Differential Behavior of Amino–Imino Constitutional Isomers in Nonlinear Optical Processes

A detailed study of the “blocked” amino–imino tautomers derived from N‐acridine‐substituted 2‐aminobenzothiazole—and their effect on the nonlinear optical response—is presented. The synthesis, characterization, and nonlinear optical properties of these frozen tautomers, namely, N‐methyl‐N‐(2‐nitroacridin‐6‐yl)‐2‐aminobenzothia‐zole and 3‐methyl‐N‐(7‐nitroacridin‐3‐yl)‐2‐iminobenzothiazole, are reported. A theoretical model based on valence–bond theory is also proposed and used to analyze the effects of the nuclear configuration corresponding to each frozen tautomer structure. In the present case, the aromatic form and the allylic‐anion‐like system of the ? N? C? N? group inherent to each isomer are crucial for understanding and analyzing the different responses of each “blocked” tautomer.     

Re-evaluation of glyphosate determination in water by liquid chromatography coupled to electrospray tandem mass spectrometry

An analytical method based on on-line solid-phase extraction-liquid chromatography coupled to electrospray tandem mass spectrometry (SPE-LC-ESI-MS/MS) for the determination of glyphosate and aminomethylphosphonic acid (AMPA) residues has been applied to the analysis of water samples within a Round Robin Study. The method had been previously validated in a variety of water samples and it fulfilled all the parameters of precision, accuracy, sensitivity and unequivocal confirmation. The results within the study that we participated were highly satisfactory in all cases with the only exception of glyphosate in groundwater samples, where surprisingly recoveries around 15% were obtained despite the use of isotope-labeled glyphosate as internal standard (I.S.). A slight modification has been introduced in the method, simply consisting of the acidification of sample with hydrochloric acid (HCl) to pH 1. Then, the sample is neutralized and immediately derivatized with 9-fluorenylmethylchloroformate (FMOC) before LC-MS/MS determination. Round Robin Study samples were reanalyzed using this approach, and the recoveries increased up to 98%. A possible explanation might be the slow kinetic interaction between glyphosate and some components of the matrix. These components might act as chelating agents, making glyphosate unavailable for derivatization and therefore for analysis. Several water samples collected at the Mediterranean area of Spain, and previously analyzed and being found to contain glyphosate, were also reanalyzed using this approach, obtaining higher concentrations (between 2 and 14 times) in most of cases.     

Assembled monolayers of Mo3S4(4+) clusters on well-defined surfaces

A class of inorganic monolayers formed by assembling the molybdenum-sulfur cluster, Mo3S4(4+), onto a well-defined Au(111) surface is presented. The monolayers have been comprehensively characterized by electrochemistry, X-ray photoelectron spectroscopy (XPS), and in situ scanning tunneling microscopy (in situ STM). The voltammetric data show strong reductive and oxidative desorption signals from Au-S interactions, supported by the presence of both S and Mo signals in XPS. In situ STM shows many small pits in the dense adlayers uniformly spread over the surface, which is a typical feature of self-assembled monolayers (SAMs) of alkanethiols. The density of the pits is ca. 23 (+/-5)% and is significantly higher than for straight-chain alkanethiol SAMs with a single -SH group. The pit shapes are irregular, suggesting multiple Au-S interactions from Mo3S4(4+). High resolution images disclose bright round spots of ca. 8 A diameter representing individual molecules in the SAM. This is the first example of in situ monolayer formation by a metal-chalcogenide cluster directly anchored onto the gold surface through core ligands and offers a simple way to prepare a new class of functionalized inorganic monolayers.     

Poly(N,N‐dimethylacrylamide‐co‐4‐(ethyl)‐morpholine methacrylamide) copolymer as coating for CE

In this work, a new physically adsorbed coating for CE is presented. This coating is based on a poly(N,N‐dimethylacrylamide‐co‐4‐(ethyl)‐morpholine methacrylamide) (DMA/MAEM) copolymer synthesized in our laboratory. It is demonstrated that the direction and magnitude of the EOF in CE can be modulated by varying the composition of the DMA/MAEM copolymer and the type and pH of the BGE. Moreover, the DMA/MAEM coating provides %RSD_n = 5 values for migration times lower than 0.9% for the same capillary and day, whereas the %RSD_n = 25 obtained for the interday assay was lower than 2.9%. The stability of the coating procedure is also tested between capillaries obtaining %RSD_n = 15 values lower than 2.9%, demonstrating that this physically adsorbed copolymer gives rise to a stable and reproducible coating in CE. Finally, the usefulness of this new cationic copolymer as CE coating is demonstrated through different applications. Namely, it is demonstrated that the CE separation of basic proteins, nucleotides and organic acids is achieved in a fast and easy way by using the DMA/MAEM coated capillary. The use of fused bare silica capillaries did not allow the separation of these compounds under the same analytical conditions. These results demonstrate that this type of coating in CE provides the option of using BGEs that are useless when utilized together with bare silica capillaries making wider the application and possibilities of this analytical technique.     

The homotopy type of the cobordism category

The embedded cobordism category under study in this paper generalizes the category of conformal surfaces, introduced by G. Segal in [S2] in order to formalize the concept of field theories. Our main result identifies the homotopy type of the classifying space of the embedded d-dimensional cobordism category for all d. For d = 2, our results lead to a new proof of the generalized Mumford conjecture, somewhat different in spirit from the original one, presented in [MW].     

Electron emission from MOS electron emitters with clean and cesium covered gold surface

MOS (metal-oxide-semiconductor) electron emitters consisting of a Si substrate, a SiO₂ tunnel barrier and a Ti (1 nm)/Au(7 nm) top-electrode, with an active area of 1 cm² have been produced and studied with surface science techniques under UHV (ultra high vacuum) conditions and their emission characteristics have been investigated. It is known, that deposition of an alkali metal on the emitting surface lowers the work function and increases the emission efficiency. For increasing Cs coverages the surface has been characterized by X-ray Photoelectron Spectroscopy (XPS), Ion Scattering Spectroscopy (ISS) and work function measurements. Energy spectra of electron emission from the devices under an applied bias voltage have been recorded for the clean Au surface and for two Cs coverages and simultaneous work function curves have been obtained. The electron emission onset is seen to appear at the surface work function. A method for cleaning the ex situ deposited Au top electrodes to a degree satisfactory to surface science studies has been developed, and a threshold for oxide damage by low-energy ion exposure between 0.5 and 1 keV has been determined.     

Contextual blending of ingroup/outgroup face stimuli and word valence: LPP modulation and convergence of measures

Background  

Several event related potential (ERP) studies have investigated the time course of different aspects of evaluative processing in social bias research. Various reports suggest that the late positive potential (LPP) is modulated by basic evaluative processes, and some reports suggest that in-/outgroup relative position affects ERP responses. In order to study possible LPP blending between facial race processing and semantic valence (positive or negative words), we recorded ERPs while indigenous and non-indigenous participants who were matched by age and gender performed an implicit association test (IAT). The task involved categorizing faces (ingroup and outgroup) and words (positive and negative). Since our paradigm implies an evaluative task with positive and negative valence association, a frontal distribution of LPPs similar to that found in previous reports was expected. At the same time, we predicted that LPP valence lateralization would be modulated not only by positive/negative associations but also by particular combinations of valence, face stimuli and participant relative position.     

Structure Sensitivity in the Electrocatalytic Reduction of CO2 with Gold Catalysts

An understanding of the influence of structural surface features on electrocatalytic reactions is vital for the development of efficient nanostructured catalysts. Gold is the most active and selective known electrocatalyst for the reduction of CO₂ to CO in aqueous electrolytes. Numerous strategies have been proposed to improve its intrinsic activity. Nonetheless, the atomistic knowledge of the nature of the active sites remains elusive. We systematically investigated the structure sensitivity of Au single crystals for electrocatalytic CO₂ reduction. Reaction kinetics for the formation of CO are strongly dependent on the surface structure. Under‐coordinated sites, such as those present in Au(110) and at the steps of Au(211), show at least 20‐fold higher activity than more coordinated configurations (for example, Au(100)). By selectively poisoning under‐coordinated sites with Pb, we have confirmed that these are the active sites for CO₂ reduction.     

The effect of Higgses and “technions” on the calculation of sin2θw and Mx

The effect of the scalar sector on the calculation of sin²θ_w and M_x in grand unified theories is studied. We consider first elementary Higgs scalars and assume the “big desert” hypothesis. It is argued that Higgses other than the usual doublet can also be light (～ M_w). One can obtain bigger values for sin²θ_w by having light (～ M_w) scalar colour sextets which can give rise to interesting phenomenology. As an example, one can build an SU(5) model giving sin²θ_w ? 0.23 at the one-loop level. We also calculate the uncertainty in sin²θ_w and M_x due to the lack of knowledge of the specific masses of superheavy Higgses. We find that this uncertainty is small for reasonable SU(5) models but large in all the SO(10) versions except the minimal. Finally (and alternatively) we consider the effect of a technicolour interaction. The pseudo-Goldstone bosons (technions) increase the calculated sin²θ_w by as much as ～0.01 but M_x remains nearly unchanged. Second-order contributions due to the technifermions tend to cancel the increase on sin²θ_w and in turn increase M_x.     

Fermion masses in grand unified theories: Effective Yukawa terms

It is argued that effective non-renormalizable terms of the type recently proposed by Ellis and Gaillard can give rise to large contributions to the fermion masses. The combined effect of this kind of term and the usual Yukawa couplings could explain the observed hierarchy of fermion masses. Two toy-models based on the gauge groups SU (5)×SU(2) _H and SO(10)×SU(2) _H (where SU(2) _H is a gauged “horizontal” symmetry) are shown in which one can obtain some interesting mass relations previously obtained under very different assumptions.