On the nonexistence of certain Hughes generalized quadrangles

In this paper, we prove that the Hermitian quadrangle is the unique generalized quadrangle Γ of order (q ², q ³) containing some subquadrangle of order (q ², q) isomorphic to such that every central elation of the subquadrangle is induced by a collineation of Γ. Dedicated to Dan Hughes on the occasion of his 80th birthday.     

Ultraviolet Absorption Induces Hydrogen‐Atom Transfer in G⋅C Watson–Crick DNA Base Pairs in Solution

Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron‐driven proton transfer (EDPT) in Watson–Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine–cytosine (G?C) Watson–Crick base pairs by ultrafast time‐resolved UV/visible and mid‐infrared spectroscopy. The formation of an intermediate biradical species (G[?H]?C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G?C Watson–Crick pairs, but up to 10 % of the initially excited molecules instead form a stable photoproduct G*?C* that has undergone double hydrogen‐atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA.     

A new construction of the Clifford-Fourier kernel

In this paper, we develop a new method based on the Laplace transform to study the Clifford-Fourier transform. First, the kernel of the Clifford-Fourier transform in the Laplace domain is obtained. When the dimension is even, the inverse Laplace transform may be computed and we obtain the explicit expression for the kernel as a finite sum of Bessel functions. We equally obtain the plane wave decomposition and find new integral representations for the kernel in all dimensions. Finally we define and compute the formal generating function for the even dimensional kernels.     

Convergence of the Two‐Dimensional Dynamic Ising‐Kac Model to

The Ising‐Kac model is a variant of the ferromagnetic Ising model in which each spin variable interacts with all spins in a neighborhood of radius γ ^{? 1} for around its base point. We study the Glauber dynamics for this model on a discrete two‐dimensional torus for a system size and for an inverse temperature close to the critical value of the mean field model. We show that the suitably rescaled coarse‐grained spin field converges in distribution to the solution of a nonlinear stochastic partial differential equation. This equation is the dynamic version of the quantum field theory, which is formally given by a reaction‐diffusion equation driven by an additive space‐time white noise. It is well‐known that in two spatial dimensions such equations are distribution valued and a Wick renormalization has to be performed in order to define the nonlinear term. Formally, this renormalization corresponds to adding an infinite mass term to the equation. We show that this need for renormalization for the limiting equation is reflected in the discrete system by a shift of the critical temperature away from its mean field value.© 2016 by the authors. Communications on Pure and Applied Mathematics is published by Wiley Periodicals, Inc., on behalf of the Courant Institute of Mathematics.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

A step toward the wet surface chemistry of glycine and alanine on Cu{110}: destabilization and decomposition in the presence of near-ambient water vapor

The coadsorption of water with organic molecules under near-ambient pressure and temperature conditions opens up new reaction pathways on model catalyst surfaces that are not accessible in conventional ultrahigh-vacuum surface-science experiments. The surface chemistry of glycine and alanine at the water-exposed Cu{110} interface was studied in situ using ambient-pressure photoemission and X-ray absorption spectroscopy techniques. At water pressures above 10(-5) Torr a significant pressure-dependent decrease in the temperature for dissociative desorption was observed for both amino acids, accompanied by the appearance of a new CN intermediate, which is not observed for lower pressures. The most likely reaction mechanisms involve dehydrogenation induced by O and/or OH surface species resulting from the dissociative adsorption of water. The linear relationship between the inverse decomposition temperature and the logarithm of water pressure enables determination of the activation energy for the surface reaction, between 213 and 232 kJ/mol, and a prediction of the decomposition temperature at the solid-liquid interface by extrapolating toward the equilibrium vapor pressure. Such experiments near the equilibrium vapor pressure provide important information about elementary surface processes at the solid-liquid interface, which can be retrieved neither under ultrahigh vacuum conditions nor from interfaces immersed in a solution.     

A Novel APPI-MS Setup for In Situ Degradation Product Studies of Atmospherically Relevant Compounds: Capillary Atmospheric Pressure Photo Ionization (cAPPI)

We report on the development of a novel atmospheric pressure photoionization setup and its applicability for in situ degradation product studies of atmospherically relevant compounds. A custom miniature spark discharge lamp was embedded into an ion transfer capillary, which separates the atmospheric pressure from the low pressure region in the first differential pumping stage of a conventional atmospheric pressure ionization mass spectrometer. The lamp operates with a continuous argon flow and produces intense light emissions in the VUV. The custom lamp is operated windowless and efficiently illuminates the sample flow through the transfer capillary on an area smaller than 1 mm². Limits of detection in the lower ppbV range, a temporal resolution of milliseconds in the positive as well as the quasi simultaneously operating negative ion mode, and a significant reduction of ion transformation processes render this system applicable to real time studies of rapidly changing chemical systems. The method termed capillary atmospheric pressure photo ionization (cAPPI) is characterized with respect to the lamp emission properties as a function of the operating conditions, temporal response, and its applicability for in situ degradation product studies of atmospherically relevant compounds, respectively.     

A case of cross-reactivity

Studies using chemical inhibitors have suggested that p38 MAP kinase is a key regulator of Wnt/β-catenin signaling. In this issue, Verkaar et?al. (2011) show that cross-reactivity of p38 inhibitors with casein kinase Iδ/? is responsible for Wnt/β-catenin pathway inhibition.