Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism

The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/1/anie201606001-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/2/anie201606001.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/3/anie201606001_am.pd

The associations between QCT-based vertebral bone measurements and prevalent vertebral fractures depend on the spinal locations of both bone measurement and fracture

Summary We examined how spinal location affects the relationships between quantitative computed tomography (QCT)-based bone measurements and prevalent vertebral fractures. Upper spine (T4–T10) fractures appear to be more strongly related to bone measures than lower spine (T11–L4) fractures, while lower spine measurements are at least as strongly related to fractures as upper spine measurements. Introduction Vertebral fracture (VF), a common injury in older adults, is most prevalent in the mid-thoracic (T7–T8) and thoracolumbar (T12–L1) areas of the spine. However, measurements of bone mineral density (BMD) are typically made in the lumbar spine. It is not clear how the associations between bone measurements and VFs are affected by the spinal locations of both bone measurements and VF. Methods A community-based case–control study includes 40 cases with moderate or severe prevalent VF and 80 age- and sex-matched controls. Measures of vertebral BMD, strength (estimated by finite element analysis), and factor of risk (load:strength ratio) were determined based on QCT scans at the L3 and T10 vertebrae. Associations were determined between bone measures and prevalent VF occurring at any location, in the upper spine (T4–T10), or in the lower spine (T11–L4). Results Prevalent VF at any location was significantly associated with bone measures, with odds ratios (ORs) generally higher for measurements made at L3 (ORs = 1.9–3.9) than at T10 (ORs = 1.5–2.4). Upper spine fracture was associated with these measures at both T10 and L3 (ORs = 1.9–8.2), while lower spine fracture was less strongly associated (ORs = 1.0–2.4) and only reached significance for volumetric BMD measures at L3. Conclusions Closer proximity between the locations of bone measures and prevalent VF does not strengthen associations between bone measures and fracture. Furthermore, VF etiology may vary by region, with VFs in the upper spine more strongly related to skeletal fragility.National Institutes of Health (U.S.) (Grants R01AR053986, R01AR/AG041398, T32AG023480, and F31AG041629)National Heart, Lung, and Blood Institute. Framingham Heart Study (NIH/NHLBI Contract N01-HC-25195

Quasifree photoproduction of η\eta mesons off protons and neutrons

Differential and total cross sections for the quasifree reactions $\gamma p\rightarrow\eta p$ and $\gamma n\rightarrow\eta n$ have been determined at the MAMI-C electron accelerator using a liquid deuterium target. Photons were produced via bremsstrahlung from the 1.5 GeV incident electron beam and energy-tagged with the Glasgow photon tagger. Decay photons of the neutral decay modes $\eta\rightarrow 2\gamma$ and $\eta\rightarrow 3\pi^0 \rightarrow 6\gamma$ and coincident recoil nucleons were detected in a combined setup of the Crystal Ball and the TAPS calorimeters. The $\eta$-production cross sections were measured in coincidence with recoil protons, recoil neutrons, and in an inclusive mode without a condition on recoil nucleons, which allowed a check of the internal consistency of the data. The effects from nuclear Fermi motion were removed by a kinematic reconstruction of the final-state invariant mass and possible nuclear effects on the quasifree cross section were investigated by a comparison of free and quasifree proton data. The results, which represent a significant improvement in statistical quality compared to previous measurements, agree with the known neutron-to-proton cross-section ratio in the peak of the $S_{11}(1535)$ resonance and confirm a peak in the neutron cross section, which is absent for the proton, at a center-of-mass energy $W = (1670\pm 5)$ MeV with an intrinsic width of $\Gamma\approx 30$ MeV

A new measurement of the neutron detection efficiency for the NaI Crystal Ball detector

We report on a measurement of the neutron detection efficiency in NaI crystals in the Crystal Ball detector obtained from a study of single p0 photoproduction on deuterium using the tagged photon beam at the Mainz Microtron. The results were obtained up to a neutron energy of 400 MeV. They are compared to previous measurements made more than 15 years ago at the pion beam at the BNL AGS

Photoproduction of pi0-mesons off neutrons in the nucleon resonance region

Precise angular distributions have been measured for the first time for the photoproduction of $\pi^{0}$-mesons off neutrons bound in the deuteron. The effects from nuclear Fermi motion have been eliminated by a complete kinematic reconstruction of the final state. The influence of final-state-interaction effects has been estimated by a comparison of the reaction cross section for quasi-free protons bound in the deuteron to the results for free protons and then applied as a correction to the quasi-free neutron data. The experiment was performed at the tagged photon facility of the Mainz Microtron MAMI with the Crystal Ball and TAPS detector setup for incident photon energies between $0.45$~GeV and $1.4$~GeV. The results are compared to the predictions from reaction models and partial-wave analyses based on data from other isospin channels. The model predictions show large discrepancies among each other and the present data will provide much tighter constraints. This is demonstrated by the results of a new analysis in the framework of the Bonn-Gatchina coupled-channel analysis which included the present data.Comment: accepted for publication in Phys; Rev. Let

K+ΛK^+\Lambda and K+Σ0K^+\Sigma^0 photoproduction with fine center-of-mass energy resolution

Measurements of $\gamma p \rightarrow K^{+} \Lambda$ and $\gamma p \rightarrow K^{+} \Sigma^0$ cross-sections have been obtained with the photon tagging facility and the Crystal Ball calorimeter at MAMI-C. The measurement uses a novel $K^+$ meson identification technique in which the weak decay products are characterized using the energy and timing characteristics of the energy deposit in the calorimeter, a method that has the potential to be applied at many other facilities. The fine center-of-mass energy ($W$) resolution and statistical accuracy of the new data results in a significant impact on partial wave analyses aiming to better establish the excitation spectrum of the nucleon. The new analyses disfavor a strong role for quark-diquark dynamics in the nucleon.Comment: 7 pages, 8 figure

Measurement of the beam-helicity asymmetry I⊙I^{\odot} in the photoproduction of π0π±\pi^0\pi^{\pm}-pairs off protons and off neutrons

Beam-helicity asymmetries have been measured at the MAMI accelerator in Mainz for the photoproduction of mixed-charge pion pairs in the reactions $\boldsymbol{\gamma}p\rightarrow n\pi^0\pi^+$ off free protons and $\boldsymbol{\gamma}d\rightarrow (p)p\pi^0\pi^-$ and $\boldsymbol{\gamma}d\rightarrow (n)n\pi^0\pi^+$ off quasi-free nucleons bound in the deuteron for incident photon energies up to 1.4 GeV. Circularly polarized photons were produced from bremsstrahlung of longitudinally polarized electrons and tagged with the Glasgow-Mainz magnetic spectrometer. The charged pions, recoil protons, recoil neutrons, and decay photons from $\pi^0$ mesons were detected in the 4$\pi$ electromagnetic calorimeter composed of the Crystal Ball and TAPS detectors. Using a complete kinematic reconstruction of the final state, excellent agreement was found between the results for free and quasi-free protons, suggesting that the quasi-free neutron results are also a close approximation of the free-neutron asymmetries. A comparison of the results to the predictions of the Two-Pion-MAID reaction model shows that the reaction mechanisms are still not well understood, in particular at low incident photon energies in the second nucleon-resonance region.Comment: accepted for publication in Eur. phys. J.

Photoproduction of π0\pi^0-pairs off protons and off neutrons

Total cross sections, angular distributions, and invariant-mass distributions have been measured for the photoproduction of $\pi^0\pi^0$ pairs off free protons and off nucleons bound in the deuteron. The experiments were performed at the MAMI accelerator facility in Mainz using the Glasgow photon tagging spectrometer and the Crystal Ball/TAPS detector. The accelerator delivered electron beams of 1508 and 1557~MeV, which produced bremsstrahlung in thin radiator foils. The tagged photon beam covered energies up to 1400~MeV. The data from the free proton target are in good agreement with previous measurements and were only used to test the analysis procedures. The results for differential cross sections (angular distributions and invariant-mass distributions) for free and quasi-free protons are almost identical in shape, but differ in absolute magnitude up to 15\%. Thus, moderate final-state interaction effects are present. The data for quasi-free neutrons are similar to the proton data in the second resonance region (final state invariant masses up to $\approx$1550~MeV), where both reactions are dominated by the $N(1520)3/2^-\rightarrow \Delta(1232)3/2^+\pi$ decay. At higher energies, angular and invariant-mass distributions are different. A simple analysis of the shapes of the invariant-mass distributions in the third resonance region is consistent with strong contributions of an $N^{\star}\rightarrow N\sigma$ decay for the proton, while the reaction is dominated by a sequential decay via a $\Delta\pi$ intermediate state for the neutron. The data are compared to predictions from the Two-Pion-MAID model and the Bonn-Gatchina coupled channel analysis.Comment: accepted for publication in Eur. Phys. J.

The isospin structure of photoproduction of pi-eta pairs from the nucleon in the threshold region

Photoproduction of $\pi\eta$-pairs from nucleons has been investigated from threshold up to incident photon energies of $\approx$~1.4~GeV. The quasi-free reactions $\gamma p\rightarrow p\pi^0\eta$, $\gamma n\rightarrow n\pi^0\eta$, $\gamma p\rightarrow n\pi^+\eta$, and $\gamma n\rightarrow p\pi^-\eta$ were for the first time measured from nucleons bound in the deuteron. The corresponding reactions from a free-proton target were also studied to investigate final-state interaction effects (for neutral pions the free-proton results could be compared to previous measurements; the $\gamma p\rightarrow n\pi^+\eta$ reaction was measured for the first time). For the $\pi^0\eta$ final state coherent production via the $\gamma d\rightarrow d\pi^0\eta$ reaction was also investigated. The experiments were performed at the tagged photon beam of the Mainz MAMI accelerator using an almost $4\pi$ coverage electromagnetic calorimeter composed of the Crystal Ball and TAPS detectors. The total cross sections for the four different final states obey the relation $\sigma(p\pi^0\eta)$ $\approx$ $\sigma(n\pi^0\eta)$ $\approx$ $2\sigma(p\pi^-\eta)$ $\approx$ $2\sigma(n\pi^+\eta)$ as expected for a dominant contribution from a $\Delta^{\star}\rightarrow\eta\Delta(1232)\rightarrow\pi\eta N$ reaction chain, which is also supported by the shapes of the invariant-mass distributions of nucleon-meson and $\pi$-$\eta$ pairs. The experimental results are compared to the predictions from an isobar reaction model.Comment: accepted for publication in Phys. Lett.

Photoproduction of π0-pairs off protons and off neutrons

Total cross sections, angular distributions, and invariant-mass distributions have been measured for the photoproduction of π0π0 pairs off free protons and off nucleons bound in the deuteron. The experiments were performed at the MAMI accelerator facility in Mainz using the Glasgow photon tagging spectrometer and the Crystal Ball/TAPS detector. The accelerator delivered electron beams of 1508 and 1557MeV, which produced bremsstrahlung in thin radiator foils. The tagged photon beam covered energies up to 1400MeV. The data from the free proton target are in good agreement with previous measurements and were only used to test the analysis procedures. The results for differential cross sections (angular distributions and invariant-mass distributions) for free and quasi-free protons are almost identical in shape, but differ in absolute magnitude up to 15%. Thus, moderate final-state interaction effects are present. The data for quasi-free neutrons are similar to the proton data in the second resonance region (final-state invariant masses up to ≈1550 MeV), where both reactions are dominated by the N(1520)3/2−→Δ(1232)3/2+π decay. At higher energies, angular and invariant-mass distributions are different. A simple analysis of the shapes of the invariant-mass distributions in the third resonance region is consistent with strong contributions of an N⋆→Nσ decay for the proton, while the reaction is dominated by a sequential decay via a Δπ intermediate state for the neutron. The data are compared to predictions from the Two-Pion-MAID model and the Bonn-Gatchina coupled-channel analysis