Transformations of bridging ligands in diiron complexes: unconventional routes to new functionalized multisite bound organic frames

The main scope of this Ph.D. thesis has concerned the possible transformations of bridging ligands in diiron complexes, in order to explore unconventional routes to the synthesis of new functionalized multisite bound organic frames. The results achieved during the Ph.D. can be summarized in the following points: 1) We have extended the assembling between small unsaturated molecules and bridging carbyne ligands in diiron complexes to other species. In particular, we have investigated the coupling between olefins and thiocarbyne, leading to the synthesis of thioallylidene bridging diiron complexes. Then, we have extended the study to the coupling between olefins and aminocarbyne. This result shows that the coupling between activated olefins and heteroatom substituted bridging carbynes has a general character. 2) As we have shown, the coupling of bridging alkylidyne ligands with alkynes and alkenes provides excellent routes to the synthesis of bridging C3 hydrocarbyl ligands. As a possible extension of these results we have examined the synthesis of C4 bridging frames through the combination of bridging alkylidynes with allenes. Also in this case the reaction has a general character. 3) Diiron complexes bearing bridging functionalized C3 organic frames display the presence of donor atoms, such as N and S, potentially able to coordinate unsaturated metal fragments. Thus, we have studied the possibility for these systems to act as ‘organometallic ligands’, in particular towards Pd and Rh. 4) The possibility of releasing the organic frame from the bridging coordination appears particularly appealing in the direction of a metal-assisted organic synthesis. Within this field, we have investigated the possibility of involving the C3 bridging ligand in cycloaddition reactions with alkynes, with the aim of generating variously functionalized five-membered cycles. The [3+2] cyclization does not lead to the complete release of the organic fragment but rather it produces its transformation into a cyclopentadienyl ring, which remains coordinated to one Fe atom. This result introduces a new approach to the formation of polyfunctionalised ferrocenes. 5) Furthermore, I have spent a research period of about six months at the Department of Inorganic Chemistry of the Barcelona University, under the supervision of Prof. Concepción López, with the aim of studying the chemistry of polydentate ferrocenyl ligands and their use in organometallic synthesis.

Automatisierte Flüssigchromatographie mit Säulenschaltung und Ultraviolettspektroskopie oder Massenspektrometrie für therapeutisches Drug Monitoring von Antipsychotika und Antidepressiva

Therapeutisches Drug Monitoring (TDM) wird zur individuellen Dosiseinstellung genutzt, um die Effizienz der Medikamentenwirkung zu steigern und das Auftreten von Nebenwirkungen zu senken. Für das TDM von Antipsychotika und Antidepressiva besteht allerdings das Problem, dass es mehr als 50 Medikamente gibt. Ein TDM-Labor muss dementsprechend über 50 verschiedene Wirkstoffe und zusätzlich aktive Metaboliten messen. Mit der Flüssigchromatographie (LC oder HPLC) ist die Analyse vieler unterschiedlicher Medikamente möglich. LC mit Säulenschaltung erlaubt eine Automatisierung. Dabei wird Blutserum oder -plasma mit oder ohne vorherige Proteinfällung auf eine Vorsäule aufgetragen. Nach Auswaschen von störenden Matrixbestandteilen werden die Medikamente auf einer nachgeschalteten analytischen Säule getrennt und über Ultraviolettspektroskopie (UV) oder Massenspektrometrie (MS) detektiert. Ziel dieser Arbeit war es, LC-Methoden zu entwickeln, die die Messung möglichst vieler Antipsychotika und Antidepressiva erlaubt und die für die TDM-Routine geeignet ist. Eine mit C8-modifiziertem Kieselgel gefüllte Säule (20 µm 10x4.0 mm I.D.) erwies sich in Vorexperimenten als optimal geeignet bezüglich Extraktionsverhalten, Regenerierbarkeit und Stabilität. Mit einer ersten HPLC-UV-Methode mit Säulenschaltung konnten 20 verschiedene Psychopharmaka einschließlich ihrer Metabolite, also insgesamt 30 verschiedene Substanzen quantitativ erfasst werden. Die Analysenzeit betrug 30 Minuten. Die Vorsäule erlaubte 150 Injektionen, die analytische Säule konnte mit mehr als 300 Plasmainjektionen belastet werden. Abhängig vom Analyten, musste allerdings das Injektionsvolumen, die Flussrate oder die Detektionswellenlänge verändert werden. Die Methode war daher für eine Routineanwendung nur eingeschränkt geeignet. Mit einer zweiten HPLC-UV-Methode konnten 43 verschiedene Antipsychotika und Antidepressiva inklusive Metaboliten nachgewiesen werden. Nach Vorreinigung über C8-Material (10 µm, 10x4 mm I.D.) erfolgte die Trennung auf Hypersil ODS (5 µm Partikelgröße) in der analytischen Säule (250x4.6 mm I.D.) mit 37.5% Acetonitril im analytischen Eluenten. Die optimale Flussrate war 1.5 ml/min und die Detektionswellenlänge 254 nm. In einer Einzelprobe, konnten mit dieser Methode 7 bis 8 unterschiedliche Substanzen gemessen werden. Für die Antipsychotika Clozapin, Olanzapin, Perazin, Quetiapin und Ziprasidon wurde die Methode validiert. Der Variationskoeffizient (VK%) für die Impräzision lag zwischen 0.2 und 6.1%. Im erforderlichen Messbereich war die Methode linear (Korrelationskoeffizienten, R2 zwischen 0.9765 und 0.9816). Die absolute und analytische Wiederfindung lagen zwischen 98 und 118 %. Die für das TDM erforderlichen unteren Nachweisgrenzen wurden erreicht. Für Olanzapin betrug sie 5 ng/ml. Die Methode wurde an Patienten für das TDM getestet. Sie erwies sich für das TDM als sehr gut geeignet. Nach retrospektiver Auswertung von Patientendaten konnte erstmalig ein möglicher therapeutischer Bereich für Quetiapin (40-170 ng/ml) und Ziprasidon (40-130 ng/ml) formuliert werden. Mit einem Massenspektrometer als Detektor war die Messung von acht Neuroleptika und ihren Metaboliten möglich. 12 Substanzen konnten in einem Lauf bestimmt werden: Amisulprid, Clozapin, N-Desmethylclozapin, Clozapin-N-oxid, Haloperidol, Risperidon, 9-Hydroxyrisperidon, Olanzapin, Perazin, N-Desmethylperazin, Quetiapin und Ziprasidon. Nach Vorreinigung mit C8-Material (20 µm 10x4.0 mm I.D.) erfolgte die Trennung auf Synergi MAX-RP C12 (4 µm 150 x 4.6 mm). Die Validierung der HPLC-MS-Methode belegten einen linearen Zusammenhang zwischen Konzentration und Detektorsignal (R2= 0,9974 bis 0.9999). Die Impräzision lag zwischen 0.84 bis 9.78%. Die für das TDM erforderlichen unteren Nachweisgrenzen wurden erreicht. Es gab keine Hinweise auf das Auftreten von Ion Suppression durch Matrixbestandteile. Die absolute und analytische Wiederfindung lag zwischen 89 und 107 %. Es zeigte sich, dass die HPLC-MS-Methode ohne Modifikation erweitert werden kann und anscheinend mehr als 30 verschiedene Psychopharmaka erfasst werden können. Mit den entwickelten flüssigchromatographischen Methoden stehen neue Verfahren für das TDM von Antipsychotika und Antidepressiva zur Verfügung, die es erlauben, mit einer Methode verschiedene Psychopharmaka und ihre aktiven Metabolite zu messen. Damit kann die Behandlung psychiatrischer Patienten insbesondere mit Antipsychotika verbessert werden.

DiepRuR

Aufbau einer föderativen Dienstlandschaft in der Ruhr-Region auf Basis von SAML mit dem Ziel eine organisationsübergreifende Nutzung von webbasierten IT-Diensten zu ermöglichen

Ankle dorsiflexion arthrodesis to salvage Chopart's amputation with anterior skin insufficiency

BACKGROUND In Chopart-level amputations the heel often deviates into equinus and varus when, due to the lack of healthy anterior soft tissue, rebalancing tendon transfers to the talar head are not possible. Consequently, anterior and lateral wound dehiscence and ulceration may occur requiring higher-level amputation to achieve wound closure, with considerable loss of function for the patients. METHODS Twenty-four consecutive patients (15 diabetes, 6 trauma, and 3 tumor) had Chopart's amputation and simultaneous or delayed additional ankle dorsiflexion arthrodesis to allow for tension-free wound closure or soft tissue reconstruction, or to treat secondary recurrent ulcerations. Percutaneous Achilles tendon lengthening and subtalar arthrodesis were added as needed. Wound healing problems, time to fusion and full weight-bearing in the prosthesis, complications in the prosthesis, and the ambulatory status were assessed. Satisfaction and function were evaluated by the AmpuPro score and the validated Prosthesis Evaluation Questionnaire scale. RESULTS Five patients had successful soft tissue healing and fusions but died of their underlying disease 2 to 46 months after the operation. Two diabetic patients required a transtibial amputation. The other 17 patients were followed for 27 months (range, 13-63). The average age of the 4 women and 13 men was 53.9 years (range, 16-87). Postoperative complications included minor wound healing problems in 8 patients, wound breakdown requiring revision in 4, phantom pain in 3, residual equinus in 1, and adjacent scar carcinoma in 1 patient. The time to full weight-bearing in the prosthesis ranged from 6 to 24 weeks (mean 10). The mean AmpuPro score was 107 points (of 120), and the mean Prosthesis Evaluation Questionnaire scale was 147 points (of 200). No complications occurred with the prosthesis. Twelve patients lost 1 to 2 mobility classes (mean 0.9). The arthrodeses all healed within 2.5 months (range, 1.5 to 5 months). CONCLUSION Adding an ankle arthrodesis to a Chopart's amputation either immediately or in a delayed fashion to treat anterior soft tissue complications was a successful salvage in most patients at this amputation level. It enabled the patients to preserve the advantages of a full-length limb with terminal weight-bearing. LEVEL OF EVIDENCE Level IV, retrospective case series.

The SanaViz: Human Centered Geovisualization to facilitate visual exploration of Public Health data

These three manuscripts are presented as a PhD dissertation for the study of using GeoVis application to evaluate telehealth programs. The primary reason of this research was to understand how the GeoVis applications can be designed and developed using combined approaches of HC approach and cognitive fit theory and in terms utilized to evaluate telehealth program in Brazil. First manuscript The first manuscript in this dissertation presented a background about the use of GeoVisualization to facilitate visual exploration of public health data. The manuscript covered the existing challenges that were associated with an adoption of existing GeoVis applications. The manuscript combines the principles of Human Centered approach and Cognitive Fit Theory and a framework using a combination of these approaches is developed that lays the foundation of this research. The framework is then utilized to propose the design, development and evaluation of “the SanaViz” to evaluate telehealth data in Brazil, as a proof of concept. Second manuscript The second manuscript is a methods paper that describes the approaches that can be employed to design and develop “the SanaViz” based on the proposed framework. By defining the various elements of the HC approach and CFT, a mixed methods approach is utilized for the card sorting and sketching techniques. A representative sample of 20 study participants currently involved in the telehealth program at the NUTES telehealth center at UFPE, Recife, Brazil was enrolled. The findings of this manuscript helped us understand the needs of the diverse group of telehealth users, the tasks that they perform and helped us determine the essential features that might be necessary to be included in the proposed GeoVis application “the SanaViz”. Third manuscript The third manuscript involved mix- methods approach to compare the effectiveness and usefulness of the HC GeoVis application “the SanaViz” against a conventional GeoVis application “Instant Atlas”. The same group of 20 study participants who had earlier participated during Aim 2 was enrolled and a combination of quantitative and qualitative assessments was done. Effectiveness was gauged by the time that the participants took to complete the tasks using both the GeoVis applications, the ease with which they completed the tasks and the number of attempts that were taken to complete each task. Usefulness was assessed by System Usability Scale (SUS), a validated questionnaire tested in prior studies. In-depth interviews were conducted to gather opinions about both the GeoVis applications. This manuscript helped us in the demonstration of the usefulness and effectiveness of HC GeoVis applications to facilitate visual exploration of telehealth data, as a proof of concept. Together, these three manuscripts represent challenges of combining principles of Human Centered approach, Cognitive Fit Theory to design and develop GeoVis applications as a method to evaluate Telehealth data. To our knowledge, this is the first study to explore the usefulness and effectiveness of GeoVis to facilitate visual exploration of telehealth data. The results of the research enabled us to develop a framework for the design and development of GeoVis applications related to the areas of public health and especially telehealth. The results of our study showed that the varied users were involved with the telehealth program and the tasks that they performed. Further it enabled us to identify the components that might be essential to be included in these GeoVis applications. The results of our research answered the following questions; (a) Telehealth users vary in their level of understanding about GeoVis (b) Interaction features such as zooming, sorting, and linking and multiple views and representation features such as bar chart and choropleth maps were considered the most essential features of the GeoVis applications. (c) Comparing and sorting were two important tasks that the telehealth users would perform for exploratory data analysis. (d) A HC GeoVis prototype application is more effective and useful for exploration of telehealth data than a conventional GeoVis application. Future studies should be done to incorporate the proposed HC GeoVis framework to enable comprehensive assessment of the users and the tasks they perform to identify the features that might be necessary to be a part of the GeoVis applications. The results of this study demonstrate a novel approach to comprehensively and systematically enhance the evaluation of telehealth programs using the proposed GeoVis Framework.

Hyperspectral images and polymerase chain reaction (PCR) for the detection of allergen (peanuts traces) in powder foods.

The addition of preservatives to some kind of foods may be a potential risk of spoilage, as it is the transformation of sorbate into the off-odour 1-3-pentadiene by certain microbial species. This is the case of the capacity of some strains of moulds and yeasts that are able to decarboxylate sorbic acid and transform it into 1-3 pentadiene, a volatile compound with an unpleasant petroleum odour. (Casas et al. 2004).

Detección de grietas en placas con técnicas multifrecuencia

Safety is one of the most important feature in the aviation industry, and this involves too many factors. One of these is the aircraft maintenance. Over time, the procedures have been changing, and improving themselves. Non Destructive Testing (NDT) appeared in the late 19th century as a great option, because it enabled to inspect any structure without damaging it. Nowadays, there are several kinds of NDT, but ultrasound is one of the most widely used. This Master Thesis is devoted to an innovative ultrasound technique for crack detection. A technique, whose main aim lies in getting a good location of defects from a few measures, breaking with the currently widespread methods, as phased array. It is not necessary to use trains of waves, only discrete excitations, which means a great saving of time and energy. This work is divided into two steps: the first is to develop a multiphysics simulator, which is able to solve linear elasticity 3D problems (via Finite Element Method, FEM). This simulator allows to obtain in a computationally efficient way the displacement field for different frequencies and excitations. The solution of this elastic problem is needed to be used in the second step, which consists of generating a code that implements a mathematical tool named topological derivative, allowing to locate defects in the studied domain. In this work, the domain is a plate, and the defect is a hidden spherical void. The simulator has been developed using open source software (Elmer, Gmsh, ...), achieving a highly versatile simulator, which allows to change the configuration easily: domain size and shape, number and position of transducers, etc. Just one comercial software is used, Matlab. It is used to implement the topological derivative. In this work, the performance of the method is tested in several examples comparing the results when one or more frequencies are considered for different configurations of emisors/receptors.

Entre économie de la fonctionnalité et monopole : la United Shoe Machinery Company dans la première moitié du XXe siècle

L’histoire de la United Shoe Machinery Company (USMC) montre que la réalité ne s’adapte pas toujours aux simplifications de la théorie. Comme le signale l’économie de la fonctionnalité, la stratégie de l’entreprise de vendre l’usage plutôt que la machine fournit plusieurs avantages importants, mais elle a également contribué au fait que les usines de chaussures subissent une véritable dépendance technologique de cette compagnie et au fait que l’USMC soit parvenue à une domination monopolistique du marché. D’autre part, en remettant en cause les rudiments généraux de la théorie économique néoclassique, cette position de monopole n’a pas empêché que l’entreprise ait un fonctionnement efficace et ait facilité la modernisation technologique de l’industrie de la chaussure, aux États-Unis et dans d’autres pays.

Post-European Parliament Elections Analysis

The 2014 European Parliament Elections might turn out to be not as "historic" as some people had predicted but many questions still need answering: Was the European Parliament on the brink of an invasion by Eurosceptics? Were these groups attempting to stop the Parliament from functioning? Had 'voter fatigue' come to an end? Or was this all hyperbole - is it all business as usual? Corina Stratulat and Janis A. Emmanouilidis analysed the impact and consequences of the 2014 European Parliament elections.

Analisi di una simulazione aziendale svolta da Claudio D’Anna gruppo ufficio sinistri

Tesi di Claudio D'Anna sulla simulazione aziendale web-based: Business Game. Analisi delle giocate del gruppo UFFICIO SINISTRI collegate all'area di Marketing Operativo.

Process orientation and information technology:customer engagement at Xerox (UK) Ltd

Xerox Customer Engagement activity is informed by the "Go To Market" strategy, and "Intelligent Coverage" sales philosophy. The realisation of this philosophy necessitates a sophisticated level of Market Understanding, and the effective integration of the direct channels of Customer Engagement. Sophisticated Market Understanding requires the mapping and coding of the entire UK market at the DMU (Decision Making Unit) level, which in turn enables the creation of tailored coverage prescriptions. Effective Channel Integration is made possible by the organisation of Customer Engagement work according to a single, process defined structure: the Selling Process. Organising by process facilitates the discipline of Task Substitution, which leads logically to creation of Hybrid Selling models. Productive Customer Engagement requires Selling Process specialisation by industry sector, customer segment and product group. The research shows that Xerox's Market Database (MDB) plays a central role in delivering the Go To Market strategic aims. It is a tool for knowledge based selling, enables productive SFA (Sales Force Automation) and, in sum, is critical to the efficient and effective deployment of Customer Engagement resources. Intelligent Coverage is not possible without the MDB. Analysis of the case evidence has resulted in the definition of 60 idiographic statements. These statements are about how Xerox organise and manage three direct channels of Customer Engagement: Face to Face, Telebusiness and Ebusiness. Xerox is shown to employ a process-oriented, IT-enabled, holistic approach to Customer Engagement productivity. The significance of the research is that it represents a detailed (perhaps unequalled) level of rich description of the interplay between IT and a holistic, process-oriented management philosophy.

Innovation in outsourcing:towards a practical framework

The outsourcing industry is now up for a new challenge: to understand how innovation can be realized from outsourcing engagements. While innovation has been explored and prized within businesses for decades, it is a relatively new topic in the context of outsourcing. And, as such, the perceptions regarding what innovation in outsourcing is, what inhibits or enables innovation in outsourcing, and what client firms are willing to do to ensure they benefit from innovation in outsourcing are still being defined. This paper provides insight into some of the critical aspects in innovation in which both client firms and vendors have taken interest in recent years. We go beyond the simplistic approach we have seen in some recent reports that advocates for the development of trust and close relationships between client firms and vendors as the main enablers of innovation in outsourcing. In our view, innovation in outsourcing can be properly understood only when both contractual and relational aspects are examined as well as the nature of the innovation, i.e. incremental or radical, is explored. Further, we posit that the sourcing model applied has also an impact on the ability to innovate. © 2011 Springer-Verlag.

Preface

This edited book is intended for use by students, academics and practitioners who take interest in outsourcing and offshoring of information technology and business processes. The book offers a review of the key topics in outsourcing and offshoring, populated with practical frameworks that serve as a tool kit to students and managers. The range of topics covered in this book is wide and diverse. Various governance and coordination mechanisms for managing outsourcing relationships are discussed in great depth and the decision-making processes and considerations regarding sourcing arrangements, including multi-sourcing and cloud services, are examined. Vendors’ capabilities for managing global software development are studied in depth. Clients’ capabilities and issues related to compliance and culture are also discussed in association with various sourcing models. Topics discussed in this book combine theoretical and practical insights regarding challenges that both clients and vendors face. Case studies from client and vendor organizations are used extensively throughout the book. Last but not least, the book examines current and future trends in outsourcing and offshoring, placing particular attention on the centrality of innovation in sourcing arrangements, and how innovation can be realized in outsourcing. The book is based on a vast empirical base brought together through years of extensive research by leading researchers in information systems, strategic management and operations.

Exploring demand and production planning challenges in the food processing industry:a case study

This paper explores demand and production management challenges in the food processing industry. The goal is to identify the main production planning constraints and secondly to explore how each of these constraints affects company’s performance in terms of costs and customer service level. A single case study methodology was preferred since it enabled the collection of in-depth data. Findings suggest that product shelf life, carcass utilization and production lead time are the main constraints affecting supply chain efficiency and hence, a single planning approach is not appropriate when different products have different technological and processing characteristics.