Living with Oxygen

Work on the electronic structures of metal–oxo complexes began in Copenhagen over 50 years ago. This work led to the prediction that tetragonal multiply bonded transition metal–oxos would not be stable beyond the iron–ruthenium–osmium oxo wall in the periodic table and that triply bonded metal–oxos could not be protonated, even in the strongest Brønsted acids. In this theory, only double bonded metal–oxos could attract protons, with basicities being a function of the electron donating ability of ancillary ligands. Such correlations of electronic structure with reactivity have gained importance in recent years, most notably owing to the widespread recognition that high-valent iron–oxos are intermediates in biological reactions critical to life on Earth. In this Account, we focus attention on the oxygenations of inert organic substrates by cytochromes P450, as these reactions involve multiply bonded iron–oxos. We emphasize that P450 iron–oxos are strong oxidants, so strong that they would destroy nearby amino acids if substrates are not oxygenated rapidly; it is our view that these high-valent iron–oxos are such dangerous reactive oxygen species that Nature surely found ways to disable them. Looking more deeply into this matter, mainly by examining many thousands of structures in the Protein Data Bank, we have found that P450s and other enzymes that require oxygen for function have chains of tyrosines and tryptophans that extend from active-site regions to protein surfaces. Tyrosines are near the heme active sites in bacterial P450s, whereas tryptophan is closest in most human enzymes. High-valent iron–oxo survival times taken from hole hopping maps range from a few nanoseconds to milliseconds, depending on the distance of the closest Trp or Tyr residue to the heme. In our proposed mechanism, multistep hole tunneling (hopping) through Tyr/Trp chains guides the damaging oxidizing hole to the protein surface, where it can be quenched by soluble protein or small molecule reductants. As the Earth’s oxygenic atmosphere is believed to have developed about 2.5 billion years ago, the increase in occurrence frequency of tyrosine and tryptophan since the last universal evolutionary ancestor may be in part a consequence of enzyme protective functions that developed to cope with the environmental toxin, O_2

Pressure Dependence of the Magnetic Anisotropy in the "Single-Molecule Magnet" [Mn4O3Br(OAc)3(dbm)3]

The anisotropy splitting in the ground state of the single-molecule magnet [Mn4O3Br(OAc)3(dbm)3] is studied by inelastic neutron scattering as a function of hydrostatic pressure. This allows a tuning of the anisotropy and thus the energy barrier for slow magnetisation relaxation at low temperatures. The value of the negative axial anisotropy parameter $D_{\rm cluster}$ changes from -0.0627(1) meV at ambient to -0.0603(3) meV at 12 kbar pressure, and in the same pressure range the height of the energy barrier between up and down spins is reduced from 1.260(5) meV to 1.213(9) meV. Since the $\rm Mn-Br$ bond is significantly softer and thus more compressible than the $\rm Mn-O$ bonds, pressure induces a tilt of the single ion Mn$^{3+}$ anisotropy axes, resulting in the net reduction of the axial cluster anisotropy.Comment: 4 pages, 3 figure

The effectiveness of mouthwashes in alleviating radiation-induced oral mucositis in head and neck cancer patients: A systematic review

Objective The aim of the study was to perform a systematic literature search and meta-analysis to reveal the most effective mouthwash for head and neck cancer patients who are experiencing radiation therapy-induced mucositis. Methods Using two electronic databases, a literature search and data interpretation were systematically performed as follows: (i) problem specification, (ii) devising of a literature search plan, (iii) literature search and retrieval of publications, and (iv) meta-analysis and data interpretation. The main problem was specified as follows: what mouthwash is effective in alleviating oral mucositis for head and neck cancer patients who are undergoing radiotherapy? Results The literature search yielded 354 titles and abstracts. After reviewing the extracted literature, 25 publications met the inclusion criteria for this study and 17 of 25 were eventually evaluated in the meta-analysis. Conclusion The results of the meta-analysis indicated that the use of a mouthwash that includes anti-inflammatory properties contributes the most to alleviating oral mucositis in patients who are undergoing radiotherapy to treat head and neck cancer

ClaimChain: Improving the Security and Privacy of In-band Key Distribution for Messaging

The social demand for email end-to-end encryption is barely supported by mainstream service providers. Autocrypt is a new community-driven open specification for e-mail encryption that attempts to respond to this demand. In Autocrypt the encryption keys are attached directly to messages, and thus the encryption can be implemented by email clients without any collaboration of the providers. The decentralized nature of this in-band key distribution, however, makes it prone to man-in-the-middle attacks and can leak the social graph of users. To address this problem we introduce ClaimChain, a cryptographic construction for privacy-preserving authentication of public keys. Users store claims about their identities and keys, as well as their beliefs about others, in ClaimChains. These chains form authenticated decentralized repositories that enable users to prove the authenticity of both their keys and the keys of their contacts. ClaimChains are encrypted, and therefore protect the stored information, such as keys and contact identities, from prying eyes. At the same time, ClaimChain implements mechanisms to provide strong non-equivocation properties, discouraging malicious actors from distributing conflicting or inauthentic claims. We implemented ClaimChain and we show that it offers reasonable performance, low overhead, and authenticity guarantees.Comment: Appears in 2018 Workshop on Privacy in the Electronic Society (WPES'18

Irreducible triangulations of surfaces with boundary

A triangulation of a surface is irreducible if no edge can be contracted to produce a triangulation of the same surface. In this paper, we investigate irreducible triangulations of surfaces with boundary. We prove that the number of vertices of an irreducible triangulation of a (possibly non-orientable) surface of genus g>=0 with b>=0 boundaries is O(g+b). So far, the result was known only for surfaces without boundary (b=0). While our technique yields a worse constant in the O(.) notation, the present proof is elementary, and simpler than the previous ones in the case of surfaces without boundary

Dispersion of Resonant Raman Peaks of CO and OH in SnO2, Mo1-x FexO2 Thin Films and SiO2 bulk glass

Resonance Raman (RR) peaks of and stretching modes and their higher harmonics have been observed superimposed on photoluminescence (PL) spectrum of thin films. Commercial fluorine doped thin films deposited by sputtering on glass and thin films deposited on Si by laser ablation have been studied. The dispersions of CO and OH stretching RR modes are ~ 600 cm-1/eV and 800 cm-1 respectively. The dispersion of the third harmonic of CO stretching mode is ~ 2000 cm-1/eV. Similar dispersion of RR peak of stretching modes and higher harmonics superimposed on PL spectra has been observed in Mo1-xFexO2 thin films and SiO2 bulk glass. Large dispersion of RR peaks seems to be a common property of oxides with impurities of and .Comment: 13 pages including three figure

A Cost-Effective Design for a Neutrino Factory

There have been active efforts in the U.S., Europe, and Japan on the design of a Neutrino Factory. This type of facility produces intense beams of neutrinos from the decay of muons in a high energy storage ring. In the U.S., a second detailed Feasibility Study (FS2) for a Neutrino Factory was completed in 2001. Since that report was published, new ideas in bunching, cooling and acceleration of muon beams have been developed. We have incorporated these ideas into a new facility design, which we designate as Study 2B (ST2B), that should lead to significant cost savings over the FS2 design.Comment: 46 pages, 38 figures; to be submitted to Physical Review Special Topics: Accelerators and Beam

Morphological, Structural, and Spectral Characteristics of Amorphous Iron Sulfates

Current or past brine hydrologic activity on Mars may provide suitable conditions for the formation of amorphous ferric sulfates. Once formed, these phases would likely be stable under current Martian conditions, particularly at low- to mid-latitudes. Therefore, we consider amorphous iron sulfates (AIS) as possible components of Martian surface materials. Laboratory AIS were created through multiple synthesis routes and characterized with total X-ray scattering, thermogravimetric analysis, scanning electron microscopy, visible/near-infrared (VNIR), thermal infrared (TIR), and Mössbauer techniques. We synthesized amorphous ferric sulfates (Fe(III)2(SO4)3 · ~ 6–8H2O) from sulfate-saturated fluids via vacuum dehydration or exposure to low relative humidity

A Realistic Description of Nucleon-Nucleon and Hyperon-Nucleon Interactions in the SU_6 Quark Model

We upgrade a SU_6 quark-model description for the nucleon-nucleon and hyperon-nucleon interactions by improving the effective meson-exchange potentials acting between quarks. For the scalar- and vector-meson exchanges, the momentum-dependent higher-order term is incorporated to reduce the attractive effect of the central interaction at higher energies. The single-particle potentials of the nucleon and Lambda, predicted by the G-matrix calculation, now have proper repulsive behavior in the momentum region q_1=5 - 20 fm^-1. A moderate contribution of the spin-orbit interaction from the scalar-meson exchange is also included. As to the vector mesons, a dominant contribution is the quadratic spin-orbit force generated from the rho-meson exchange. The nucleon-nucleon phase shifts at the non-relativistic energies up to T_lab=350 MeV are greatly improved especially for the 3E states. The low-energy observables of the nucleon-nucleon and the hyperon-nucleon interactions are also reexamined. The isospin symmetry breaking and the Coulomb effect are properly incorporated in the particle basis. The essential feature of the Lambda N - Sigma N coupling is qualitatively similar to that obtained from the previous models. The nuclear saturation properties and the single-particle potentials of the nucleon, Lambda and Sigma are reexamined through the G-matrix calculation. The single-particle potential of the Sigma hyperon is weakly repulsive in symmetric nuclear matter. The single-particle spin-orbit strength for the Lambda particle is very small, in comparison with that of the nucleons, due to the strong antisymmetric spin-orbit force generated from the Fermi-Breit interaction.Comment: Revtex v2.09, 69 pages with 25 figure

Atmospheric response to solar radiation absorbed by phytoplankton

Phytoplankton alter the absorption of solar radiation, affecting upper ocean temperature and circulation. These changes, in turn, influence the atmosphere through modification of the sea surface temperature (SST). To investigate the effects of the present-day phytoplankton concentration on the atmosphere, an atmospheric general circulation model was forced by SST changes due to phytoplankton. The modified SST was obtained from ocean general circulation model runs with space- and time-varying phytoplankton abundances from Coastal Zone Color Scanner data. The atmospheric simulations indicate that phytoplankton amplify the seasonal cycle of the lowest atmospheric layer temperature. This amplification has an average magnitude of 0.3°K but may reach over 1°K locally. The surface warming in the summer is marginally larger than the cooling in the winter, so that on average annually and globally, phytoplankton warm the lowest layer by about 0.05°K. Over the ocean the surface air temperature changes closely follow the SST changes. Significant, often amplified, temperature changes also occur over land. The climatic effect of phytoplankton extends throughout the troposphere, especially in middle latitudes where increased subsidence during summer traps heat. The amplification of the seasonal cycle of air temperature strengthens tropical convection in the summer hemisphere. In the eastern tropical Pacific Ocean a decreased SST strengthens the Walker circulation and weakens the Hadley circulation. These significant atmospheric changes indicate that the radiative effects of phytoplankton should not be overlooked in studies of climate change.Keywords: Atmospheric general circulation model (AGCM), seasonal cycle, Phytoplankton, sea surface temperature (SST), Absorption of solar radiatio