Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Optimal Rehabilitation Strategy In Water Distribution Systems Considering Reduction In Greenhouse Gas Emissions

Most of water distribution systems (WDS) need rehabilitation due to aging infrastructure leading to decreasing capacity, increasing leakage and consequently low performance of the WDS. However an appropriate strategy including location and time of pipeline rehabilitation in a WDS with respect to a limited budget is the main challenge which has been addressed frequently by researchers and practitioners. On the other hand, selection of appropriate rehabilitation technique and material types is another main issue which has yet to address properly. The latter can affect the environmental impacts of a rehabilitation strategy meeting the challenges of global warming mitigation and consequent climate change. This paper presents a multi-objective optimization model for rehabilitation strategy in WDS addressing the abovementioned criteria mainly focused on greenhouse gas (GHG) emissions either directly from fossil fuel and electricity or indirectly from embodied energy of materials. Thus, the objective functions are to minimise: (1) the total cost of rehabilitation including capital and operational costs; (2) the leakage amount; (3) GHG emissions. The Pareto optimal front containing optimal solutions is determined using Non-dominated Sorting Genetic Algorithm NSGA-II. Decision variables in this optimisation problem are classified into a number of groups as: (1) percentage proportion of each rehabilitation technique each year; (2) material types of new pipeline for rehabilitation each year. Rehabilitation techniques used here includes replacement, rehabilitation and lining, cleaning, pipe duplication. The developed model is demonstrated through its application to a Mahalat WDS located in central part of Iran. The rehabilitation strategy is analysed for a 40 year planning horizon. A number of conventional techniques for selecting pipes for rehabilitation are analysed in this study. The results show that the optimal rehabilitation strategy considering GHG emissions is able to successfully save the total expenses, efficiently decrease the leakage amount from the WDS whilst meeting environmental criteria.

Static potential in QED(3) with nonminimal coupling

Here we study the effect of the nonminimal coupling j(mu)epsilon(munualpha)partial derivative(nu)A(alpha) on the static potential in multiflavor QED(3). Both cases of four and two components fermions are studied separately at leading order in the 1/N expansion. Although a nonlocal Chern-Simons term appears, in the four components case the photon is still massless leading to a confining logarithmic potential similar to the classical one. In the two components case, as expected, the parity breaking fermion mass term generates a traditional Chern-Simons term which makes the photon massive and we have a screening potential which vanishes at large intercharge distance. The extra nonminimal couplings have no important influence on the static potential at large intercharge distances. However, interesting effects show up at finite distances. In particular, for strong enough nonminimal coupling we may have a new massive pole in the photon propagator, while in the opposite limit there may be no poles at all in the irreducible case. We also found that, in general, the nonminimal couplings lead to a finite range repulsive force between charges of opposite signs.

Multi-objective evolutionary particle swarm optimization in the assessment of the impact of distributed generation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A linear optimization approach to the combined production planning model

Two fundamental processes usually arise in the production planning of many industries. The first one consists of deciding how many final products of each type have to be produced in each period of a planning horizon, the well-known lot sizing problem. The other process consists of cutting raw materials in stock in order to produce smaller parts used in the assembly of final products, the well-studied cutting stock problem. In this paper the decision variables of these two problems are dependent of each other in order to obtain a global optimum solution. Setups that are typically present in lot sizing problems are relaxed together with integer frequencies of cutting patterns in the cutting problem. Therefore, a large scale linear optimizations problem arises, which is exactly solved by a column generated technique. It is worth noting that this new combined problem still takes the trade-off between storage costs (for final products and the parts) and trim losses (in the cutting process). We present some sets of computational tests, analyzed over three different scenarios. These results show that, by combining the problems and using an exact method, it is possible to obtain significant gains when compared to the usual industrial practice, which solve them in sequence. (C) 2010 The Franklin Institute. Published by Elsevier Ltd. All rights reserved.

Visible to infrared energy conversion in Pr3+-Yb3+ co-doped fluoroindate glasses

Processes involving visible to infrared energy conversion are presented for Pr3+-Yb3+ co-doped fluoroindate glasses. The emission in the visible and infrared regions, the luminescence decay time of the Pr 3+:3P0 → 3H4 (482 nm), Pr3+:1D2 → 3H6 (800 nm), Yb3+:2F5/2 → 2F 7/2 (1044 nm) transitions and the photoluminescence excitation spectra were measured in Pr3+ samples and in Pr3+-Yb 3+ samples as a function of the Yb3+ concentration. In addition, energy transfer efficiencies were estimated from Pr3+: 3P0 and Pr3+:1D2 levels to Yb3+:2F7/2 level. Down-Conversion (DC) emission is observed due to a combination of two different processes: 1-a one-step cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) resulting in one photon emitted by Pr3+ (1G4 → 3H5) and one photon emitted by Yb3+ (2F7/2 → 2F5/2); 2-a resonant two-step first order energy transfer, where the first part of energy is transferred to Yb3+ neighbor through cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) followed by a second energy transfer step (Pr 3+:1G4 → 3H4; Yb3+:2F7/2 → 2F5/2). A third process leading to one IR photon emission to each visible photon absorbed involves cross relaxation energy transfer (Pr3+: 1D2 → 3F4; Yb 3+:2F7/2 → 2F5/2). © 2013 Elsevier B.V. All rights reserved.

Ultrasound effect in the removal of intraradicular posts cemented with different materials

This study evaluated the effect of ultrasonic vibration on the tensile strength required to remove intraradicular post cemented with different materials. Bovine teeth were selected, and 7 mm of the cervical root canals were prepared to size 5 Largo drill, the posts were cemented with zinc phosphate, Enforce (resin) or Rely X (glass ionomer). The specimens were divided into six groups (n = 10), according to the following procedures: GI-cementation with zinc phosphate associated with traction force; GII-cementation with zinc phosphate associated with ultrasonic activation and traction force; G111-cementation with Enforce associated with traction force; GIV-cementation with Enforce associated with ultrasonic activation and traction force; GV-cementation with Rely X associated with traction force; and GVI-cementation with Rely X associated with ultrasonic activation and traction force. The tensile test was conducted using the electromechanical testing machine, the force was determined by a specialized computer program and ultrasonic activation using the Jet Sonic Four Plus (Gnatus) device in 10P. Concerning to average ranking, GI showed statistically significant difference in comparison with GII and GVI (p < 0.05); there was no statistical difference in GIII and GIV when compared to other groups (p > 0.05). The ultrasound favored the intraradicular post traction regardless of the employed cement in greater or lesser extent. The post removal is a routine practice in the dental office, therefore, new solutions and better alternatives are need to the practitioner. We did not find in the literature many articles referring to this practice. Thus, the results from this study are relevant in the case planning and to promote more treatment options.

Hepatitis C infection: challenges in dental management and diagnosis of extrahepatic manifestations

Hepatitis C is associated with autoimmune diseases, hepatocellular carcinoma,and extrahepatic manifestations that, in conjunction, may seriously compromise the patient's quality of life. We herein describe a case of chronic hepatitis C with oral manifestations and discuss some implications for diagnosis and treatment. A 63-year-old woman complaining of spontaneous bleeding of the oral mucosa presented with bilateral asymmetric ulcers surrounded by white papules and striae on the buccal mucosa. Her medical history revealed leucopenia, thrombocytopenia, and skin lesions associated with chronic hepatitis C. Propranolol and ranitidine had recently been prescribed. Lichen planus, lichenoid reaction, and erythema multiforme were considered in the differential diagnosis. Histopathological analysis revealed lymphocytic infiltrate in a lichenoid pattern. The lesions partially healed after 1 week and completely regressed after 6 months, despite the maintenance of all medications; no recurrence was observed. The final diagnosis was oral lichen planus associated with hepatitis C. Chronic hepatitis C may present oral manifestations, which demand adjustments in dental treatment planning. Medication side effects may interfere with the clinical presentation and course of the disease and should be accounted for in the differential diagnosis. The possibility of spontaneous remission of oral lichen planus should always be considered, especially when putative etiological factors of a lichenoid lesion are withdrawn in an attempt to differentiate oral lichen planus from lichenoid lesions. This case emphasizes the importance of recognizing the extrahepatic manifestations of hepatitis C as a cause of increased morbidity.

Cross-taxon congruence of alpha and beta diversity among five leaf litter arthropod groups in Colombia

In this study alpha and beta diversity patterns of five leaf litter arthropod groups (ants, predatory ants, oribatid mites, spiders and other arachnids) were described and compared in 39 sampling patches of a transformed landscape in southwestern Colombia, that represented five vegetation types: secondary forest, riparian forest, giant bamboo forest, pasture and sugarcane crop. It was also assessed whether some taxa could be used as diversity surrogates. A total of 6,765 individuals grouped in 290 morphospecies were collected. Species richness in all groups was lower in highly transformed vegetation types (pasture, sugarcane crop) than in native ones (forests). In contrast, there were no clear tendencies of beta diversity among vegetation types. Considering sampling patches, 0.1-42% of the variation in alpha diversity of one taxonomic group could be explained from the alpha diversity of another, and 0.2-33% of the variation of beta diversity of a given taxon was explained by that in other groups. Contrary to recent findings, we concluded that patterns of alpha diversity are more congruent than patterns of beta diversity. This fact could be attributed to a sampling effect that promotes congruence in alpha diversity and to a lack of a clear regional ecological gradient that could promote congruent patterns of beta diversity. We did not find evidence for an ideal diversity surrogate although diversity patterns of predatory ants had the greatest congruencies. These results support earlier multi-taxon evaluations in that conservation planning should not be based on only one leaf litter arthropod group.

What Happened to Participation? Urban Development and Authoritarian Upgrading in Cairo's Informal Neighbourhoods

Participation appeared in development discourses for the first time in the 1970s, as a generic call for the involvement of the poor in development initiatives. Over the last three decades, the initial perspectives on participation intended as a project method for poverty reduction have evolved into a coherent and articulated theoretical elaboration, in which participation figures among the paraphernalia of good governance promotion: participation has acquired the status of “new orthodoxy”. Nevertheless, the experience of the implementation of participatory approaches in development projects seemed to be in the majority of cases rather disappointing, since the transformative potential of ‘participation in development’ depends on a series of factors in which every project can actually differ from others: the ultimate aim of the approach promoted, its forms and contents and, last but not least, the socio-political context in which the participatory initiative is embedded. In Egypt, the signature of a project agreement between the Arab Republic of Egypt and the Federal Republic of Germany, in 1998, inaugurated a Participatory Urban Management Programme (PUMP) to be implemented in Greater Cairo by the German Technical Cooperation (Deutsche Gesellschaft für Technische Zusammenarbeit, GTZ) and the Ministry of Planning (now Ministry of Local Development) and the Governorates of Giza and Cairo as the main counterparts. Now, ten years after the beginning of the PUMP/PDP and close to its end (December 2010), it is possible to draw some conclusions about the scope, the significance and the effects of the participatory approach adopted by GTZ and appropriated by the Egyptian counterparts in dealing with the issue of informal areas and, more generally, of urban development. Our analysis follows three sets of questions: the first set regards the way ‘participation’ has been interpreted and concretised by PUMP and PDP. The second is about the emancipating potential of the ‘participatory approach’ and its ability to ‘empower’ the ‘marginalised’. The third focuses on one hand on the efficacy of GTZ strategy to lead to an improvement of the delivery service in informal areas (especially in terms of planning and policies), and on the other hand on the potential of GTZ development intervention to trigger an incremental process of ‘democratisation’ from below.

The evolution of massive clumps in star forming regions

In this thesis two related arguments are investigated: - The first stages of the process of massive star formation, investigating the physical conditions and -properties of massive clumps in different evolutionary stages, and their CO depletion; - The influence that high-mass stars have on the nearby material and on the activity of star formation. I characterise the gas and dust temperature, mass and density of a sample of massive clumps, and analyse the variation of these properties from quiescent clumps, without any sign of active star formation, to clumps likely hosting a zero-age main sequence star. I briefly discuss CO depletion and recent observations of several molecular species, tracers of Hot Cores and/or shocked gas, of a subsample of these clumps. The issue of CO depletion is addressed in more detail in a larger sample consisting of the brightest sources in the ATLASGAL survey: using a radiative tranfer code I investigate how the depletion changes from dark clouds to more evolved objects, and compare its evolution to what happens in the low-mass regime. Finally, I derive the physical properties of the molecular gas in the photon-dominated region adjacent to the HII region G353.2+0.9 in the vicinity of Pismis 24, a young, massive cluster, containing some of the most massive and hottest stars known in our Galaxy. I derive the IMF of the cluster and study the star formation activity in its surroundings. Much of the data analysis is done with a Bayesian approach. Therefore, a separate chapter is dedicated to the concepts of Bayesian statistics.

First doubly polarised photoproduction on 3 He at the photon beam of MAMI

Im Juli 2009 wurde am Mainzer Mikrotron (MAMI) erstmal ein Experiment durchgeführt, bei dem ein polarisiertes 3He Target mit Photonen im Energiebereich von 200 bis 800 MeV untersucht wurde. Das Ziel dieses Experiments war die Überprüfung der Gerasimov-Drell-Hearn Summenregel am Neutron. Die Verwendung der Messdaten welche mit dem polarisierten 3He Target gewonnen wurden, geben - im Vergleich mit den bereits existieren Daten vom Deuteron - aufgrund der Spin-Struktur des 3He einen komplementären und direkteren Zugang zum Neutron. Die Messung des totalen helizitätsabhängigen Photoabsorptions-Wirkungsquerschnitts wurde mittels eines energiemarkierten Strahls von zirkular polarisierten Photonen, welcher auf das longitudinal polarisierte 3He Target trifft, durchgeführt. Als Produktdetektoren kamen der Crystal Ball (4π Raumabdeckung), TAPS (als ”Vorwärtswand”) sowie ein Schwellen-Cherenkov-Detektor (online Veto zur Reduktion von elektromagnetischen Ereignissen) zum Einsatz. Planung und Aufbau der verschiedenen komponenten Teile des 3He Experimentaufbaus war ein entscheidender Teil dieser Dissertation und wird detailliert in der vorliegenden Arbeit beschrieben. Das Detektorsystem als auch die Analyse-Methoden wurden durch die Messung des unpolarisierten, totalen und inklusiven Photoabsoprtions-Wirkungsquerschnitts an flüssigem Wasserstoff getestet. Hierbei zeigten die Ergebnisse eine gute Übereinstimmung mit bereits zuvor publizierten Daten. Vorläufige Ergebnisse des unpolarisierten totalen Photoabsorptions-Wirkungsquerschnitts sowie der helizitätsabhängige Unterschied zwischen Photoabsorptions-Wirkungsquerschnitten an 3He im Vergleich zu verschiedenen theoretischen Modellen werden vorgestellt.

Femtosecond laser-based investigations of magnetic circular dichroism in near-threshold photoemission

During the last decades magnetic circular dichroism (MCD) has attracted much interest and evolved into various experimental methods for the investigation of magnetic thin films. For example, synchrotron-based X-ray magnetic circular dichroism (XMCD) displays the absolute values of spin and orbital magnetic moments. It thereby benefits from large asymmetry values of more than 30% due to the excitation of atomic core-levels. Similarly large values are also expected for threshold photoemission magnetic circular dichroism (TPMCD). Using lasers with photon energies in the range of the sample work function this method gives access to the occupied electronic structure close to the Fermi level. However, except for the case of Ni(001) there exist only few studies on TPMCD moreover revealing much smaller asymmetries than XMCD-measurements. Also the basic physical mechanisms of TPMCD are not satisfactorily understood. In this work we therefore investigate TPMCD in one- and two-photon photoemission (1PPE and 2PPE) for ferromagnetic Heusler alloys and ultrathin Co films using ultrashort pulsed laser light. The observed dichroism is explained by a non-conventional photoemission model using spin-resolved band-structure calculations and linear response theory. For the two Heusler alloys Ni2MnGa and Co2FeSi we give first evidence of TPMCD in the regime of two-photon photoemission. Systematic investigations concerning general properties of TPMCD in 1PPE and 2PPE are carried out at ultrathin Co films grown on Pt(111). Here, photon-energy dependent measurements reveal asymmetries of 1.9% in 1PPE and 11.7% in 2PPE. TPMCD measurements at decreased work function even yield larger asymmetries of 6.2% (1PPE) and 17% (2PPE), respectively. This demonstrates that enlarged asymmetries are also attainable for the TPMCD effect on Co(111). Furthermore, we find that the TPMCD asymmetry is bulk-sensitive for 1PPE and 2PPE. This means that the basic mechanism leading to the observed dichroism must be connected to Co bulk properties; surface effects do not play a crucial role. Finally, the enhanced TPMCD asymmetries in 2PPE compared to the 1PPE case are traced back to the dominant influence of the first excitation step and the existence of a real intermediate state. The observed TPMCD asymmetries cannot be interpreted by conventional photoemission theory which only considers direct interband transitions in the direction of observation (Γ-L). For Co(111), these transitions lead to evanescent final states. The excitation to such states, however, is incompatible with the measured bulk-sensitivity of the asymmetry. Therefore, we generalize this model by proposing the TPMCD signal to arise mostly from direct interband transitions in crystallographic directions other than (Γ-L). The necessary additional momentum transfer to the excited electrons is most probably provided by electron-phonon or -magnon scattering processes. Corresponding calculations on the basis of this model are in reasonable agreement with the experimental results so that this approach represents a promising tool for a quantitative description of the TPMCD effect. The present findings encourage an implementation of our experimental technique to time- and spatially-resolved photoemission electron microscopy, thereby enabling a real time imaging of magnetization dynamics of single excited states in a ferromagnetic material on a femtosecond timescale.

Surgical planning tool for robotically assisted hearing aid implantation

PURPOSE : For the facilitation of minimally invasive robotically performed direct cochlea access (DCA) procedure, a surgical planning tool which enables the surgeon to define landmarks for patient-to-image registration, identify the necessary anatomical structures and define a safe DCA trajectory using patient image data (typically computed tomography (CT) or cone beam CT) is required. To this end, a dedicated end-to-end software planning system for the planning of DCA procedures that addresses current deficiencies has been developed. METHODS :    Efficient and robust anatomical segmentation is achieved through the implementation of semiautomatic algorithms; high-accuracy patient-to-image registration is achieved via an automated model-based fiducial detection algorithm and functionality for the interactive definition of a safe drilling trajectory based on case-specific drill positioning uncertainty calculations was developed. RESULTS :    The accuracy and safety of the presented software tool were validated during the conduction of eight DCA procedures performed on cadaver heads. The plan for each ear was completed in less than 20 min, and no damage to vital structures occurred during the procedures. The integrated fiducial detection functionality enabled final positioning accuracies of [Formula: see text] mm. CONCLUSIONS :    Results of this study demonstrated that the proposed software system could aid in the safe planning of a DCA tunnel within an acceptable time.

QUANTUM CORRELATIONS OF LIGHTS IN MACROSCOPIC ENVIRONMENTS

This dissertation presents a detailed study in exploring quantum correlations of lights in macroscopic environments. We have explored quantum correlations of single photons, weak coherent states, and polarization-correlated/polarization-entangled photons in macroscopic environments. These included macroscopic mirrors, macroscopic photon number, spatially separated observers, noisy photons source and propagation medium with loss or disturbances. We proposed a measurement scheme for observing quantum correlations and entanglement in the spatial properties of two macroscopic mirrors using single photons spatial compass state. We explored the phase space distribution features of spatial compass states, such as chessboard pattern by using the Wigner function. The displacement and tilt correlations of the two mirrors were manifested through the propensities of the compass states. This technique can be used to extract Einstein-Podolsky-Rosen correlations (EPR) of the two mirrors. We then formulated the discrete-like property of the propensity Pb(m,n), which can be used to explore environmental perturbed quantum jumps of the EPR correlations in phase space. With single photons spatial compass state, the variances in position and momentum are much smaller than standard quantum limit when using a Gaussian TEM00 beam. We observed intrinsic quantum correlations of weak coherent states between two parties through balanced homodyne detection. Our scheme can be used as a supplement to decoy-state BB84 protocol and differential phase-shift QKD protocol. We prepared four types of bipartite correlations ±cos2(θ12) that shared between two parties. We also demonstrated bits correlations between two parties separated by 10 km optical fiber. The bits information will be protected by the large quantum phase fluctuation of weak coherent states, adding another physical layer of security to these protocols for quantum key distribution. Using 10 m of highly nonlinear fiber (HNLF) at 77 K, we observed coincidence to accidental-coincidence ratio of 130±5 for correlated photon-pair and Two-Photon Interference visibility >98% entangled photon-pair. We also verified the non-local behavior of polarization-entangled photon pair by violating Clauser-Horne-Shimony-Holt Bell’s inequality by more than 12 standard deviations. With the HNLF at 300 K (77 K), photon-pair production rate about factor 3(2) higher than a 300 m dispersion-shifted fiber is observed. Then, we studied quantum correlation and interference of photon-pairs; with one photon of the photon-air experiencing multiple scattering in a random medium. We observed that depolarization noise photon in multiple scattering degrading the purity of photon-pair, and the existence of Raman noise photon in a photon-pair source will contribute to the depolarization affect. We found that quantum correlation of polarization-entangled photon-pair is better preserved than polarization-correlated photon-pair as one photon of the photon-pair scattered through a random medium. Our findings showed that high purity polarization-entangled photon-pair is better candidate for long distance quantum key distribution.