39 resultados para Mechanisms of coordination and integration


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Large-scale introduction of Organic Solar Cells (OSCs) onto the market is currently limited by their poor stability in light and air, factors present in normal working conditions for these devices. Thus, great efforts have to be undertaken to understand the photodegradation mechanisms of their organic materials in order to find solutions that mitigate these effects. This study reports on the elucidation of the photodegradation mechanisms occurring in a low bandgap polymer, namely, Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]). Complementary analytical techniques (AFM, HS-SPME-GC-MS, UV-vis and IR spectroscopy) have been employed to monitor the modification of the chemical structure of the polymer upon photooxidative aging and the subsequent consequences on its architecture and nanomechanical properties. Furthermore, these different characterization techniques have been combined with a theoretical approach based on quantum chemistry to elucidate the evolution of the polymer alkyl side chains and backbone throughout exposure. Si-PCPDTBT is shown to be more stable against photooxidation than the commonly studied p-type polymers P3HT and PCDTBT, while modeling demonstrated the benefits of using silicon as a bridging atom in terms of photostability. (Figure Presented).

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Protein oxidation is increasingly recognised as an important modulator of biochemical pathways controlling both physiological and pathological processes. While much attention has focused on cysteine modifications in reversible redox signalling, there is increasing evidence that other protein residues are oxidised in vivo with impact on cellular homeostasis and redox signalling pathways. A notable example is tyrosine, which can undergo a number of oxidative post-translational modifications to form 3-hydroxy-tyrosine, tyrosine crosslinks, 3-nitrotyrosine and halogenated tyrosine, with different effects on cellular functions. Tyrosine oxidation has been studied extensively in vitro, and this has generated detailed information about the molecular mechanisms that may occur in vivo. An important aspect of studying tyrosine oxidation both in vitro and in biological systems is the ability to monitor the formation of oxidised derivatives, which depends on a variety of analytical techniques. While antibody-dependent techniques such as ELISAs are commonly used, these have limitations, and more specific assays based on spectroscopic or spectrometric techniques are required to provide information on the exact residues modified and the nature of the modification. These approaches have helped understanding of the consequences of tyrosine oxidation in biological systems, especially its effects on cell signalling and cell dysfunction, linking to roles in disease. There is mounting evidence that tyrosine oxidation processes are important in vivo and can contribute to cellular pathology.

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In dimensional metrology, often the largest source of uncertainty of measurement is thermal variation. Dimensional measurements are currently scaled linearly, using ambient temperature measurements and coefficients of thermal expansion, to ideal metrology conditions at 20˚C. This scaling is particularly difficult to implement with confidence in large volumes as the temperature is unlikely to be uniform, resulting in thermal gradients. A number of well-established computational methods are used in the design phase of product development for the prediction of thermal and gravitational effects, which could be used to a greater extent in metrology. This paper outlines the theory of how physical measurements of dimension and temperature can be combined more comprehensively throughout the product lifecycle, from design through to the manufacturing phase. The Hybrid Metrology concept is also introduced: an approach to metrology, which promises to improve product and equipment integrity in future manufacturing environments. The Hybrid Metrology System combines various state of the art physical dimensional and temperature measurement techniques with established computational methods to better predict thermal and gravitational effects.

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Purpose: To establish and sustain their KM programs organizations need to establish mechanisms to ensure their governance. KM programs require business integration, senior management involvement and decision making authority. The present research investigates the KM governance mechanisms organizations use to guide and control their KM programs. The research seeks to contribute to a better understanding of the governance of KM and to support organizations in the development of their KM programs. Methodology: The study employs multiple case research methodology to analyze the KM governance arrangements of twelve international organizations and identify patterns in their governance configurations. Findings: The analysis identifies a range of structural, process and relational mechanisms that are critical for governing an organizational KM program. Different patterns among the KM governance mechanisms are identified which lead to the development of generic KM governance typologies. Research implications: The development of the KM governance framework allows future research to systematically investigate the KM governance phenomenon. As the present study is based on a configurational analysis future research should particularly target the performance implications of different KM governance configurations. Practical implications: The research provides insights into the diversity of KM governance mechanisms and their impact on a KM program. The KM governance framework can assist managers in reviewing their present and prospective KM programs and thereby support benchmarking or re-organization efforts. Originality: Building on prior research that has focused on individual KM governance aspects, the present study adopts a comprehensive perspective integrating structural, process and relational governance mechanisms.

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Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

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Waste biomass is generated during the conservation management of semi-natural habitats, and represents an unused resource and potential bioenergy feedstock that does not compete with food production. Thermogravimetric analysis was used to characterise a representative range of biomass generated during conservation management in Wales. Of the biomass types assessed, those dominated by rush (Juncus effuses) and bracken (Pteridium aquilinum) exhibited the highest and lowest volatile compositions respectively and were selected for bench scale conversion via fast pyrolysis. Each biomass type was ensiled and a sub-sample of silage was washed and pressed. Demineralization of conservation biomass through washing and pressing was associated with higher oil yields following fast pyrolysis. The oil yields were within the published range established for the dedicated energy crops miscanthus and willow. In order to examine the potential a multiple output energy system was developed with gross power production estimates following valorisation of the press fluid, char and oil. If used in multi fuel industrial burners the char and oil alone would displace 3.9 × 105 tonnes per year of No. 2 light oil using Welsh biomass from conservation management. Bioenergy and product development using these feedstocks could simultaneously support biodiversity management and displace fossil fuels, thereby reducing GHG emissions. Gross power generation predictions show good potential.

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Based on a review of the servant leadership, well-being, and performance literatures, the first study develops a research model that examines how and under which conditions servant leadership is related to follower performance and well-being alike. Data was collected from 33 leaders and 86 of their followers working in six organizations. Multilevel moderated mediation analyses revealed that servant leadership was indeed related to eudaimonic well-being and lead-er-rated performance via followers’ positive psychological capital, but that the strength and di-rection of the examined relationships depended on organizational policies and practices promot-ing employee health, and in the case of follower performance on a developmental team climate, shedding light on the importance of the context in which servant leadership takes place. In addi-tion, two more research questions resulted from a review of the training literature, namely how and under which conditions servant leadership can be trained, and whether follower performance and well-being follow from servant leadership enhanced by training. We subsequently designed a servant leadership training and conducted a longitudinal field experiment to examine our sec-ond research question. Analyses were based on data from 38 leaders randomly assigned to a training or control condition, and 91 of their followers in 36 teams. Hierarchical linear modeling results showed that the training, which addressed the knowledge of, attitudes towards, and ability to apply servant leadership, positively affected leader and follower perceptions of servant leader-ship, but in the latter case only when leaders strongly identified with their team. These findings provide causal evidence as to how and when servant leadership can be effectively developed. Fi-nally, the research model of Study 1 was replicated in a third study based on 58 followers in 32 teams drawn from the same population used for Study 2, confirming that follower eudaimonic well-being and leader-rated performance follow from developing servant leadership via increases in psychological capital, and thus establishing the directionality of the examined relationships.

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Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.