Laser-Accelerated proton beams as diagnostics for cultural heritage

This paper introduces the first use of laser-generated proton beams as diagnostic for materials of interest in the domain of Cultural Heritage. Using laser-accelerated protons, as generated by interaction of a high-power short-pulse laser with a solid target, we can produce proton-induced X-ray emission spectroscopies (PIXE). By correctly tuning the proton flux on the sample, we are able to perform the PIXE in a single shot without provoking more damage to the sample than conventional methodologies. We verify this by experimentally irradiating materials of interest in the Cultural Heritage with laser-accelerated protons and measuring the PIXE emission. The morphological and chemical analysis of the sample before and after irradiation are compared in order to assess the damage provoked to the artifact. Montecarlo simulations confirm that the temperature in the sample stays safely below the melting point. Compared to conventional diagnostic methodologies, laser-driven PIXE has the advantage of being potentially quicker and more efficien

Chemical Magnetoreception: Bird Cryptochrome 1a Is Excited by Blue Light and Forms Long-Lived Radical-Pairs

Cryptochromes (Cry) have been suggested to form the basis of light-dependent magnetic compass orientation in birds. However, to function as magnetic compass sensors, the cryptochromes of migratory birds must possess a number of key biophysical characteristics. Most importantly, absorption of blue light must produce radical pairs with lifetimes longer than about a microsecond. Cryptochrome 1a (gwCry1a) and the photolyase-homology-region of Cry1 (gwCry1-PHR) from the migratory garden warbler were recombinantly expressed and purified from a baculovirus/Sf9 cell expression system. Transient absorption measurements show that these flavoproteins are indeed excited by light in the blue spectral range leading to the formation of radicals with millisecond lifetimes. These biophysical characteristics suggest that gwCry1a is ideally suited as a primary light-mediated, radical-pair-based magnetic compass receptor

Determining Material Response for Polyvinyl Butyral (PVB) in Blast Loading Situations

Protecting structures from the effect of blast loads requires the careful design of all building components. In this context, the mechanical properties of Polyvinyl Butyral (PVB) are of interest to designers as the membrane behaviour will affect the performance of laminated glass glazing when loaded by explosion pressure waves. This polymer behaves in a complex manner and is difficult to model over the wide range of strain rates relevant to blast analysis. In this study, data from experimental tests conducted at strain rates from 0.01 s−1 to 400 s−1 were used to develop material models accounting for the rate dependency of the material. Firstly, two models were derived assuming Prony series formulations. A reduced polynomial spring and a spring derived from the model proposed by Hoo Fatt and Ouyang were used. Two fits were produced for each of these models, one for low rate cases, up to 8 s−1, and one for high rate cases, from 20 s−1. Afterwards, a single model representing all rates was produced using a finite deformation viscoelastic model. This assumed two hyperelastic springs in parallel, one of which was in series with a non-linear damper. The results were compared with the experimental results, assessing the quality of the fits in the strain range of interest for blast loading situations. This should provide designers with the information to choose between the available models depending on their design needs

Relationship between inpatient satisfaction and nurse absenteeism: an exploratory study using WHO-PATH performance indicators in France

<p>Abstract</p> <p>Background</p> <p>Indicators describing results of care are widely explored in term of patient satisfaction (PS). Among factors explaining PS, human resources indicators have been studied in terms of burnout or job satisfaction among healthcare professionals. No research work has set out to explore the effect of absenteeism on PS scores. The objective of this study was to explore interaction between rate of absenteeism among nurses and PS results.</p> <p>Methods</p> <p>France has taken part in a project named PATH (Performance Assessment Tool for Hospitals) of the World Health Organization, aiming to develop a tool for the assessment of hospital performance. In the first semester 2008, 25 volunteering short-stay hospitals (teaching, general and private) provide complete data on nurse short-absenteeism (periods of up to 7 consecutive days of sick leave) and on PS (a cross-sectional postal survey using a standardized validated French-language scale EQS-H exploring "quality of medical information" (MI) and "relationships with staff and daily routine" (RS)). A multi-level model was used to take into account of the hierarchical nature of the data.</p> <p>Results</p> <p>Two thousand and sixty-five patients responded to the satisfaction questionnaire (participation rate: 40.9%). The mean age of respondents was 58 yrs (± 19), 41% were men. The mean duration of hospitalisation was 7.5 days (± 11.1). The mean absenteeism rate for nurses was 0.24% (± 0.14).</p> <p>All the PS scores were significantly and negatively correlated with rate of short-absenteeism among nurses (MI score: <it>ρ </it>= -0.55, <it>p </it>< 0.01), RS score <it>ρ </it>= -0.47, <it>p </it>= 0.02). The mixed model found a significant relationship between rate of absenteeism among nurses and PS scores (MI: <it>p </it>= 0.027; RS: <it>p </it>= 0.017).</p> <p>Conclusion</p> <p>Results obtained in this study show that short-term absenteeism among nurses seems to be significantly and negatively correlated with PS. Our findings are an invitation to deepen our understanding of the impact of human resources on PS and to develop more specific projects.</p

Probing the orientation of porphyrin oligomers in a liquid crystal solvent -a triplet state electron paramagnetic resonance study

Linear porphyrin oligomers have found various applications as synthetic molecular wires in the context of light harvesting, solar energy conversion and molecular electronics. In many of these applications a partial ordering of the molecules helps to improve the reaction efficiency or device performance. In this work we study the orientational properties of the building blocks of such porphyrin-based molecular wires, namely a porphyrin monomer and the corresponding butadiyne-bridged dimer. The porphyrins have been embedded in the nematic liquid crystal solvent 4-cyano-4’-pentylbiphenyl (5CB) and the anisotropic properties of their photogenerated triplet states were characterised by transient electron paramagnetic resonance (EPR) spectroscopy. When aligned in strong magnetic fields, the liquid crystal molecules impose their orientational anisotropy onto the solute guest molecules whose orientation-dependent magnetic properties can then be explored. The line shape analysis of the porphyrin triplet state EPR spectra − highly sensitive to small conformational changes − confirms the orientation of the zero-field-splitting (ZFS) tensors previously determined for these molecules by magnetophotoselection experiments. A biaxial distribution function is shown to be necessary to simulate the experimental EPR data. The biaxial behaviour, in conjunction with symmetry considerations, allows an unambiguous assignment of the three ZFS tensor axes to the molecular axes. From the determined orientational distributions of the porphyrins in 5CB, the biaxial order parameters for both molecules were calculated

Triplet state delocalization in a conjugated porphyrin dimer probed by transient electron paramagnetic resonance techniques

The delocalization of the photoexcited triplet state in a linear butadiyne-linked porphyrin dimer is investigated by time-resolved and pulse electron paramagnetic resonance (EPR) with laser excitation. The transient EPR spectra of the photoexcited triplet states of the porphyrin monomer and dimer are characterized by significantly different spin polarizations and an increase of the zero-field splitting parameter D from monomer to dimer. The proton and nitrogen hyperfine couplings, determined using electron nuclear double resonance (ENDOR) and X- and Q-band HYSCORE, are reduced to about half in the porphyrin dimer. These data unequivocally prove the delocalization of the triplet state over both porphyrin units, in contrast to the conclusions from previous studies on the triplet states of closely related porphyrin dimers. The results presented here demonstrate that the most accurate estimate of the extent of triplet state delocalization can be obtained from the hyperfine couplings, while interpretation of the zero-field splitting parameter D can lead to underestimation of the delocalization length, unless combined with quantum chemical calculations. Furthermore, orientation-selective ENDOR and HYSCORE results, in combination with the results of density functional theory (DFT) calculations, allowed determination of the orientations of the zero-field splitting tensors with respect to the molecular frame in both porphyrin monomer and dimer. The results provide evidence for a reorientation of the zero-field splitting tensor and a change in the sign of the zero-field splitting D value. The direction of maximum dipolar coupling shifts from the out-of-plane direction in the porphyrin monomer to the vector connecting the two porphyrin units in the dimer. This reorientation, leading to an alignment of the principal optical transition moment and the axis of maximum dipolar coupling, is also confirmed by magnetophotoselection experiments

Probing the orientation of porphyrin oligomers in a liquid crystal solvent -a triplet state electron paramagnetic resonance study

Linear porphyrin oligomers have found various applications as synthetic molecular wires in the context of light harvesting, solar energy conversion and molecular electronics. In many of these applications a partial ordering of the molecules helps to improve the reaction efficiency or device performance. In this work we study the orientational properties of the building blocks of such porphyrin-based molecular wires, namely a porphyrin monomer and the corresponding butadiyne-bridged dimer. The porphyrins have been embedded in the nematic liquid crystal solvent 4-cyano-4’-pentylbiphenyl (5CB) and the anisotropic properties of their photogenerated triplet states were characterised by transient electron paramagnetic resonance (EPR) spectroscopy. When aligned in strong magnetic fields, the liquid crystal molecules impose their orientational anisotropy onto the solute guest molecules whose orientation-dependent magnetic properties can then be explored. The line shape analysis of the porphyrin triplet state EPR spectra − highly sensitive to small conformational changes − confirms the orientation of the zero-field-splitting (ZFS) tensors previously determined for these molecules by magnetophotoselection experiments. A biaxial distribution function is shown to be necessary to simulate the experimental EPR data. The biaxial behaviour, in conjunction with symmetry considerations, allows an unambiguous assignment of the three ZFS tensor axes to the molecular axes. From the determined orientational distributions of the porphyrins in 5CB, the biaxial order parameters for both molecules were calculated

Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers

The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins

Possible involvement of superoxide and dioxygen with cryptochrome in avian magnetoreception: Origin of Zeeman resonances observed by in vivo EPR spectroscopy

The radical pair model of the avian magnetic compass centres around magnetically sensitive chemical reactions in the retina. Recent studies of migratory birds subjected to oscillating magnetic fields found remarkably sensitive disorientation responses when the frequency of the applied field (∼1.3 MHz) matched the EPR condition of a radical with g ≈ 2 in the Earth's magnetic field (∼47 μT). The occurrence of such 'Zeeman resonances' can be understood if one of the radical pair partners is devoid of hyperfine interactions. Here we examine the possibility that this radical is either superoxide or dioxygen and conclude that neither offers a very credible explanation for these in vivo EPR 'signals'. © 2009 Elsevier B.V. All rights reserved