(Supplementary Table 1) Mercury isotope values for common and thick-billed murre (Uria aalge, Uria lomvia) eggs from Alaska

Atmospheric deposition of mercury to remote areas has increased threefold since pre-industrial times. Mercury deposition is particularly pronounced in the Arctic. Following deposition to surface oceans and sea ice, mercury can be converted into methylmercury, a biologically accessible form of the toxin, which biomagnifies along the marine food chain. Mass-independent fractionation of mercury isotopes accompanies the photochemical breakdown of methylmercury to less bioavailable forms in surface waters. Here we examine the isotopic composition of mercury in seabird eggs collected from colonies in the North Pacific Ocean, the Bering Sea and the western Arctic Ocean, to determine geographical variations in methylmercury breakdown at northern latitudes. We find evidence for mass-independent fractionation of mercury isotopes. The degree of mass-independent fractionation declines with latitude. Foraging behaviour and geographic variations in mercury sources and solar radiation fluxes were unable to explain the latitudinal gradient. However, mass-independent fractionation was negatively correlated with sea-ice cover. We conclude that sea-ice cover impedes the photochemical breakdown of methylmercury in surface waters, and suggest that further loss of Arctic sea ice this century will accelerate sunlight-induced breakdown of methylmercury in northern surface waters.

Microprocesos láser para la mejora de dispositivos fotovoltaicos basados en silicio cristalino

En los últimos años la tecnología láser se ha convertido en una herramienta imprescindible en la fabricación de dispositivos fotovoltaicos, ayudando a la consecución de dos objetivos claves para que esta opción energética se convierta en una alternativa viable: reducción de costes de fabricación y aumento de eficiencia de dispositivo. Dentro de las tecnologías fotovoltaicas, las basadas en silicio cristalino (c-Si) siguen siendo las dominantes en el mercado, y en la actualidad los esfuerzos científicos en este campo se encaminan fundamentalmente a conseguir células de mayor eficiencia a un menor coste encontrándose, como se comentaba anteriormente, que gran parte de las soluciones pueden venir de la mano de una mayor utilización de tecnología láser en la fabricación de los mismos. En este contexto, esta Tesis hace un estudio completo y desarrolla, hasta su aplicación en dispositivo final, tres procesos láser específicos para la optimización de dispositivos fotovoltaicos de alta eficiencia basados en silicio. Dichos procesos tienen como finalidad la mejora de los contactos frontal y posterior de células fotovoltaicas basadas en c-Si con vistas a mejorar su eficiencia eléctrica y reducir el coste de producción de las mismas. En concreto, para el contacto frontal se han desarrollado soluciones innovadoras basadas en el empleo de tecnología láser en la metalización y en la fabricación de emisores selectivos puntuales basados en técnicas de dopado con láser, mientras que para el contacto posterior se ha trabajado en el desarrollo de procesos de contacto puntual con láser para la mejora de la pasivación del dispositivo. La consecución de dichos objetivos ha llevado aparejado el alcanzar una serie de hitos que se resumen continuación: - Entender el impacto de la interacción del láser con los distintos materiales empleados en el dispositivo y su influencia sobre las prestaciones del mismo, identificando los efectos dañinos e intentar mitigarlos en lo posible. - Desarrollar procesos láser que sean compatibles con los dispositivos que admiten poca afectación térmica en el proceso de fabricación (procesos a baja temperatura), como los dispositivos de heterounión. - Desarrollar de forma concreta procesos, completamente parametrizados, de definición de dopado selectivo con láser, contactos puntuales con láser y metalización mediante técnicas de transferencia de material inducida por láser. - Definir tales procesos de forma que reduzcan la complejidad de la fabricación del dispositivo y que sean de fácil integración en una línea de producción. - Mejorar las técnicas de caracterización empleadas para verificar la calidad de los procesos, para lo que ha sido necesario adaptar específicamente técnicas de caracterización de considerable complejidad. - Demostrar su viabilidad en dispositivo final. Como se detalla en el trabajo, la consecución de estos hitos en el marco de desarrollo de esta Tesis ha permitido contribuir a la fabricación de los primeros dispositivos fotovoltaicos en España que incorporan estos conceptos avanzados y, en el caso de la tecnología de dopado con láser, ha permitido hacer avances completamente novedosos a nivel mundial. Asimismo los conceptos propuestos de metalización con láser abren vías, completamente originales, para la mejora de los dispositivos considerados. Por último decir que este trabajo ha sido posible por una colaboración muy estrecha entre el Centro Láser de la UPM, en el que la autora desarrolla su labor, y el Grupo de Investigación en Micro y Nanotecnologías de la Universidad Politécnica de Cataluña, encargado de la preparación y puesta a punto de las muestras y del desarrollo de algunos procesos láser para comparación. También cabe destacar la contribución de del Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, en la preparación de experimentos específicos de gran importancia en el desarrollo del trabajo. Dichas colaboraciones se han desarrollado en el marco de varios proyectos, tales como el proyecto singular estratégico PSE-MICROSIL08 (PSE-iv 120000-2006-6), el proyecto INNDISOL (IPT-420000-2010-6), ambos financiados por el Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” y el MICINN, y el proyecto del Plan Nacional AMIC (ENE2010-21384-C04-02), cuya financiación ha permitido en gran parte llevar a término este trabajo. v ABSTRACT. Last years lasers have become a fundamental tool in the photovoltaic (PV) industry, helping this technology to achieve two major goals: cost reduction and efficiency improvement. Among the present PV technologies, crystalline silicon (c-Si) maintains a clear market supremacy and, in this particular field, the technological efforts are focussing into the improvement of the device efficiency using different approaches (reducing for instance the electrical or optical losses in the device) and the cost reduction in the device fabrication (using less silicon in the final device or implementing more cost effective production steps). In both approaches lasers appear ideally suited tools to achieve the desired success. In this context, this work makes a comprehensive study and develops, until their implementation in a final device, three specific laser processes designed for the optimization of high efficiency PV devices based in c-Si. Those processes are intended to improve the front and back contact of the considered solar cells in order to reduce the production costs and to improve the device efficiency. In particular, to improve the front contact, this work has developed innovative solutions using lasers as fundamental processing tools to metalize, using laser induced forward transfer techniques, and to create local selective emitters by means of laser doping techniques. On the other side, and for the back contact, and approached based in the optimization of standard laser fired contact formation has been envisaged. To achieve these fundamental goals, a number of milestones have been reached in the development of this work, namely: - To understand the basics of the laser-matter interaction physics in the considered processes, in order to preserve the functionality of the irradiated materials. - To develop laser processes fully compatible with low temperature device concepts (as it is the case of heterojunction solar cells). - In particular, to parameterize completely processes of laser doping, laser fired contacts and metallization via laser transfer of material. - To define such a processes in such a way that their final industrial implementation could be a real option. - To improve widely used characterization techniques in order to be applied to the study of these particular processes. - To probe their viability in a final PV device. Finally, the achievement of these milestones has brought as a consequence the fabrication of the first devices in Spain incorporating these concepts. In particular, the developments achieved in laser doping, are relevant not only for the Spanish science but in a general international context, with the introduction of really innovative concepts as local selective emitters. Finally, the advances reached in the laser metallization approached presented in this work open the door to future developments, fully innovative, in the field of PV industrial metallization techniques. This work was made possible by a very close collaboration between the Laser Center of the UPM, in which the author develops his work, and the Research Group of Micro y Nanotecnology of the Universidad Politécnica de Cataluña, in charge of the preparation and development of samples and the assessment of some laser processes for comparison. As well is important to remark the collaboration of the Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, in the preparation of specific experiments of great importance in the development of the work. These collaborations have been developed within the framework of various projects such as the PSE-MICROSIL08 (PSE-120000-2006-6), the project INNDISOL (IPT-420000-2010-6), both funded by the Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” and the MICINN, and the project AMIC (ENE2010-21384-C04-02), whose funding has largely allowed to complete this work.

Relativistic high-current electron-beam stopping-power characterization in solids and plasmas: collisional versus resistive effects.

We present experimental and numerical results on intense-laser-pulse-produced fast electron beams transport through aluminum samples, either solid or compressed and heated by laser-induced planar shock propagation. Thanks to absolute K� yield measurements and its very good agreement with results from numerical simulations, we quantify the collisional and resistive fast electron stopping powers: for electron current densities of � 8 � 1010 A=cm2 they reach 1:5 keV=�m and 0:8 keV=�m, respectively. For higher current densities up to 1012 A=cm2, numerical simulations show resistive and collisional energy losses at comparable levels. Analytical estimations predict the resistive stopping power will be kept on the level of 1 keV=�m for electron current densities of 1014 A=cm2, representative of the full-scale conditions in the fast ignition of inertially confined fusion targets.

Protonation dynamics of the extracellular and cytoplasmic surface of bacteriorhodopsin in the purple membrane.

The dynamics of proton binding to the extracellular and the cytoplasmic surfaces of the purple membrane were measured by laser-induced proton pulses. Purple membranes, selectively labeled by fluorescein at Lys-129 of bacteriorhodopsin, were pulsed by protons released in the aqueous bulk from excited pyranine (8-hydroxy-1,3,6-pyrenetrisulfonate) and the reaction of protons with the indicators was measured. Kinetic analysis of the data imply that the two faces of the membrane differ in their buffer capacities and in their rates of interaction with bulk protons. The extracellular surface of the purple membrane contains one anionic proton binding site per protein molecule with pK = 5.1. This site is within a Coulomb cage radius (approximately 15 A) from Lys-129. The cytoplasmic surface of the purple membrane bears 4-5 protonable moieties (pK = 5.1) that, due to close proximity, function as a common proton binding site. The reaction of the proton with this cluster is at a very fast rate (3.10(10) M-1.s-1). The proximity between the elements is sufficiently high that even in 100 mM NaCl they still function as a cluster. Extraction of the chromophore retinal from the protein has a marked effect on the carboxylates of the cytoplasmic surface, and two to three of them assume positions that almost bar their reaction with bulk protons. The protonation dynamics determined at the surface of the purple membrane is of relevance both for the vectorial proton transport mechanism of bacteriorhodopsin and for energy coupling, not only in halobacteria, but also in complex chemiosmotic systems such as mitochondrial and thylakoid membranes.

DNA-protein binding assays from a single sea urchin egg: a high-sensitivity capillary electrophoresis method.

A capillary electrophoresis method has been developed to study DNA-protein complexes by mobility-shift assay. This method is at least 100 times more sensitive than conventional gel mobility-shift procedures. Key features of the technique include the use of a neutral coated capillary, a small amount of linear polymer in the separation medium, and use of covalently dye-labeled DNA probes that can be detected with a commercially available laser-induced fluorescence monitor. The capillary method provides quantitative data in runs requiring < 20 min, from which dissociation constants are readily determined. As a test case we studied interactions of a developmentally important sea urchin embryo transcription factor, SpP3A2. As little as 2-10 x 10(6) molecules of specific SpP3A2-oligonucleotide complex were reproducibly detected, using recombinant SpP3A2, crude nuclear extract, egg lysates, and even a single sea urchin egg lysed within the capillary column.

Characterization of the interfaces between Au(hkl) single crystal basal plane electrodes and [Emmim][Tf2N] ionic liquid

The interface between Au(hkl) basal planes and the ionic liquid 1-Ethyl-2,3-dimethyl imidazolium bis(trifluoromethyl)sulfonil imide was investigated by using both cyclic voltammetry and laser-induced temperature jump. Cyclic voltammetry showed characteristic features, revealing surface sensitive processes at the interfaces Au(hkl)/[Emmim][Tf2N]. From laser-induced heating the potential of maximum entropy (pme) is determined. Pme is close to the potential of zero charge (pzc) and, therefore, the technique provides relevant interfacial information. The following order for the pme values has been found: Au(111) > Au(100) > Au(110). This order correlates well with work function data and values of pzc in aqueous solutions.

(Table 1) I, Br, B, d11B and Mn concentrations in ODP Site 131-808

This study of the interstitial water concentration-depth distributions of iodide, bromide, boron, d11B, and dissolved organic carbon, as represented by absorbance at 325 nm (yellow substance: YS) and laser-induced fluorescence (LIF), is a follow-up of the extensive shipboard program of interstitial water analysis during ODP Leg 131. Most of the components studied are associated with processes involving the diagenesis of organic matter in these sediments. Three zones of the sediment column are discussed separately because of the different processes involved in causing concentration changes: 1. The upper few hundreds of meters: In this zone, characterized by very high sedimentation rates (>1200 m/m.y.), interstitial waters show very sharp increases in alkalinity, ammonia, iodide, bromide, YS, and LIF, mainly as a result of the diagenesis of organic carbon; 2. Whereas below 200 mbsf concentration gradients all show a decreasing trend, the zone at ~ 365 mbsf is characterized by concentration reversals, mainly due to the recent emplacement of deeper sediments above this depth as a result of thrust-faulting; 3. The décollement zone (945-964 mbsf) is characterized by concentration anomalies in various constituents (bromide, boron, d11B, manganese, LIF). These data are interpreted as resulting from an advective input of fluids along the zone of décollement as recent as ~ 200 ka. Possibly periodic inputs of anomalous fluids still seem to occur along this décollement zone.

Radiofrequency ablation of liver tumors - A systematic review

Objectives: To systematically review radiofrequency ablation (RFA) for treating liver tumors. Data Sources: Databases were searched in July 2003. Study Selection: Studies comparing RFA with other therapies for hepatocellular carcinoma (HCC) and colorectal liver metastases (CLM) plus selected case series for CLM. Data Extraction: One researcher used standardized data extraction tables developed before the study, and these were checked by a second researcher. Data Synthesis: For HCC, 1.3 comparative studies were included, 4 of which were randomized, controlled trials. For CLM, 13 studies were included, 2 of which were nonrandomized comparative studies and 11 that were case series. There did not seem to be any distinct differences in the complication rates between RFA and any of the other procedures for treatment of HCC. The local recurrence rate at 2 years showed a statistically significant benefit for RFA over percutaneous ethanol injection for treatment of HCC (6% vs 26%, 1 randomized, controlled trial). Local recurrence was reported to be more common after RFA than after laser-induced thermotherapy, and a higher recurrence rate and a shorter time to recurrence were dassociated with RFA compared with surgical resection (1 nonrandomized study each). For CLM, the postoperative complication rate ranged from 0% to 33% (3 case series). Survival after diagnosis was shorter in the CLM group treated with RFA than in the surgical resection group (1 nonrandomized study). The CLM local recurrence rate after RFA ranged from 4% to 55% (6 case series). Conclusions: Radiofrequency ablation may be more effective than other treatments in terms of less recurrence of HCC and may be as sale, although the evidence is scant. There was not enough evidence to determine the safety or efficacy of RFA for treatment of CLM.

Interactions between oligoamines and superoxide anion

1- Oligoamines and EDTA inhibited the reduction of cytochrome-C and nitrobule tetrazolium (NBT) induced by the hypoxanthine/xanthine oxidase superoxide anion generating system in the following order of effectiveness: putrescine > diaminopropane > spermidine > EDTA > spermine > cadaverine. 2- Oligoamines and EDTA did not affect the rate of urate formation from the hypoxanthine/xanthine oxidase system. 3- Oligoamines and EDTA inhibited the reduction of cytochrome-C induced by stimulated PMNL's in the same order of effectiveness as mentioned before. 4- Oligoamines and EDTA inhibited luminol dependent stimulated PMNL's chemiluminescence. 5- Oligoamines and EDTA inhibited the aerobic photoreduction of NBT. 6- Oligoamines-copper sulphate complexes inhibited the reduction of cytochrome-C induced by the hypoxanthine/xanthine oxidase system more effectively than oligoamines or copper sulphate individually. 7- Superoxide anion, hydrogen peroxide and hydroxyl radical induced breakdown of isolated intact guinea pig liver lysosomes. 8- Oligoamines and EDTA protected isolated intact guinea pig liver lysosomes from the lytic effect of superoxide anion generated either by the hypoxanthine/xanthine oxidase system or by stimulated PMNL's. 9- Oligoamines and EDTA have no stabilizing effect on isolated intact guinea pig liver lysosomes. 10- The uptake of oligoamines by lysosomes was in the following order: putrescine > spermidine > spermine. 11- Oligoamines were metabolised into aldehyde compounds either by the hypoxanthine/xanthine oxidase system or stimulated PMNL's. 12- Oligoamines and EDTA have no effect on the activities of free lysosomal enzymes (acid phosphatase and -glucosaminidase). 13- Oligoamines and EDTA inhibited lipid peroxidation in guinea pig liver lysosomes induced either by the hypoxanthine/xanthine oxidase or ascorbic acid-ferrous sulphate. 14- Oligoamines and EDTA have no effect on the release of PGE_2 from stimulated peritoneal guinea pig PMNL's. 15- Oligoamines increased the uptake of (^3H)thymidine and (^3H)leucine by stimulated peritoneal guinea pig macrophages in the following order of effectiveness: spermine > spermidine > putrescine > cadaverine. 16- PGE_2, dibutyryl Cyclic AMP, and theophylline inhibited luminol dependent stimulated peritoneal guinea pig PMNL's chemiluminescence.

Improved estimation of postmortem interval with Cardiac Troponin T and improved analytical methods

Accurate knowledge of the time since death, or postmortem interval (PMI), has enormous legal, criminological, and psychological impact. In this study, an investigation was made to determine whether the relationship between the degradation of the human cardiac structure protein Cardiac Troponin T and PMI could be used as an indicator of time since death, thus providing a rapid, high resolution, sensitive, and automated methodology for the determination of PMI. ^ The use of Cardiac Troponin T (cTnT), a protein found in heart tissue, as a selective marker for cardiac muscle damage has shown great promise in the determination of PMI. An optimized conventional immunoassay method was developed to quantify intact and fragmented cTnT. A small sample of cardiac tissue, which is less affected than other tissues by external factors, was taken, homogenized, extracted with magnetic microparticles, separated by SDS-PAGE, and visualized with Western blot by probing with monoclonal antibody against cTnT. This step was followed by labeling and available scanners. This conventional immunoassay provides a proper detection and quantitation of cTnT protein in cardiac tissue as a complex matrix; however, this method does not provide the analyst with immediate results. Therefore, a competitive separation method using capillary electrophoresis with laser-induced fluorescence (CE-LIF) was developed to study the interaction between human cTnT protein and monoclonal anti-TroponinT antibody. ^ Analysis of the results revealed a linear relationship between the percent of degraded cTnT and the log of the PMI, indicating that intact cTnT could be detected in human heart tissue up to 10 days postmortem at room temperature and beyond two weeks at 4C. The data presented demonstrates that this technique can provide an extended time range during which PMI can be more accurately estimated as compared to currently used methods. The data demonstrates that this technique represents a major advance in time of death determination through a fast and reliable, semi-quantitative measurement of a biochemical marker from an organ protected from outside factors. ^

XFEL resonant photo-pumping of dense plasmas and dynamic evolution of autoionizing core hole states

Similarly to the case of LIF (Laser-Induced Fluorescence), an equally revolutionary impact to science is expected from resonant X-ray photo-pumping. It will particularly contribute to a progress in high energy density science: pumped core hole states create X-ray transitions that can escape dense matter on a 10 fs-time scale without essential photoabsorption, thus providing a unique possibility to study matter under extreme conditions. In the first proof of principle experiment at the X-ray Free Electron Laser LCLS at SCLAC [Seely, J., Rosmej, F.B., Shepherd, R., Riley, D., Lee, R.W. Proposal to Perform the 1^st High Energy Density Plasma Spectroscopic Pump/Probe Experiment", approved LCLS proposal L332 (2010)] we have successfully pumped inner-shell X-ray transitions in dense plasmas. The plasma was generated with a YAG laser irradiating solid Al and Mg targets attached to a rotating cylinder. In parallel to the optical laser beam, the XFEL was focused into the plasma plume at different delay times and pump energies. Pumped X-ray transitions have been observed with a spherically bent crystal spectrometer coupled to a Princeton CCD. By using this experimental configuration, we have simultaneously achieved extremely high spectral (λ/δλ ≈ 5000) and spatial resolution (δx≈70 μm) while maintaining high luminosity and a large spectral range covered (6.90 - 8.35 Å). By precisely measuring the variations in spectra emitted from plasma under action of XFEL radiation, we have successfully demonstrated transient X- ray pumping in a dense plasma.

Air Entrainment in the Turbulent Ship Hull Boundary Layer

Turbulent fluctuations in the vicinity of the water free surface along a flat, vertically oriented surface-piercing plate are studied experimentally using a laboratory-scale experiment. In this experiment, a meter-wide stainless steel belt travels horizontally in a loop around two rollers with vertically oriented axes, which are separated by 7.5 meters. This belt device is mounted inside a large water tank with the water level set just below the top edge of the belt. The belt, rollers, and supporting frame are contained within a sheet metal box to keep the device dry except for one 6-meter-long straight test section between rollers. The belt is launched from rest with an acceleration of up to 3-g in order to quickly reach steady state velocity. This creates a temporally evolving boundary layer analogous to the spatially evolving boundary layer created along a flat-sided ship moving at the same velocity, with a length equivalent to the length of belt that has passed the measurement region since the belt motion began. Surface profile measurements in planes normal to the belt surface are conducted using cinematic Laser Induced Fluorescence and quantitative surface profiles are extracted at each instant in time. Using these measurements, free surface fluctuations are examined and the propagation behavior of these free surface ripples is studied. It is found that free surface fluctuations are generated in a region close to the belt surface, where sub-surface velocity fluctuations influence the behavior of these free surface features. These rapidly-changing surface features close to the belt appear to lead to the generation of freely-propagating waves far from the belt, outside the influence of the boundary layer. Sub-surface PIV measurements are performed in order to study the modification of the boundary layer flow field due to the effects of the water free surface. Cinematic planar PIV measurements are performed in horizontal planes parallel to the free surface by imaging the flow from underneath the tank, providing streamwise and wall-normal velocity fields. Additional planar PIV experiments are performed in vertical planes parallel to the belt surface in order to study the bahvior of streamwise and vertical velocity fields. It is found that the boundary layer grows rapidly near the free surface, leading to an overall thicker boundary layer close to the surface. This rapid boundary layer growth appears to be linked to a process of free surface bursting, the sudden onset of free surface fluctuations. Cinematic white light movies are recorded from beneath the water surface in order to determine the onset location of air entrainment. In addition, qualitative observations of these processes are made in order to determine the mechanisms leading to air entrainment present in this flow.

Surface photochemistry: photodegradation study of pyrene adsorbed onto microcrystalline cellulose and silica

Ground-state diffuse reflectance, time resolved laser-induced luminescence, diffuse reflectance laser flash-photolysis transient absorption and chromatographic techniques were used to elucidate the photodegradation processes of pyrene adsorbed onto microcrystalline cellulose and silica. Ground-state diffuse reflectance showed that on both substrates low concentrations display absorption of pyrene monomers. At high concentrations spectral changes attributed to aggregate formation were observed. Laser induced fluorescence showed that pyrene onto microcrystalline cellulose mainly presents fluorescence from monomers, while for silica, excimer-like emission was observed from low surface loadings (greater than or equal to 0.5 mumol g(-1)). Transient absorption and photodegradation studies were performed at concentrations where mainly monomers exist. On silica, pyrene presents transient absorption from its radical cation. On microcrystalline cellulose both radical cation, radical anion and pyrene triplet-triplet absorption were detected. Irradiation followed by chromatographic analysis showed that pyrene decomposes on both substrates. For pyrene on microcrystalline cellulose 1-hydroxypyrene was the main identified photoproduct since in the absence of oxygen further oxidation of 1-hydroxypyrene was very slow. For pyrene on silica photodegradation was very efficient. Almost no 1-hydroxypyrene was detected since in the presence of oxygen it is quickly oxidized to other photooxidation products. On both substrates, pyrene radical cation is the intermediate leading to photoproducts and oxygen it is not involved in its formation.

A diffuse reflectance comparative study of benzil inclusion within microcrystalline cellulose and beta-cyclodextrin

Diffuse reflectance and laser-induced techniques were used to study photochemical and photophysical processes of benzil adsorbed on two solid powdered supports, microcrystalline cellulose and beta-cyclodextrin. In both substrates, a distribution of ground-state benzil conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. Room temperature phosphorescence was observed in air-equilibrated samples in both cases. The decay times vary greatly and the largest lifetime was obtained for benzil/beta-cyclodextrin, showing that this host's cavity accommodates benzil well, enhancing its room temperature phosphorescence. Triplet - triplet absorption of benzil entrapped in cellulose was detected and benzil ketyl radical formation also occurred. With benzil included into beta-cyclodextrin, and following laser excitation, benzoyl radicals were detected on the millisecond timescale. Product analysis and identification of laser-irradiated benzil samples in the two hosts clearly showed that the main degradation photoproducts were benzoic acid and benzaldehyde. The main differences were a larger benzoic acid/benzaldehyde ratio in the case of cellulose and the formation of benzyl alcohol in this support.

A diffuse reflectance comparative study of benzil inclusion within p-tert-butylcalix[n]arenes (n=4, 6, and 8) and silicalite

Diffuse reflectance and laser-induced techniques were used to access photochemical and photophysical processes of benzil in solid supports, namely p-tert-butylcalix[n]arenes with n = 4, 6, and 8. A comparative study was performed using these results and those obtained with another electronically inert support, silicalite, which is a hydrophobic zeolite. In the latter substrate, ground-state benzil has the two carbonyl groups in an s-trans planar conformation while in the calixarenes a distribution of conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. In all substrates, room-temperature phosphorescence was obtained in air-equilibrated samples. The decay times vary greatly and the largest lifetime was obtained for benzil/p-tert-butylcalix[6]arene, showing that this host cavity well accommodates benzil, enhancing its room-temperature phosphorescence. p-tert-Butylcalix[6] and [8]arene molecules provide larger hydrophobic cavities than silicalite, and inclusion complexes are formed with these hosts and benzil as guest; p-tert-butylcalix[4]arene does not include benzil. This probe is deposited outside the calix[41 cavity, in the form of microcrystals. Triplet-triplet absorption of benzil was detected in all cases and is predominant in the silicalite channel inclusion case. Benzil ketyl radical formation occurs with inclusion in calix[6]arene and calix[8]arene. In the three cases, benzoyl radical was detected at long times (in the millisecond time scale). Product analysis and identification clearly show that the main detected degradation photoproducts in all substrates are benzoyl radical derivatives. Calix[6] and [8]arenes are able to supply hydrogen atoms that allow also another reaction, the reduction to benzoin through benzil ketyl radical formation.