A motivic study of generalized Burniat surfaces

Generalized Burniat surfaces are surfaces of general type with \(p_g=q\) and Euler number \(e=6\) obtained by a variant of Inoue’s construction method for the classical Burniat surfaces. I prove a variant of the Bloch conjecture for these surfaces. The method applies also to the so-called Sicilian surfaces introduced by Bauer et al. in (J Math Sci Univ Tokyo 22(2–15):55–111, 2015. arXiv:1409.1285v2). This implies that the Chow motives of all of these surfaces are finite-dimensional in the sense of Kimura.     

Benchmarking the ACEnano Toolbox for Characterisation of Nanoparticle Size and Concentration by Interlaboratory Comparisons

ACEnano is an EU-funded project which aims at developing, optimising and validating methods for the detection and characterisation of nanomaterials (NMs) in increasingly complex matrices to improve confidence in the results and support their use in regulation. Within this project, several interlaboratory comparisons (ILCs) for the determination of particle size and concentration have been organised to benchmark existing analytical methods. In this paper the results of a number of these ILCs for the characterisation of NMs are presented and discussed. The results of the analyses of pristine well-defined particles such as 60 nm Au NMs in a simple aqueous suspension showed that laboratories are well capable of determining the sizes of these particles. The analysis of particles in complex matrices or formulations such as consumer products resulted in larger variations in particle sizes within technologies and clear differences in capability between techniques. Sunscreen lotion sample analysis by laboratories using spICP-MS and TEM/SEM identified and confirmed the TiO₂ particles as being nanoscale and compliant with the EU definition of an NM for regulatory purposes. In a toothpaste sample orthogonal results by PTA, spICP-MS and TEM/SEM agreed and stated the TiO₂ particles as not fitting the EU definition of an NM. In general, from the results of these ILCs we conclude that laboratories are well capable of determining particle sizes of NM, even in fairly complex formulations.     

A simple synthesis of functionalized 3-methyl-1-pyridinyl-1H-imidazolium salts as bidentate N-heterocyclic-carbene precursors and their application in Ir-catalyzed arene borylation

The selective alkylation of functionalized 2-(1H-imidazol-1-yl)pyridines 1 furnishes 3-methyl-1-pyridinyl-1H-imidazolium salts 2, which can be deprotonated to deliver strongly electron-donating bidentate N-heterocyclic carbene ligands (NHC). The synthesis of these ligands and their application in the iridium-catalyzed C-H activated borylation of arenes with its current scope and limitations are reported.     

An advanced Gibbs-Duhem integration method: theory and applications

The conventional Gibbs-Duhem integration method is very convenient for the prediction of phase equilibria of both pure components and mixtures. However, it turns out to be inefficient. The method requires a number of lengthy simulations to predict the state conditions at which phase coexistence occurs. This number is not known from the outset of the numerical integration process. Furthermore, the molecular configurations generated during the simulations are merely used to predict the coexistence condition and not the liquid- and vapor-phase densities and mole fractions at coexistence. In this publication, an advanced Gibbs-Duhem integration method is presented that overcomes above-mentioned disadvantage and inefficiency. The advanced method is a combination of Gibbs-Duhem integration and multiple-histogram reweighting. Application of multiple-histogram reweighting enables the substitution of the unknown number of simulations by a fixed and predetermined number. The advanced method has a retroactive nature; a current simulation improves the predictions of previously computed coexistence points as well. The advanced Gibbs-Duhem integration method has been applied for the prediction of vapor-liquid equilibria of a number of binary mixtures. The method turned out to be very convenient, much faster than the conventional method, and provided smooth simulation results. As the employed force fields perfectly predict pure-component vapor-liquid equilibria, the binary simulations were very well suitable for testing the performance of different sets of combining rules. Employing Lorentz-Hudson-McCoubrey combining rules for interactions between unlike molecules, as opposed to Lorentz-Berthelot combining rules for all interactions, considerably improved the agreement between experimental and simulated data.     

Spectroscopic properties and electronic structure of five- and six-coordinate iron(II) porphyrin NO complexes: Effect of the axial N-donor ligand

In this paper, the differences in the spectroscopic properties and electronic structures of five- and six-coordinate iron(II) porphyrin NO complexes are explored using [Fe(TPP)(NO)] (1; TPP = tetraphenylporphyrin) and [Fe(TPP)(MI)(NO)] (2; MI = 1-methylimidazole) type systems. Binding of N-donor ligands in axial position trans to NO to five-coordinate complexes of type 1 is investigated using UV-vis absorption and 1H NMR spectroscopies. This way, the corresponding binding constants Keq are determined and the 1H NMR spectra of 1 and 2 are assigned for the first time. In addition, 1H NMR allows for the determination of the degree of denitrosylation in solutions of 1 with excess base. The influence of the axial ligand on the properties of the coordinated NO is then investigated. Vibrational spectra (IR and Raman) of 1 and 2 are presented and assigned using isotope substitution and normal-coordinate analysis. Obtained force constants are 12.53 (N-O) and 2.98 mdyn/A (Fe-NO) for 1 compared to 11.55 (N-O) and 2.55 mdyn/A (Fe-NO) for 2. Together with the NMR results, this provides experimental evidence that binding of the trans ligand weakens the Fe-NO bond. The principal bonding schemes of 1 and 2 are very similar. In both cases, the Fe-N-O subunit is strongly bent. Donation from the singly occupied pi* orbital of NO into d(z2) of iron(II) leads to the formation of an Fe-NO sigma bond. In addition, a medium-strong pi back-bond is present in these complexes. The most important difference in the electronic structures of 1 and 2 occurs for the Fe-NO sigma bond, which is distinctively stronger for 1 in agreement with the experimental force constants. The increased sigma donation from NO in 1 also leads to a significant transfer of spin density from NO to iron, as has been shown by magnetic circular dichroism (MCD) spectroscopy in a preceding Communication (Praneeth, V. K. K.; Neese, F.; Lehnert, N. Inorg. Chem. 2005, 44, 2570-2572). This is confirmed by the 1H NMR results presented here. Hence, further experimental and computational evidence is provided that complex 1 has noticeable Fe(I)NO+ character relative to 2, which is an Fe(II)NO(radical) complex. Finally, using MCD theory and quantum chemical calculations, the absorption and MCD C-term spectra of 1 and 2 are assigned for the first time.     

Enantioselective epoxidation of terminal alkenes to (R)- and (S)-epoxides by engineered cytochromes P450 BM-3

Cytochrome P450 BM-3 from Bacillus megaterium was engineered for enantioselective epoxidation of simple terminal alkenes. Screening saturation mutagenesis libraries, in which mutations were introduced in the active site of an engineered P450, followed by recombination of beneficial mutations generated two P450 BM-3 variants that convert a range of terminal alkenes to either (R)- or (S)-epoxide (up to 83 % ee) with high catalytic turnovers (up to 1370) and high epoxidation selectivities (up to 95 %). A biocatalytic system using E. coli lysates containing P450 variants as the epoxidation catalysts and in vitro NADPH regeneration by the alcohol dehydrogenase from Thermoanaerobium brockii generates each of the epoxide enantiomers, without additional cofactor.     

Echo-shifted multislice EPI for high-speed fMRI

The advantages of event-related functional Magnetic Resonance Imaging (fMRI) and the increasing use of fMRI in cognitive experiments are both driving the development of techniques that allow images sensitive to the blood oxygen level-dependent effect to be acquired at ever-higher temporal resolution. Here, we present a technique based on the use of echo shifting (ES) in conjunction with a multislice (MS) echo planar imaging (EPI) readout, which allows T2*-weighted images to be generated with a repetition time per slice that is less than the echo time (TE). Using this ES-MS-EPI approach, it is shown that images with a TE of 40 ms can be acquired with an acquisition time per slice of only 27 ms. The utility of the MS-ES-EPI sequence is demonstrated in a visual-motor, event-related fMRI study in which nine-slice image volumes are acquired continuously at a rate of 4.1 Hz. The sequence is shown to produce reliable activation associated with both visual stimuli and motor actions.     

Synthetic T1-weighted brain image generation with incorporated coil intensity correction using DESPOT1

The increased use of phased-array and surface coils in magnetic resonance imaging, the push toward increased field strength and the need for standardized imaging across multiple sites during clinical trials have resulted in the need for methods that can ensure consistency of intensity both within the image and across multiple subjects/sites. Here, we describe a means of addressing these concerns through an extension of the rapid T(1) mapping technique - driven equilibrium single-pulse observation of T(1). The effectiveness of the proposed approach was evaluated using human brain T(1) maps acquired at 1.5 T with a multichannel phased-array coil. Corrected "synthetic" T(1)-weighted images were reconstructed by substituting the T(1) values back into the governing signal intensity equation while assuming a constant value for the equilibrium magnetization. To demonstrate signal normalization across a longitudinal study, we calculated synthetic T(1)-weighted images from data acquired from the same healthy subject at four different time points. Signal intensity profiles between the acquired and synthetic images were compared to determine the improvements with our proposed approach. Following correction, the images demonstrate obvious qualitative improvement with increased signal uniformity across the image. Near-perfect signal normalization was also observed across the longitudinal study, allowing direct comparison between the images. In addition, we observe an increase in contrast-to-noise ratio (compared with regular T(1)-weighted images) for synthetic images created, assuming uniform proton density throughout the volume. The proposed approach permits rapid correction for signal intensity inhomogeneity without significantly lengthening exam time or reducing image signal-to-noise ratio. This technique also provides a robust method for signal normalization, which is useful in multicenter longitudinal MR studies of disease progression, and allows the user to reconstruct T(1)-weighted images with arbitrary T(1) weighting.     

Observation of e(+)e(-) annihilation into the C = +1 hadronic final states rho(0)rho(0) and phirho(0)

We report the first observation of e(+)e(-) annihilation into states of positive C parity, namely, rho(0)rho(0) and phirho(0). The two states are observed in the pi(+)pi(-)pi(+)pi(-) and K(+)K(-)pi(+)pi(-) final states, respectively, in a data sample of 225 fb(-1) collected by the BABAR experiment at the Positron-Electron Project II e(+)e(-) storage rings at energies near sqrt[s]=10.58 GeV. The distributions of costheta(*), where theta(*) is the center-of-mass polar angle of the phi meson or the forward rho(0) meson, suggest production by two-virtual-photon annihilation. We measure cross sections within the range |costheta(*)|<0.8 of sigma(e(+)e(-)-->rho(0)rho(0))=20.7+/-0.7(stat)+/-2.7(syst) fb and sigma(e(+)e(-)-->phirho(0))=5.7+/-0.5(stat)+/-0.8(syst) fb.