Multiparameter kinetic analysis of alkaline hydrolysis of a series of aryl diphenylphosphinothioates: models for P=S neurotoxins

Alkaline hydrolysis of a series of X‐substituted‐phenyl diphenylphosphinothioates ( 2a‐i ) in 80 mol%/20 mol% DMSO at 25.0 ± 0.1°C has been studied kinetically and assessed through a multiparameter approach. Substrates 2a to 2i are approximately 12 to 22 times less reactive than their P=O analogues 1a to 1i (ie, the thio effect). The Brønsted‐type plot for the reactions of 2a to 2i is linear with β_lg = ?0.43, consistent with a concerted mechanism. Hammett plots correlated with σ^o and σ^? constants also support a concerted mechanism; the Yukawa‐Tsuno plot results in an excellent linear correlation with ρ_X = 1.26 and r = 0.30, indicating that expulsion of the leaving group occurs in the rate‐determining step (RDS). The ΔH^? value increases from 10.5 to 11.7 and 13.9 kcal/mol as substituent X in the leaving group changes from 3,4‐(NO₂)₂ to 4‐NO₂ and H, in turn, while TΔS^? remains constant at ?6.0 kcal/mol. The strong dependence of ΔH^? on the electronic nature of substituent X also indicates that the leaving group departs in the RDS. The reaction mechanism and origin of the thio effect are discussed by comparison of the current kinetic results with those reported for the reactions of 1a to 1i . The results suggest that for useful OP neurotoxins the mechanism of abiotic hydrolysis is concerted (with varying degrees of asynchronicity) when the substrate bears good leaving groups.     

Colorizing mechanism of brass surface by femtosecond laser induced microstructures

In this paper, we exhibit the colorizing of brass surfaces by forming femtosecond laser induced microstructures on the sample surfaces. A variety of single colors such as brown, yellow, green, and black are introduced on brass surfaces by engineering periodic microgratings, microholes, and ring-shaped micro-patterns using Single Beam Direct Laser Writing (SBDLW) technique. The color of the micro-structured brass surfaces is certainly dependent on the width, depth, and period of the microstructures. Finally, we explain, in brief, the colorizing mechanism of metals by femtosecond laser induced microstructures.     

Soft X‐ray absorption spectroscopy and resonant inelastic X‐ray scattering spectroscopy below 100 eV: probing first‐row transition‐metal M‐edges in chemical complexes

X‐ray absorption and scattering spectroscopies involving the 3d transition‐metal K‐ and L‐edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M‐edges, which are below 100 eV. Synchrotron‐based X‐ray sources can have higher energy resolution at M‐edges. M‐edge X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) could therefore provide complementary information to K‐ and L‐edge spectroscopies. In this study, M_2,3‐edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M_2,3‐edge RIXS on NiO, NiF₂ and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M‐edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high‐sensitivity and high‐resolution superconducting tunnel junction X‐ray detectors below 100 eV is also illustrated and discussed.     

Engineering silicon-based photonic crystal cavities for NV-center quantum information processing

Silicon slab photonic crystal micro cavities designed for of-resonant coupling to nitrogen vacancy (NV) centers were simulated and fabricated. FDTD-simulations show the partial density of states spectrally near the NV-center electric dipole transition can be tuned to reduce decoherence of an excited NV-center despite this transition being above the silicon electronic band gap. The partial density of states at the NV-center transition can be made to dip below half of the free-space partial density of states without significantly affecting the cavity mode quality factor. These promising results sustain the merits of using silicon as a base photonic crystal material for quantum information processing even when integrated emitters radiate above the electronic band gap of silicon.     

Two-proton correlations in the target fragmentation region of nuclear collisions at 200A GeV

Correlations between protons are studied in the target fragmentation region of reactions of protons and¹⁶O with C, Cu, Ag, Au and of³²S with Al and Au at 200A GeV. The emitted protons were measured with the Plastic Ball detector in the WA80 experiment at the CERN SPS. The comparison of the correlation function with calculations, assuming a spherical, gaussian shaped source with a lifetime τ=0 fm/c, allows the extraction of radius parameters. The values are very close to those expected from the geometry of the target nuclei and increase with the target mass as αA _Target ^1/3 . Even in proton induced reactions the whole target nucleus is involved. The dependence of the radii on centrality, polar angleθ _lab, and energy, and their relation to measured proton yields are presented.     

Modified gap states in Fe/MgO/SrTiO3 interfaces studied with scanning tunneling microscopy

The geometric and electronic structures of Fe islands on MgO film layers were studied with scanning tunneling microscopy and spectroscopy. The MgO layers were grown on a Nb-doped single crystal SrTiO₃ (100) surface. Deposited Fe atoms aggregate into islands, the height and diameter of which are about 2.5 and 9.4 nm respectively. Fe islands modify the electronic structure of MgO surface; a ring type depression in the scanning tunneling microscope topography appears by lowered local electron density of states around Fe islands. We find that adsorbed Fe atoms reduce the gap states of MgO layers around Fe islands, which is attributed to the reason for the depletion of the electronic density of states.     

Relative density-based classification noise detection

Classification noise is a common byproduct of traditional data mining approaches, and no specialized approach for detecting classification noise is currently available. Methods for outlier detection are well-developed, but outliers and classification noise have characteristics different enough to make outlier detection algorithms unsuitable for classification noise detection. In this paper, a new, specialized approach to detect classification noise is proposed, named relative density based classification noise detection (RDBCND). Computational experiments in artificial data sets described herein show that RDBCND has time complexity of O(n log n), indicating greater efficiency than traditional approaches, which exhibit time complexity of at least O(n²). The use of classification noise detection to improve the generalization ability of common classifier algorithms is also described. In particular, a new unified approach based on RDBCND is compared to a cross validation approach applied to a BP neural network. Trials in both artificial and real-life datasets show that the RDBCND-based approach can greatly accelerate the process of identifying the best decision function. The novel method can also eliminate underfitting, as the algorithm simply searches for the highest training accuracy. The experiments also show that the RDBCND-based method has greater accuracy and lower cpu time in reaching global solutions than the cross-validation method. Since the relative density is a local concept, our new approach can be directly used in nonlinear datasets without data transformation. It is a great advantage compared to some linear classifier algorithms. As in current linear classifiers, the kernel functions or other transformations need to be used to make them suitable for non-linear datasets, and that will increase their complexity.     

Effect of instrumental particle sizing resolution on the modelling of aerosol radiative parameters

A more realistic estimation of the scattering and hemispheric backscattering coefficients, σ_sp and σ_bsp, and their respective optical cross section, C_sca and C_bk, of aerosol particles is presented on the basis of the exact resolution of the width of the size bins of the particle counter instruments when size distribution measurements are used, and, with the exact optical detector instruments ability. The scattering and hemispheric backscattering cross sections, C_sca and C_bk, of the particles are averaged over the full size bins of the particle counter instrument, while these quantities are usually estimated only on the value of the mean geometric diameter of each size bin. Six instruments, the APS, ASASP-X, DMPS, FSSP-100, ELPI, and SMPS frequently used in particle size distribution measurements are reviewed, for spherical sea-salt particles at a wavelength λ=0.55 μm. The comparison using the conventional geometric mean diameter versus the use of the full size bin leads to large amount of errors for the optical cross section with non-negligible effects on their respective optical coefficients. The maximal accuracy expected for these optical quantities depend on the particle diameter as well as on the channel width of the instruments, and are also function of the angular detector probe used to measure them.