southward magnetic field in the neutral sheet produced by wavy motions Propagating in the dawn‐dusk direction”

In a recent paper Nakagawa and Nishida [1989] have suggested that wavy motions of the neutral sheet can be generated by the Kelvin‐Helmholtz instability if the dawn‐dusk flow of only several tens of km/s is present. However, their mathematical analysis is based on the choice of particular magnetic field directions in the three regions consisting of north, south lobes and the neutral sheet. In an earlier paper Uberoi [1986] discussed the Kelvin‐Helmholtz instability of a similar structured plasma layer without any assumptions either on velocity field directions or on the magnetic field directions, thus pointing out the angle effect due to variation in magnetic field directions on the instability criterion. The relevance of these results to the problem of wavy motions of the neutral sheet are pointed out. In particular it is found that when the y‐component of the magnetic field in each lobe is taken into consideration the Kelvin‐Helmholtz instability can be exicted only when the dawn‐dusk flow is of several hundreds of km/s a order of ten higher than that arrived in the analysis by Nakagawa and Nishida [1989].

Synthetic, spectroscopic, magnetic, and x-ray structural studies on a vitamin B6-amino acid Schiff base complex, aqua(5'-phosphopyridoxylidenetyrosinato)copper(II) tetrahydrate

A Schiff base metal complex, [Cu(II)(PLP-DL-tyrosinato)(H2O)].4H2O (PLP = pyridoxal phosphate), with the molecular formula CuC17O13N2H27P has been prepared and characterized by magnetic, spectral, and X-ray structural studies. The compound crystallizes in the triclinic space group P1BAR with a = 8.616 (2) angstrom, b = 11.843 (3) angstrom, c = 12.177 (3) angstrom, alpha = 103.40 (2)degrees, beta = 112.32 (2)degrees, gamma = 76.50 (1)degrees, and Z = 2. The structure was solved by the heavy-atom method and refined by least-squares techniques to a final R value of 0.057 for 3132 independent reflections. The coordination geometry around Cu(II) is distorted square pyramidal with phenolic oxygen, imino nitrogen, and carboxylate oxygen from the Schiff base ligand and water oxygen as basal donor atoms. The axial site is occupied by a phosphate oxygen from a neighboring molecule, thus resulting in a one-dimensional polymer. The structure reveals pi-pi interaction of the aromatic side chain of the amino acid with the pyridoxal pi system. A comparative study is made of this complex with similar Schiff base complexes. The variable-temperature magnetic behavior of this compound shows a weak antiferromagnetic interaction.