559 research outputs found
Magnetic field control of cycloidal domains and electric polarization in multiferroic BiFeO
The magnetic field induced rearrangement of the cycloidal spin structure in
ferroelectric mono-domain single crystals of the room-temperature multiferroic
BiFeO is studied using small-angle neutron scattering (SANS). The cycloid
propagation vectors are observed to rotate when magnetic fields applied
perpendicular to the rhombohedral (polar) axis exceed a pinning threshold value
of 5\,T. In light of these experimental results, a phenomenological model
is proposed that captures the rearrangement of the cycloidal domains, and we
revisit the microscopic origin of the magnetoelectric effect. A new coupling
between the magnetic anisotropy and the polarization is proposed that explains
the recently discovered magnetoelectric polarization to the rhombohedral axis
Metal-only Lewis pairs between group 10 metals and Tl(I) or Ag(I): insights into the electronic consequences of Z-type ligand bindingâ€
Complexes bearing electron rich transition metal centers, especially those displaying coordinative unsaturation, are well-suited to form reverse-dative σ-interactions with Lewis acids. Herein we demonstrate the generality of zerovalent, group 10 m-terphenyl isocyanide complexes to form reverse-dative σ-interactions to Tl(I) and Ag(I) centers. Structural and spectroscopic investigations of these metal-only Lewis pairs (MOLPs) has allowed insight into the electronic consequences of Lewis-acid ligation within the primary coordination sphere of a transition metal center. Treatment of the bis-isocyanide complex, Pt(CNArDipp2)2 (ArDipp2 = 2,6-(2,6-(i-Pr)2C6H3)2C6H3) with TlOTf (OTf = [O3SCF3]−) yields the Pt/Tl MOLP [TlPt(CNArDipp2)2]OTf (1). 1H NMR and IR spectroscopic studies on 1, and its Pd congener [TlPd(CNArDipp2)2]OTf (2), demonstrate that the M → Tl interaction is labile in solution. However, treatment of complexes 1 and 2 with Na[BArF4] (ArF = 3,5-(CF3)2C6H3) produces [TlPt(CNArDipp2)2]BArF4 (3) and [TlPd(CNArDipp2)2]BArF4 (4), in which Tl(I) binding is shown to be static by IR spectroscopy and, in the case of 3, 195Pt NMR spectroscopy as well. This result provides strong evidence that the M → Tl linkages can be attributed primarily to σ-donation from the group 10 metal to Tl, as loss of ionic stabilization of Tl by the triflate anion is compensated for by increasing the degree of M → Tl σ-donation. In addition, X-ray Absorption Near-Edge Spectroscopy (XANES) on the Pd/Tl and Ni/Tl MOLPs, [TlPd(CNArDipp2)2]OTf (2) and [TlNi(CNArMes2)3]OTf, respectively, is used to illustrate that the formation of a reverse-dative σ-interaction with Tl(I) does not alter the spectroscopic oxidation state of the group 10 metal. Also reported is the ability of M(CNArDipp2)2 (M = Pt, Pd) to form MOLPs with Ag(I), yielding the complexes [AgM(CNArDipp2)2]OTf (5, M = Pt; 6, M = Pd). As was determined for the Tl-containing MOLPs 1–4, it is shown that the spectroscopic oxidation states of the group 10 metal in 5 and 6 are essentially unchanged compared to the zerovalent precursors M(CNArDipp2)2. However, in the case of 5 and 6, the formation of a dative M → Ag σ-bonding interaction facilitates the binding of Lewis bases to the group 10 metal trans to Ag, illustrating the potential of acceptor fragments to open up new coordination sites on transition metal complexes without formal, two-electron oxidation
Carbon Monoxide Binding to the Iron–Molybdenum Cofactor of Nitrogenase: a Detailed Quantum Mechanics/Molecular Mechanics Investigation
Carbon monoxide (CO) is a well-known inhibitor of nitrogenase activity. Under turnover conditions, CO binds to FeMoco, the active site of Mo nitrogenase. Time-resolved IR measurements suggest an initial terminal CO at 1904 cm–1 that converts to a bridging CO at 1715 cm–1, and an X-ray structure shows that CO can displace one of the bridging belt sulfides of FeMoco. However, the CO-binding redox state(s) of FeMoco (En) and the role of the protein environment in stabilizing specific CO-bound intermediates remain elusive. In this work, we carry out an in-depth analysis of the CO–FeMoco interaction based on quantum chemical calculations addressing different aspects of the electronic structure. (1) The local electronic structure of the Fe–CO bond is studied through diamagnetically substituted FeMoco. (2) A cluster model of FeMoco within a polarizable continuum illustrates how CO binding may affect the spin-coupling between the metal centers. (3) A QM/MM model incorporates the explicit influence of the amino acid residues surrounding FeMoco in the MoFe protein. The QM/MM model predicts both a terminal and a bridging CO in the E1 redox state. The scaled calculated CO frequencies (1922 and 1716 cm–1, respectively) are in good agreement with the experimentally observed IR bands supporting CO binding to the E1 state. Alternatively, an E2 state QM/MM model, which has the same atomic structure as the CO-bound X-ray structure, features a semi-bridging CO with a scaled calculated frequency (1718 cm–1) similar to the bridging CO in the E1 model
Structure–Spectroscopy Correlations for Intermediate Q of Soluble Methane Monooxygenase: Insights from QM/MM Calculations
The determination of the diiron core intermediate structures involved in the catalytic cycle of soluble methane monooxygenase (sMMO), the enzyme that selectively catalyzes the conversion of methane to methanol, has been a subject of intense interest within the bioinorganic scientific community. Particularly, the specific geometry and electronic structure of the intermediate that precedes methane binding, known as intermediate Q (or MMOHQ), has been debated for over 30 years. Some reported studies support a bis-μ-oxo-bridged Fe(IV)2O2 closed-core conformation Fe(IV)2O2 core, whereas others favor an open-core geometry, with a longer Fe–Fe distance. The lack of consensus calls for a thorough re-examination and reinterpretation of the spectroscopic data available on the MMOHQ intermediate. Herein, we report extensive simulations based on a hybrid quantum mechanics/molecular mechanics approach (QM/MM) approach that takes into account the complete enzyme to explore possible conformations for intermediates MMOHox and MMOHQ of the sMMOH catalytic cycle. High-level quantum chemical approaches are used to correlate specific structural motifs with geometric parameters for comparison with crystallographic and EXAFS data, as well as with spectroscopic data from Mössbauer spectroscopy, Fe K-edge high-energy resolution X-ray absorption spectroscopy (HERFD XAS), and resonance Raman 16O–18O difference spectroscopy. The results provide strong support for an open-core-type configuration in MMOHQ, with the most likely topology involving mono-oxo-bridged Fe ions and alternate terminal Fe-oxo and Fe-hydroxo groups that interact via intramolecular hydrogen bonding. The implications of an open-core intermediate Q on the reaction mechanism of sMMO are discussed
High-energy magnetic excitations in overdoped LaSrCuO studied by neutron and resonant inelastic X-ray scattering
We have performed neutron inelastic scattering and resonant inelastic X-ray
scattering (RIXS) at the Cu- edge to study high-energy magnetic
excitations at energy transfers of more than 100 meV for overdoped
LaSrCuO with ( K) and
(non-superconducting) using identical single crystal samples for the two
techniques. From constant-energy slices of neutron scattering cross-sections,
we have identified magnetic excitations up to ~250 meV for . Although
the width in the momentum direction is large, the peak positions along the (pi,
pi) direction agree with the dispersion relation of the spin-wave in the
non-doped LaCuO (LCO), which is consistent with the previous RIXS
results of cuprate superconductors. Using RIXS at the Cu- edge, we have
measured the dispersion relations of the so-called paramagnon mode along both
(pi, pi) and (pi, 0) directions. Although in both directions the neutron and
RIXS data connect with each other and the paramagnon along (pi, 0) agrees well
with the LCO spin-wave dispersion, the paramagnon in the (pi, pi) direction
probed by RIXS appears to be less dispersive and the excitation energy is lower
than the spin-wave of LCO near (pi/2, pi/2). Thus, our results indicate
consistency between neutron inelastic scattering and RIXS, and elucidate the
entire magnetic excitation in the (pi, pi) direction by the complementary use
of two probes. The polarization dependence of the RIXS profiles indicates that
appreciable charge excitations exist in the same energy range of magnetic
excitations, reflecting the itinerant character of the overdoped sample. A
possible anisotropy in the charge excitation intensity might explain the
apparent differences in the paramagnon dispersion in the (pi, pi) direction as
detected by the X-ray scattering.Comment: 7 pages, 7 figure
Pauli Paramagnetic Effects on Vortices in Superconducting TmNi2B2C
The magnetic field distribution around the vortices in TmNi2B2C in the
paramagnetic phase was studied experimentally as well as theoretically. The
vortex form factor, measured by small-angle neutron scattering, is found to be
field independent up to 0.6 Hc2 followed by a sharp decrease at higher fields.
The data are fitted well by solutions to the Eilenberger equations when
paramagnetic effects due to the exchange interaction with the localized 4f Tm
moments are included. The induced paramagnetic moments around the vortex cores
act to maintain the field contrast probed by the form factor.Comment: 4 pages, 4 figure
Structural Transition Kinetics and Activated Behavior in the Superconducting Vortex Lattice
Using small-angle neutron scattering, we investigated the behavior of a
metastable vortex lattice state in MgB2 as it is driven towards equilibrium by
an AC magnetic field. This shows an activated behavior, where the AC field
amplitude and cycle count are equivalent to, respectively, an effective
"temperature" and "time". The activation barrier increases as the metastable
state is suppressed, corresponding to an aging of the vortex lattice.
Furthermore, we find a cross-over from a partial to a complete suppression of
metastable domains depending on the AC field amplitude, which may empirically
be described by a single free parameter. This represents a novel kind of
collective vortex behavior, most likely governed by the nucleation and growth
of equilibrium vortex lattice domains.Comment: 5 pages plus 3 pages of supplemental materia
Role of nitric oxide in Salmonella typhimurium-mediated cancer cell killing
Background: Bacterial targeting of tumours is an important anti-cancer strategy. We previously showed that strain SL7838 of Salmonella typhimurium targets and kills cancer cells. Whether NO generation by the bacteria has a role in SL7838 lethality to cancer cells is explored. This bacterium has the mechanism for generating NO, but also for decomposing it. Methods: Mechanism underlying Salmonella typhimurium tumour therapy was investigated through in vitro and in vivo studies. NO measurements were conducted either by chemical assays (in vitro) or using Biosensors (in vivo). Cancer cells cytotoxic assay were done by using MTS. Bacterial cell survival and tumour burden were determined using molecular imaging techniques. Results: SL7838 generated nitric oxide (NO) in anaerobic cell suspensions, inside infected cancer cells in vitro and in implanted 4T1 tumours in live mice, the last, as measured using microsensors. Thus, under these conditions, the NO generating pathway is more active than the decomposition pathway. The latter was eliminated, in strain SL7842, by the deletion of hmp- and norV genes, making SL7842 more proficient at generating NO than SL7838. SL7842 killed cancer cells more effectively than SL7838 in vitro, and this was dependent on nitrate availability. This strain was also ca. 100% more effective in treating implanted 4T1 mouse tumours than SL7838
Advancing Critical Chemical Processes for a Sustainable Future: Challenges for Industry and the Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT)
Catalysis is involved in around 85 % of manufacturing industry and contributes an estimated 25 % to the global domestic product, with the majority of the processes relying on heterogeneous catalysis. Despite the importance in different global segments, the fundamental understanding of heterogeneously catalysed processes lags substantially behind that achieved in other fields. The newly established Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT) targets innovative concepts that could contribute to the scientific developments needed in the research field to achieve net zero greenhouse gas emissions in the chemical industries. This Viewpoint Article presents some of our research activities and visions on the current and future challenges of heterogeneous catalysis regarding green industry and the circular economy by focusing explicitly on critical processes. Namely, hydrogen production, ammonia synthesis, and carbon dioxide reduction, along with new aspects of acetylene chemistry
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