X-ray crystallographic and NMR studies of pantothenate synthetase provide insights into the mechanism of homotropic inhibition by pantoate

The structural basis for the homotropic inhibition of pantothenate synthetase by the substrate pantoate was investigated by X-ray crystallography and high-resolution NMR spectroscopic methods. The tertiary structure of the dimeric N-terminal domain of Escherichia coli pantothenate synthetase, determined by X-ray crystallography to a resolution of 1.7 Å, showed a second molecule of pantoate bound in the ATP-binding pocket. Pantoate binding to the ATP-binding site induced large changes in structure, mainly for backbone and side chain atoms of residues in the ATP binding HXGH(34–37) motif. Sequence-specific NMR resonance assignments and solution secondary structure of the dimeric N-terminal domain, obtained using samples enriched in 2H, 13C, and 15N, indicated that the secondary structural elements were conserved in solution. Nitrogen-15 edited two-dimensional solution NMR chemical shift mapping experiments revealed that pantoate, at 10 mm, bound at these two independent sites. The solution NMR studies unambiguously demonstrated that ATP stoichiometrically displaced pantoate from the ATP-binding site. All NMR and X-ray studies were conducted at substrate concentrations used for enzymatic characterization of pantothenate synthetase from different sources [Jonczyk R & Genschel U (2006) J Biol Chem 281, 37435–37446]. As pantoate binding to its canonical site is structurally conserved, these results demonstrate that the observed homotropic effects of pantoate on pantothenate biosynthesis are caused by competitive binding of this substrate to the ATP-binding site. The results presented here have implications for the design and development of potential antibacterial and herbicidal agents.

Effect of dimerization on dynamics of spin-charge separation in Pariser-Parr-Pople model: A time-dependent density matrix renormalization group study

We investigate the effect of static electron-phonon coupling on real-time dynamics of spin and charge transport in pi-conjugated polyene chains. The polyene chain is modeled by the Pariser-Parr-Pople Hamiltonian with dimerized nearest-neighbor parameter t(0)(1 + delta) for short bonds and t(0)(1 - delta) for long bonds, and long-range electron-electron interactions. We follow the time evolution of the spin and charge using time-dependent density matrix renormalization group technique when a hole is injected at one end of the chain in its ground state. We find that spin and charge dynamics followed through spin and charge velocities depend both on chain length and extent of dimerization delta. Analysis of the results requires focusing on physical quantities such as average spin and charge polarizations, particularly in the large dimerization limit. In the dimerization range 0.0 <= delta <= 0.15, spin-charge dynamics is found to have a well-defined behavior, with spin-charge separation (measured as the ratio of charge velocity to spin velocity) as well as the total amount of charge and spin transported in a given time along the chain decreasing as dimerization increases. However, in the range 0.3 <= delta <= 0.5, it is observed that the dynamics of spin and charge transport becomes complicated. It is observed that, for large delta values, spin-charge separation is suppressed and the injected hole fails to travel the entire length of the chain.

The influence of termites on soil sheeting properties varies depending on the materials on which they feed

Fungus-growing termites are involved in many ecological processes and play a central role in influencing soil dynamics in the tropics. The physical and chemical properties of their nest structures have been largely described; however less information is available concerning the relatively temporary structures made above-ground to access food items and protect the foraging space (the soil `sheetings'). This study investigated whether the soil physical and chemical properties of these constructions are constant or if they vary depending on the type of food they cover. Soil samples and soil sheetings were collected in a forest in India, from leaves on the ground (LEAF), fallen branches (WOOD), and vertical soil sheetings covering the bark of trees (TREE). In this environment, termite diversity was dominated by Odontotermes species, and especially Odontotermes feae and Odontotermes obesus. However, there was no clear niche differentiation and, for example, O. feae termites were found on all the materials. Compared with the putative parent soil (control), TREE sheetings showed the greatest (and most significant) differences (higher clay content and smaller clay particle sizes, lower C and N content and smaller delta C-13 and delta N-15), while LEAF sheetings were the least modified, though still significantly different than the control soil. We suggest that the termite diversity is a less important driver of potential soil modification than sheeting diversity. Further, there is evidence that construction properties are adapted to their prospective life-span, with relatively long-lasting structures being most different from the parent soil. (C) 2015 Elsevier Masson SAS. All rights reserved.

A combined XPS-UPS-EELS study of nitrogen adsorbed on clean and barium-promoted iron surfaces: The nature of the precursor to dissociation

For N2 on a clean Fe surface, the adsorbed precursor in a parallel orientation becomes predominant around 110 K, while at lower temperatures it coexists with a weakly adsorbed species. On a Ba-promoted Fe surface, however, N2 is present exclusively in the precursor state in the temperature range 80–150 K following moderate exposure. Besides exhibiting a low N-N stretching frequency of 1530 cm−1, the precursor shows a clear separation between the 5σ and 1π levels in the UPS; the precursor dissociates to give a nitridic species around 160 K.

Force Measurements on a Reflex Cambered Delta Wing

AREFLEX spanwise cambered delta wing with a conical camber designed for M= 1.4, using the method of Ref. 1, was tested at the design Mach number as well as off-design Mach number M=0.15 and 2.3, respectively. The test results are compared with those of a plane wing and also with the available theoretical results at the design condition. At subsonic speed, the cambered wing has less lift at a given incidence and higher lift-to-drag ratio at a given lift than the plane wing, while at supersonic speeds, both of these quantities were less on the cambered wing. At supersonic speed, at the design incidence and Mach number, there is good agreement between results from theory and experiment. The center of pressure on the cambered wing is ahead of that on the plane wing at subsonic speed, while the reverse is true at supersonic speeds. Finally, it is found that over a useful range of lift the cambered wing is aerodynamically more efficient at subsonic speeds, and less so at supersonic speeds, than the plane wing.

CD4+ alpha beta T cell and gamma delta T cell responses to Mycobacterium tuberculosis. Similarities and differences in Ag recognition, cytotoxic effector function, and cytokine production.

CD4+ and gamma delta T cells are activated readily by Mycobacterium tuberculosis. To examine their role in the human immune response to M. tuberculosis, CD4+ and gamma delta T cells from healthy tuberculin-positive donor were studied for patterns of Ag recognition, cytotoxicity, and cytokine production in response to M. tuberculosis-infected mononuclear phagocytes. Both T cell subsets responded to intact M. tuberculosis and its cytosolic Ags. However, CD4+ and gamma delta T cells differed in the range of cytosolic Ags recognized: reactivity to a wide m.w. range of Ags for CD4+ T cells, and a restricted pattern for gamma delta T cells, with dominance of Ags of 10 to 15 kDa. Both T cell subsets were equally cytotoxic for M. tuberculosis-infected monocytes. Furthermore, both CD4+ and gamma delta T cells produced large amounts of IFN-gamma: mean pg/ml of IFN-gamma in supernatants was 2458 +/- 213 for CD4+ and 2349 +/- 245 for gamma delta T cells. By filter-spot ELISA (ELISPOT), the frequency of IFN-gamma-secreting gamma delta T cells was one-half of that of CD4+ T cells in response to M. tuberculosis, suggesting that gamma delta T cells on a per cell basis were more efficient producers of IFN-gamma than CD4+ T cells. In contrast, CD4+ T cells produced more IL-2 than gamma delta T cells, which correlated with diminished T cell proliferation of gamma delta T cells compared with CD4+ T cells. These results indicate that CD4+ and gamma delta T cell subsets have similar effector functions (cytotoxicity, IFN-gamma production) in response to M. tuberculosis-infected macrophages, despite differences in the Ags recognized, IL-2 production, and efficiency of IFN-gamma production.

Electrochemical insertion of Sr2+ ions onto nano delta-MnO2 particles

Manganese dioxide is known to be an important electroactive material for supercapacitors. Generally, delta-MnO2 is subjected to electrochemical characterization studies in aqueous electrolytes of Na2SO4. It exhibits capacitance behaviour in the potential range between 0 and 1.0 V vs. SCE (saturated calomel electrode). In the present study, it is shown that delta-MnO2 exhibits capacitance behaviour in Sr(NO3)(2) electrolytes also. The suitable potential range in this electrolyte is also found to be 0-1.0 V. Specific capacitancemeasured in Sr(NO3)(2) electrolyte is 192 F g(-1). X-ray photoelectron spectroscopy data confirm that Sr2+ ions get inserted onto delta-MnO2 anoparticles. (C) 2010 Elsevier B.V. All rights reserved.

Pt2+ Dispersed in Ce0.83Ti0.15O2-delta: Significant Improvement in PROX Activity by Ti Substitution in CeO2 in Hydrogen Rich Stream

Pt2+ ion dispersed in CeO2, Ce1-xTixO2-delta and TiO2 have been tested for preferential oxidation of carbon monoxide (PROX) in hydrogen rich stream. It is found that Pt2+ substituted CeO2 and Ce(1-x)TixO(2-delta) in the form of solid solution Ce0.98Pt0.02O2-delta and Ce0.83Ti0.15Pt0.02O2-delta are highly CO selective low temperature PROX catalysts in hydrogen rich stream. Just 15% of Ti substitution in CeO2 improves the overall PROX activity.

Enhanced reducibility of Ce1-xTixO2 compared to that of CeO2 and higher redox catalytic activity of Ce1-x-yTixPtyO2-delta compared to that of Ce1-xPtxO2-delta

Nanocrystalline Ce1-xTixO2 (0 <= x <= 0.4) and Ce1-xTixPtyO2-delta (x = 0.15, gamma = 0.01, 0.02) solid solutions crystallizing in fluorite structure have been prepared by a single step solution combustion method. Temperature programmed reduction and XPS study of Ce1-xTixO2 (x = 0.0-04) show complete reduction of Ti4+ to Ti3+ and reduction of similar to 20% Ce4+ to Ce3+ state compared to 8% Ce4+ to Ce3+ in the case of pure CeO2 below 675 degrees C. The substitution of Ti ions in CeO2 enhances the reducibility of CeO2. Ce0.84Ti0.15Pt0.01O2-delta crystallizes in fluorite structure and Pt is ionically substituted with 2+ and 4+ oxidation states. The H/Pt atomic ratio at 30 degrees C over Ce0.84Ti0.15Pt0.01O2-delta is 5 and that over Ce0.99Pt0.01O2-delta is 4 against just 0.078 for 8 nm Pt metal particles. Carbon monoxide and hydrocarbon oxidation activity are much higher over Ce1-x-yTixPtyO2 (x = 0.15, 0.01, 0.02) compared to Ce1-xPtxO2 (x = 0.01, 0.02). Synergistic involvement of Pt2+/Pt degrees and Ti4+/Ti3+ redox couples in addition to Ce4+/Ce3+ due to the overlap of Pt(5d), Ti(3d), and Ce(4f) bands near E-F is shown to be responsible for improved redox property and higher catalytic activity.

Evidence for decoupled two-dimensional vortex behavior of YBa2Cu3O7-delta in La0.7Sr0.3MnO3/YBa2Cu3O7-delta/La0.7Sr0.3MnO3 trilayer

We investigate the vortex behavior of YBa2Cu3O7-delta thin films sandwiched between two ferromagnetic layers (La0.7Sr0.3MnO3/YBa2Cu3O7-delta/La0.7Sr0.3MnO3). The magnetization study on La0.7Sr0.3MnO3/YBa2Cu3O7-delta/La0.7Sr0.3MnO3 trilayers conspicuously shows the presence of both ferromagnetic and diamagnetic phases. The magnetotransport study on the trilayers reveals a significant reduction in the activation energy (U) for the vortex motion in YBa2Cu3O7-delta. Besides, the ``U'' exhibits a logarithmic dependence on the applied magnetic field which directly indicates the existence of decoupled two-dimensional (2D) pancake vortices present in the CuO2 layers. The evidence of 2D decoupled vortex behavior in La0.7Sr0.3MnO3/YBa2Cu3O7-delta/La0.7Sr0.3MnO3 is believed to arise from (a) the weakening of superconducting coherence length along the c-axis and (b) enhanced intraplane vortex-vortex interaction due to the presence of ferromagnetic layers. (C) 2010 American Institute of Physics. doi: 10.1063/1.3524545]

Interaction of nitrogen and oxygen with C60

Evidence is presented for the strong interaction of nitrogen and oxygen with buckminsterfullerene.

Low cycle fatigue behaviour of a nitrogen modified 316L stainless steel at 823 K

Strain controlled low cycle fatigue tests on solution annealed nitrogen modified 316L stainless steel have been conducted in air at 823 K to ascertain the influence of strain rate and strain amplitude. Effect of strain rate was examined from 3x10(-5) s(-1) to 3 x 10(-2) at a fixed strain amplitude of +/- 0.6%. The influence of strain amplitude was evaluated between +/- 0.25 % and +/- 1.0% at a constant strain rate of 3x10(-3) s(-1). The cyclic stress response at all testing conditions is characterized by an initial hardening followed by saturation. Serrated flow, a characteristic feature of dynamic strain ageing (DSA) was seen at strain rates lower than 3x10(-3) s(-1). Fatigue life was found to decrease with decrease in strain rate. The reduction in fatigue resistance is attributed mainly to the detrimental effects associated with DSA.

Substitution of chromium for univalent copper in superconducting Pb2Sr2(Ca,Y)Cu3O8+delta

Following considerations of geometry and the similarity between chromate and carbonate groups in terms of size and charge, we have investigated the possibility of replacing the two-coordinate Cu-I in superconducting lead cuprates of the general formula Pb2Sr2(Ca, Y)CU3O8 by Cr. A high-resolution electron microscopy study coupled with energy dispersive X-ray analysis on small crystals of the title phases suggests that between 10 and 15% of the Cu-I can be replaced by Cr. While from the present structural study using HRTEM and Rietveld refinement of X-ray powder data we are unable to precisely obtain the oxidation state and oxygen coordination of Cr, we suggest in analogy with Cr substitution in other similar cuprates that in the title phases (CuO2)-O-I rods are partially replaced by tetrahedral CrO42- groups. Infrared spectroscopy supports the presence of CrO42- groups. The phases Pb1.75Sr2Ca0.2Y0.8O8+delta and Pb1.75Sr2Ca0.2Y0.8CCu2.85Cr0.15O8+delta are superconducting as-prepared, but the substitution of Cr for Cu-I results in a decrease of the Te as well as the superconducting volume fraction. (C) 1996 Academic Press, lnc.

Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Structural Transitions of Nitrogen Confined in Slit Graphite Pores

The structure of ordered phases that are formed when nitrogen is confined in slit graphite pores of height h is investigated using Monte Carlo simulations. The pore wall consists of a single-structured graphite sheet. Canonical ensemble simulations are carried out for temperatures ranging from 15 to 70Kwith layer density distributions, in-plane, out-of-plane angular distributions and snapshots evaluated at different temperatures. At each pore height the pore densities are obtained from independent grand ensemble simulations. At the smallest pore height studied (h)7 Å), where a single layer of molecules is accommodated at the center of the pore, the orientations are predominantly wall parallel, forming a biaxially incommensurate herringbone structure.Whentwo or more fluid layers are formed in the slit pore, the orientation of molecules adsorbed next to the wall can exist in either the herringbone or hexagonal phases. In all the multilayered cases studied, with the exception of the h ) 10 Å pore, where both wall layers form a commensurate herringbone structure, the low-temperature wall structures are incommensurate, possessing 6-fold hexagonal symmetry. The presence of the pinwheel structures, which were observed at low temperatures in the h ) 12 Å and h ) 14 Å pores, is determined by the pore height or the proximity and/or density of the adjacent fluid layers when inner layers are present.