Imaging the photodissociation of CH3SH in the first and second absorption bands: the CH3(X2A1)+SH(X2Pi) channel

The CH3(X2A1)+SH(X2Pi) channel of the photodissociation of CH3SH has been investigated at several wavelengths in the first 1 1A"<--X 1A' and second 2 1A"<--X1A' absorption bands by means of velocity map imaging of the CH3 fragment. A fast highly anisotropic (beta=-1+/-0.1) CH3(X2A1) signal has been observed in the images at all the photolysis wavelengths studied, which is consistent with a direct dissociation process from an electronically excited state by cleavage of the C-S bond in the parent molecule. From the analysis of the CH3 images, vibrational populations of the SH(X2Pi) counterfragment have been extracted. In the second absorption band, the SH fragment is formed with an inverted vibrational distribution as a consequence of the forces acting in the crossing from the bound 2 1A" second excited state to the unbound 1 1A" first excited state. The internal energy of the SH radical increases as the photolysis wavelength decreases. In the case of photodissociation via the first excited state, the direct production of CH3 leaves the SH counterfragment with little internal excitation. Moreover, at the longer photolysis wavelengths corresponding to excitation to the 1 1A" state, a slower anisotropic CH3 channel has been observed (beta=-0.8+/-0.1) consistent with a two step photodissociation process, where the first step corresponds to the production of CH3S(X2E) radicals via cleavage of the S-H bond in CH3SH, followed by photodissociation of the nascent CH3S radicals yielding CH3(X2A1)+S(X3P0,1,2).     

Epitaxy and magnetic properties of surfactant-mediated growth of bcc cobalt

High resolution core level photoemission spectroscopy, photoelectron diffraction, and x-ray magnetic circular dicroism (XMCD) have been used to characterize the structural and magnetic properties of bcc-cobalt films grown on GaAs(110) substrates by using Sb as a surfactant. We have unambiguously disentangled the surfactant role played by the Sb which improves the crystallinity and reduces the lattice distortion of the metallic films as well as changes the interdiffusion process at the interface compared to the Co/GaAs(110) system. As a consequence of these combined effects, an improvement on the magnetic response of the grown Co thin films has been observed by XMCD measurements.     

Bacterial base excision repair enzyme Fpg recognizes bulky N7-substituted-FapydG lesion via unproductive binding mode

Fpg is a bacterial base excision repair enzyme that removes oxidized purines from DNA. This work shows that Fpg and its eukaryote homolog Ogg1 recognize with high affinity FapydG and bulky N7-benzyl-FapydG (Bz-FapydG). The comparative crystal structure analysis of stable complexes between Fpg and carbocyclic cFapydG or Bz-cFapydG nucleoside-containing DNA provides the molecular basis of the ability of Fpg to bind both lesions with the same affinity and to differently process them. To accommodate the steric hindrance of the benzyl group, Fpg selects the adequate rotamer of the extrahelical Bz-cFapydG formamido group, forcing the bulky group to go outside the binding pocket. Contrary to the binding mode of cFapydG, the particular recognition of Bz-cFapydG leads the BER enzymes to unproductive complexes which would hide the lesion and slow down its repair by the NER machinery.     

A characterization of convex TU games by means of the Mas-Colell bargaining set (à la Shimomura)

Within the class of zero-monotonic games, we prove that a cooperative game with transferable utility is convex if and only if the core of the game coincides with the Mas-Colell bargaining set (à la Shimomura, in Int J Game Theory 26:283–302, 1997).     

Generalizations of Maxwell (super)algebras by the expansion method

The Lie algebras expansion method is used to show that the four-dimensional spacetime Maxwell (super)algebras and some of their generalizations can be derived in a simple way as particular expansions of o(3,2)$o(3,2)$ and osp(N|4)$\mathit{osp}(N|4)$.     

Porosity estimation of concrete by ultrasonic NDE

The increasing number of concrete structures with symptoms of premature deterioration due to environmental action demands procedures to estimate the durability of this type of component. Concrete durability is related to porosity, which determines the intensity of interactions of the material with aggressive agents. The pores and capillaries inside the structure facilitate the destructive processes that generally begin in the surface. In this work, an ultrasonic NDE technique to estimate the porosity of concrete is developed. The method is based on the analysis of the mechanical behaviour of mortar probes built with calibrated sand, in which the concentration of water-cement mixture has been varied. In this sense, data of sound velocity are correlated with data of porosity, which have been previously measured by destructive measurements.     

Phase behavior and nano-emulsion formation by the phase inversion temperature method

Formation of oil-in-water nano-emulsions has been studied in the water/C12E4/isohexadecane system by the phase inversion temperature emulsification method. Emulsification started at the corresponding hydrophilic-lipophilic balance temperature, and then the samples were quickly cooled to 25 degrees C. The influence of phase behavior on nano-emulsion droplet size and stability has been studied. Droplet size was determined by dynamic light scattering, and nano-emulsion stability was assessed, measuring the variation of droplet size as a function of time. The results obtained showed that the smallest droplet sizes were produced in samples where the emulsification started in a bicontinuous microemulsion (D) phase region or in a two-phase region consisting of a microemulsion (D) and a liquid crystalline phase (L(alpha)). Although the breakdown process of nano-emulsions could be attributed to the oil transference from the smaller to the bigger droplets, the increase in instability found with the increase in surfactant concentration may be related to the higher surfactant excess, favoring the oil micellar transport between the emulsion droplets.     

Low cost and compact analytical microsystem for carbon dioxide determination in production processes of wine and beer

The design, construction and evaluation of a low cost, cyclic olefin copolymer (COC)-based continuous flow microanalyzer, with optical detection, to monitor carbon dioxide in bottled wines and beers as well as in fermentation processes, is presented. The microsystem, constructed by computer numerically controlled (CNC) micromilling and using a multilayer approach, integrates microfluidics, gas-diffusion module and an optical flow-cell in a single polymeric substrate. Its size is slightly bigger than a credit card, exactly 45 × 60 × 4 mm in the microfluidic and diffusion module zone and 22.5 × 40 × 3 mm in the flow-cell zone. The gas-diffusion module is based on a hydrophobic polyvinylidene fluoride (PVDF) membrane, which allows the transfer of the carbon dioxide present in the sample to a bromothymol blue (BTB) pH-sensitive acceptor solution, where the color change is measured optically. The detection system consisted of a LED with an emission peak at 607 nm and a photodiode integrated in a printed circuit board (PCB). The obtained analytical features after the optimization of the microfluidic platform and hydrodynamic variables are a linear range from 255 to 10000 mg L⁻¹ of CO₂ and a detection limit of 83 mg L⁻¹ with a sampling rate of 30 samples h⁻¹.     

Scanning electrochemical microscopy studies for the characterization of localized corrosion reactions at cut edges of coil-coated steel

The local distribution of anodic and cathodic sites in a corroding cut edge using the scanning electrochemical microscope is presented. Platinum and antimony microdiscs were used as tips for combined amperometric/potentiometric operation. Local changes in electrochemical activity, oxygen concentration and pH distribution associated to the onset of localized anodes and cathodes were imaged in situ, as well as their evolution with time. Local alkalization and oxygen consumption related to cathodic activity were detected above the zinc layer covered with the thinner polymeric coating, providing a direct evidence of a differential aeration process effectively operating in an asymmetrical cut edge, in addition to the galvanic coupling of aluzinc and steel. Anodic activity leading to local acidification occurred at the other aluzinc layer at all exposures.