The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Static and dynamic bimolecular fluorescence quenching of porphyrin dendrimers in solution

The fluorescence quenching kinetics of two porphyrin dendrimer series (GnTPPH(2) and GnPZn) by different type of quenchers is reported. The microenvironment surrounding the core in GnPZn was probing by core-quencher interactions using benzimidazole. The dependence of quencher binding constant (K(a) ) on generation indicates the presence of a weak interaction between branches and the core of the porphyrin dendrimer. The similar free volume in dendrimers of third and fourth generation suggests that structural collapse in high generations occurs by packing of the dendrimer peripheral layer. Dynamic fluorescence quenching of the porphyrin core by 1,3-dicyanomethylene-2-methyl-2-pentyl-indan (PDCMI) in GnTPPH(2) is a distance dependent electron transfer process with an exponential attenuation factor beta=0.33 angstrom(-1). The quenching by 1,2-dibromobenzene occurs by diffusion process of the quencher toward to the porphyrin core, and its rate constant is practically independent of dendrimer generation.

Biocompatible in-tube solid phase microextraction coupled with liquid chromatography-fluorescence detection for determination of interferon alpha in plasma samples

The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN alpha(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN alpha(2a) analyses in plasma sample were carried out within 25 min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0 MIU mL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN alpha(2a) in plasma samples for therapeutic drug monitoring. (C) 2010 Elsevier B.V. All rights reserved.

Characterization by Fluorescence of Organic Matter from Oxisols under Sewage Sludge Applications

Sewage sludge from wastewater treatment contains organic matter and plant nutrients that can play an important role in agricultural production and the maintenance of soil fertility, The present study has aimed to evaluate the degree of humification following sewage sludge application of soil organic matter by laser-induced fluorescence and humic acids using ultraviolet-visible fluorescence, and including comparison with Fourier-transform infrared spectroscopy and elemental analysis. Sewage sludge applications to the soil caused a decrease in the degree of humification of the soil organic matter and humic acids for both a Typic Eutrorthox (clayey) soil and a Typic Haplorthox (sandy) soil of around 14 and 27%, respectively. This effect is probably clue to incorporation of newly formed humic substances from the sewage sludge into the characteristics of less humified material, and to the indigenous soil humic substances. The minor alterations observed in the clay soil probably occurred due to both the greater mineral association, which better stabilized the indigenous soil organic matter, and the higher microbial activity in this soil, which accelerated sewage sludge mineralization. Sewage sludge applications increased the C content for the clay and sandy soils by 7.4 and 15.4 g kg(-1), respectively, suggesting a positive effect on these two soils.

Determination of urea using high-performance liquid chromatography with fluorescence detection after automated derivatisation with Xanthydrol

A high-performance liquid chromatography (HPLC) method for the determination of urea that incorporates automated derivatisation with xanthydrol (9H-xanthen-9-ol) is described. Unlike the classic xanthydrol approach for the determination of urea, which involves the precipitation of dixanthylurea (N,N′-di-9H-xanthen-9-ylurea), the derivatisation procedure employed in this method produces N-9H-xanthen-9-ylurea, which remains in solution and can be quantified using fluorescence detection (λ_ex = 213 nm; λ_em = 308 nm) after chromatographic separation from interferences. The limit of detection for urea was 5 × 10⁻⁸ M (0.003 mg L⁻¹). This method was applied to the determination of urea in human and animal urine and in wine.

Time-resolved fluorescence microscopy of gunshot residue: an application to forensic science

Time-resolved fluorescence microscopy has rapidly emerged as the technique of choice for many researchers aiming to gain specific insights into the dynamics of intricate biological systems. Although the unique advantages the technique provides over other methods have proven to be particularly useful in the biosciences, to date they have been largely unexploited by other research disciplines. In this paper, we demonstrate the capacity of time-resolved fluorescence microscopy as a practical analytical tool in the forensic sciences via the imaging of gunshot residues that are expelled when a firearm is discharged. This information may prove to be useful for determination of the true sequence of events that took place in a firearm related crime.

Fluorescence and conductivity studies on wool

An optimized synthetic method for the production of fluorescent conductive wool using pyrene, rhodamine B and fluorescein is reported. The application of fluorescent conductive polymers to wool was studied using solution and mist polymerization techniques. The effects of incorporating fluorescent dopants into the polymerization solution as well as the encapsulation of fluorescent dyes in a polypyrrole (PPy) micelle were also investigated. It was determined on the basis of both conductivity and fluorescence measurements that the encapsulation of dyes in PPy onto the surface of textiles gave the best results.

Ultraviolet vision, fluorescence and mate choice in a parrot, the budgerigar Melopsittacus undulatus

As in many parrots, the plumage of the budgerigar Melopsittacus undulatus reflects near-ultraviolet (UVA) wavelengths (300-400 nm) and exhibits UVA-induced fluorescence. However, there have, to our knowledge, been no tests of whether the yellow fluorescence observed under intense UVA illumination has any role in signalling. Four experiments were carried out on wild-type budgerigars, where the presence and absence of UV reflectance and fluorescence were manipulated using filters. Few studies have attempted to separate the contribution of UV reflectance to plumage hue as opposed to brightness or distinguish between a role in sexual as opposed to social preferences. However, our first experiments show that not only do females consistently prefer UV-reflecting males, but also that the observed preferences are due to removal of UV affecting the perceived hue rather than brightness. Furthermore, we found no effect Of the light environment on male response to females, suggesting that the female preferences relate to plumage colour per se. Whilst UV reflectance appears important in heterosexual choice by, females, it has no detectable influence on same-sex association preferences. The results from the second series of experiments suggest that enhancement of the budgerigar's yellow coloration through fluorescence has no effect on male attractiveness. However, the fluorescent plumage may play a role in signalling by virtue of the fact that it absorbs UVA and so increases contrast with nearby UV-reflecting plumage. Our study provides convincing evidence that UV reflectances can play a role in mate choice in non-passerines, but no evidence that the yellow fluorescence observed under UVA illumination is itself important as a signal.

The role of ultraviolet-A reflectance and ultraviolet-A-induced fluorescence in budgerigar mate choice

Many parrots have plumage that either reflects strongly in the ultraviolet-A (UVA) waveband, between 315-400 nm, or exhibits UVA-induced fluorescence. Previous experimental work on budgerigars (Melopsittacus undulatus) suggests that UVA reflectance plays a role in mate choice, as in other diurnal birds, but evidence for fluorescent cues playing a role is unconvincing. Here we report two experiments on budgerigars, designed to determine whether fluorescent cues play a role in signalling when UVA reflectances are absent, an approach which separates removal of UVA reflectance from removal of fluorescence. First, we determined whether the choices of different females are correlated under these treatment conditions. Secondly, we investigated female preferences for fluorescing and non-fluorescing males when UVA reflections are absent, to determine whether the yellow emissions of fluorescence are playing a role in mate choice. Results from experiment 1 do not suggest that females agree on which males are attractive when UVA reflectances are absent, with only half of the subjects choosing the same male. Neither did different females make the same choices in experiment 2. This lack of agreement provides further evidence that UVA reflectances from males play an important role in female choice in this species. Experiment 2 provides no evidence to suggest that UVA-induced fluorescence plays a role in mate choice. Overall, our study supports previous findings showing that UVA reflectance plays a role in sexual signalling in this species, but provides no evidence to suggest the same for fluorescence when UVA reflectances are absent.

The role of ultraviolet-A reflectance and ultraviolet-A induced fluorescence in the appearance of budgerigar plumage: insights from spectrofluorometry and reflectance spectrophotometry

Fluorescence has so far been found in 52 parrot species when illuminated with ultraviolet-A (UVA) 'black' lamps, and two attempts have been made to determine whether such fluorescence plays any role in sexual signalling. However, the contribution of the reflectance versus fluorescence to the total radiance from feathers, even in the most studied species to date (budgerigars), is unclear. Nor has the plumage of this study species been systematically assessed to determine the distribution of fluorescent patches. We therefore used spectrofluorometry to determine which areas of budgerigars fluoresce and the excitation and emission spectra involved; this is the first time that such a technique has been applied to avian plumage. We found that both the yellow crown and (normally hidden) white downy chest feathers exhibit strong UVA-induced fluorescence, with peak emissions at 527 nm and 436 nm, respectively. Conversely, the bright-green chest and dark-blue tail feathers do not fluoresce. When comparing reflectance spectra (400700 nm) from the yellow crown using illuminants with a proportion of UVA comparable to daylight, and illuminants with all UVA removed, no measurable difference resulting from fluorescence was found. This suggests that under normal daylight the contribution of fluorescence to radiance is probably trivial. Furthermore, these spectra revealed that males had fluorescent crowns with substantially higher reflectance than those of females, in both the UV waveband and at longer wavelengths. Reflectance spectrophotometry was also performed on a number of live wild-type male budgerigars to investigate the chromatic contrast between the different plumage areas. This showed that many plumage regions are highly UV-reflective. Overall our results suggest that rapid surveys using UVA black lamps may overestimate the contribution of fluorescence to plumage coloration, and that any signalling role of fluorescence emissions, at least from the yellow crown of budgerigars, may not be as important as previously thought.

Structural characterization of conducting polypyrrole using 13C cross-polarization/magic-angle spinning solid-state nuclear magnetic resonance spectroscopy

¹³C nuclear magnetic resonance (n.m.r.) has been used to study polypyrrole and N-substituted polypyrrole in the solid state. The extent of oxidation appears to be counterion-dependent; in particular, the quinoid structure appears favoured in the films prepared with dodecyl sulfate. Resonances associated with the quinoid unit are lost upon reduction of the polypyrrole film, which supports the idea that the quinoid structure is associated with the oxidized form of polypyrrole. N-substituted polypyrroles have a more distinct resonance at 110 ppm, which is linked to lower degrees of oxidation or charge delocalization in these systems. The decrease in conductivity of polypyrrole upon thermal ageing in air is associated with both the loss of counterion (‘thermal dedoping’) and the decomposition of the quinoid structure in the polymer backbone. There is no indication of carbonyl formation in the solid-state n.m.r. spectra obtained in the present study.

On the components of the dielectric constants of ionic liquids : ionic polarization?

According to dielectric spectroscopy measurements, ionic liquids (ILs) have rather modest dielectric constants that reflect contributions from distortion and electronic polarization caused by the molecular polarizability as well as the orientation polarization caused by the permanent dipole moment of the ions. To understand the relative importance of these various contributions, the electronic polarizabilities of 27 routinely used ionic liquid ions of different symmetry and size were calculated using ab initio-based methods such as HF and MP2. Using the Clausius–Mossotti equation, these polarizabilities were then used to obtain the electronic polarization contribution (ε_op) to the dielectric constants of six ionic liquids, [C₂mim][BF₄], [C₂mpyr][N(CN)₂], [C₂mim][CF₃SO₃], [EtNH₃][NO₃], [C₂mim][NTf₂] and [C₂mim][EtSO₄]. Theoretical ε_op values were compared to experimental refractive indices of these ionic liquids as well as to those of traditional molecular solvents such as water, tetrahydrofuran (THF), dimethylsulfoxide (DMSO) and formamide. The dipole moments of the ions were also calculated, and from these it is shown that the molecular reorientation component of the dielectric constants of the ionic liquids consisting of ions with small or negligible dipole moments is quite small. Thus it is concluded that a contribution from a form of “ionic polarization” must be present.

The in situ physiology of "Nostocoida limicola" II, a filamentous bacterial morphotype in bulking activated sludge, using fluorescence in situ hybridization and microautoradiography

The in situ physiology of the actinobacterial bulking and foaming filamentous bacterium "Nostocoida limicola" II was studied by fluorescence in situ hybridization/microautoradiography. Substrate assimilation patterns of pure cultures of this bacterium were different to those seen in activated sludge biomass samples. There was no evidence to suggest that "N. limicola" II preferred hydrophobic substrates, but evidence was produced to support the view that it is metabolically active under anaerobic conditions in activated sludge.