Dissertationen zum Thema „Hybrid complete“
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Wayson, Michael B. „Complete internal photon dosimetry characterization of the University of Florida newborn hybrid computational phantoms“. [Gainesville, Fla.] : University of Florida, 2009. http://purl.fcla.edu/fcla/etd/UFE0041356.
Der volle Inhalt der QuelleQazali, Ahmad A. „Surface changes and screw loosening of the titanium abutments for one-piece implant supported fixed complete denture“. The Ohio State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=osu1466018689.
Der volle Inhalt der QuelleTran, Trong Hieu. „Méthodes d'optimisation hybrides pour des problèmes de routages avec profits“. Electronic Thesis or Diss., Toulouse 3, 2023. http://www.theses.fr/2023TOU30367.
Der volle Inhalt der QuelleCombinatorial optimization is an essential branch of computer science and mathematical optimization that deals with problems involving a discrete and finite set of decision variables. In such problems, the main objective is to find an assignment that satisfies a set of specific constraints and optimizes a given objective function. One of the main challenges is that these problems can be hard to solve in practice. In many cases, incomplete methods are preferred to complete methods since the latter may have difficulties in solving large-scale problems within a limited amount of time. On the other hand, incomplete methods can quickly produce high-quality solutions, which is a critical point in numerous applications. In this thesis, we investigate hybrid approaches that enhance incomplete search by exploiting complete search techniques. For this, we deal with a concrete case study, which is the vehicle routing problem with profits. In particular, we aim to boost incomplete search algorithms by extracting some knowledge during the search process and reasoning with the knowledge acquired in the past. The core idea is two-fold: (i) to learn conflicting solutions (that violate some constraints or that are suboptimal) and exploit them to avoid reconsidering the same solutions and guide search, and (ii) to exploit good features of elite solutions in order to hopefully generate new solutions having a higher quality. Furthermore, we investigate the development of a generic framework by decomposing and exchanging information between sub-modules to efficiently solve complex routing problems possibly involving optional customers, multiple vehicles, multiple time windows, multiple side constraints, and/or time-dependent transition times. The effectiveness of the approaches proposed is shown by various experiments on both standard benchmarks (e.g., the Orienteering Problem and its variants) and real-life datasets from the aerospace domain (e.g., the Earth Observation Satellite scheduling problem), and possibly involving uncertain profits
Ben, Salah Jaâfar. „Analyse et commande des systèmes non linéaires complexes : application aux systèmes dynamiques à commutation“. Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00599364.
Der volle Inhalt der QuelleJones, Claire Frances. „Lanthanide complexes of bulky hybrid ligands“. Thesis, University of Newcastle upon Tyne, 2017. http://hdl.handle.net/10443/4009.
Der volle Inhalt der QuelleRomanenko, Iuliia. „Preparation of well-defined Ir(I)-NHC based catalytic material for the hydrogenation of functional olefins“. Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10262/document.
Der volle Inhalt der QuelleAlkene hydrogenation is a key in many bulk and fine chemicals production processes. Major efforts were therefore directed towards the preparation of ever more productive and selective catalysts. Among the large number of homogeneous and heterogeneous catalysts, promising Iridium (I) organometallic complexes were prepared since the discovery of the well-known Crabtree’s catalyst, [Ir(COD)(py)(PCy3)]BF4, to address selectivity issues in homogeneous asymmetric hydrogenation or hydrogenation of highly hindered tetrasubstituted olefins. However, the industrial use of Ir organometallic complexes as catalysts is limited by their fast decomposition leading to the formation of highly stable and inactive polynuclear iridium hydridebridged complexes. The goal of this PhD project was to elaborate supported Ir(I)-NHC catalytic material to prevent such bimolecular deactivation processes. The targeted supported Ir complexes were based on hybrid organic-inorganic material containing regularly distributed imidazolium units along the pore-channels of the silica framework. Beside the Ir-site isolation on the silica support, this catalytic system was also expected to ease catalyst recovery at the end of the hydrogenation. The preparation of the final systems relies on the preparation of supported silver carbenes first, and further transmetallation with an Ir-precursor, namely [Ir(COD)Cl]2. The materials were characterized by several techniques as for example advanced solid state NMR using Dynamic Nuclear Polarization to gain insight into the molecular structure of the Ir surface sites. Catalytic performances of the supported Ir-NHC complexes were tested in alkene hydrogenation and compared to those of homogeneous homologues. Several different substrates and reaction conditions were tested. The results showed that the supported catalyst was much more stable and 50 times more active in term of rate and productivity. A polymer supported Ir-complex was also elaborated using a telechelic polyethylene iodide as support. The polymeric materials were fully characterized by NMR and MALDI-TOF experiments and their catalytic performances were compared to those of molecular analogues and those of silica supported systems
Adimoolam, Santosh Arvind. „A Calculus of Complex Zonotopes for Invariance and Stability Verification of Hybrid Systems“. Thesis, Université Grenoble Alpes (ComUE), 2018. http://www.theses.fr/2018GREAM027/document.
Der volle Inhalt der QuelleComputing reachable sets is a de facto approach used in many formal verification methods for hybrid systems. But exact computation of the reachable set is an in- tractable problem for many kinds of hybrid systems, either due to undecidability or high computational complexity. Alternatively, quite a lot of research has been focused on using set representations that can be efficiently manipulated to com- pute sufficiently accurate over-approximation of the reachable set. Zonotopes are a useful set representation in reachability analysis because of their closure and low complexity for computing linear transformation and Minkowski sum operations. But for approximating the unbounded time reachable sets by positive invariants, zonotopes have the following drawback. The effectiveness of a set representation for computing a positive invariant depends on efficiently encoding the directions for convergence of the states to an equilibrium. In an affine hybrid system, some of the directions for convergence can be encoded by the complex valued eigen- vectors of the transformation matrices. But the zonotope representation can not exploit the complex eigenstructure of the transformation matrices because it only has real valued generators.Therefore, we extend real zonotopes to the complex valued domain in a way that can capture contraction along complex valued vectors. This yields a new set representation called complex zonotope. Geometrically, complex zonotopes repre- sent a wider class of sets that include some non-polytopic sets as well as polytopic zonotopes. They retain the merit of real zonotopes that we can efficiently perform linear transformation and Minkowski sum operations and compute the support function. Additionally, we show that they can capture contraction along complex valued eigenvectors. Furthermore, we develop computationally tractable approx- imations for inclusion-checking and intersection with half-spaces. Using these set operations on complex zonotopes, we develop convex programs to verify lin- ear invariance properties of discrete time affine hybrid systems and exponential stability of linear impulsive systems. Our experiments on some benchmark exam- ples demonstrate the efficiency of the verification techniques based on complex zonotopes
Hartung, Sophia. „Analyzing Protein-Nucleic Acid Complexes using Hybrid Methods“. Diss., lmu, 2008. http://nbn-resolving.de/urn:nbn:de:bvb:19-101265.
Der volle Inhalt der QuelleHarbaoui, Houda. „Ordonnancement d’un système de production industriel complexe : flow shop hybride avec des machines dédiées soumis à différentes contraintes temporelles“. Thesis, Ecole nationale supérieure Mines-Télécom Atlantique Bretagne Pays de la Loire, 2018. http://www.theses.fr/2018IMTA0114/document.
Der volle Inhalt der QuelleIncreasing profits, through the improvement of productivity and minimizing waste, is a primary objective for industrial companies. In this thesis, we are interested insolving a real complex industrial problem with time constraints. Firstly, we were interested in minimizing completion time (Cmax). Secondly, we focused on minimizing of non-recyclable waste. As a first step, we formulated the problem by mathematical models, which we solved using a solver. In a second step, we proposed an approximate method in the form of evolutionary algorithms. Both methods were applied to the two objectives mentioned above separately. Then, a third method which is a tree-search algorithm was applied only to the main objective. We tested the proposed algorithms on instances inspired from a real case; from an agri-food business, and also on instances inspired from the literature
Vo, Tan Phuoc. „Théorie du contrôle et systèmes hybrides dans un contexte cryptographique“. Phd thesis, Institut National Polytechnique de Lorraine - INPL, 2009. http://tel.archives-ouvertes.fr/tel-00452699.
Der volle Inhalt der QuelleSinn, Stephan. „Pt(II) complexes as scaffolds in supramolecular assemblies“. Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF015/document.
Der volle Inhalt der QuelleThe presented thesis focused on the synthesis and photophysical investigation of luminescent Pt(II) complexes and their resulting assemblies that form upon aggregation. Multiple supramolecular motifs were utilized in order to gain control over the assembling behavior of the square-planar complexes. Crown-ether scaffolds were tethered with the phosphorescent metal complexes rendering a supramolecular switch that can be triggered by potassium cations. Moreover, alteration of the Pt(II)-stacking arrangement upon ligand coordination was exploited to realize a chemosensor that can be employed for of differential detection of aza-heterocycles. Furthermore, the installation of a H-bond motif to a luminescent Pt(II) complex was established, which resulted in a compound forming a two-dimensional organization on graphene. Finally, amphiphilic Pt(II) complexes were synthesized that self-assemble into highly luminescent aggregates in aqueous solutions. The series of water soluble neutral and negatively charged metal complexes were characterized with respect to their photophysical parameters and their interactions with virus coat proteins
Lopes, Leandro. „Étude et caractérisation de matrices hybrides polyether-siloxane utilisées pour la libération contrôlée de Diclofenac de Sodium et de complexes à base de Platine“. Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112146/document.
Der volle Inhalt der QuelleThe capacity of hydrophilic (POE) or hydrophobic (POP) siloxane-polyether hybrid matrixes to incorporate platinum based compounds like platinum (IV) tetrachloride (PtCl₄), cisplatin (CisPt), Zeise salt and sodium diclofenac (SDF) was studied. These compounds present academic interest and are applied in cancer disease treatment (CisPt) or catalysis (Zeise salt).The decrease in melting temperature of the semi-crystalline POE1900 hybrid and the decrease of the Tg values together with the Raman results confirm the interactions between SDF and the POE chains of the hybrid matrix. The coexistence of a crystalline and amorphous hybrid phase was clearly evinced by the bimodal drug release pattern achieved for the POE1900 matrix. Optimum amounts for the preparation of homogeneous matrix with CisPt are 5.4% m/m and with PEO1900 1.8% m/m with PPO2000. The local structure of CisPt inside the matrices is preserved. SAXS measurements show that the intensity of the correlation peak between siloxane crosslinks is affected by the CisPt incorporation in the matrix. The observed decrease in intensity without shift in position is interpreted as resulting from the filling of the space between the SiO2 nodes by CisPt. The release profiles of PEO1900 matrices show that the release is independent of the CisPt concentration and that the swelling of the matrix is the dominant process for explaining the release mechanism.For hybrids incorporating (PtCl₄), it has been shown the existence of two Pt entities, a Pt(II) species and a Pt (IV) ones. The Pt(II) species is identified as(PtCl₄)²⁻ whereas the Pt(IV) species is (PtCl₄) dissolved in the matrix. The ratio of Pt(II) and Pt(IV) species is dependent on the matrix nature: The Pt(II) species is dominant for the PEO-based matrices whereas Pt(II) and Pt(IV) proportions are almost equal for matrices based on PPO. It is proposed that the (PtCl₄)²⁻ species interact with the urea groups located at the ends of the polymeric chain and with the by ether groups of the polymer chains. These interactions are facilitated by the anionic nature of the species Pt(II). The neutral species PtCl₄ interact with the matrix in the same way that the CisPt, ie by filling the empty space between the polymer chains. During release essays, the neutral PtCl₄ species is easily released in aqueous solution, the anionic Pt (II) species remaining embedded inside the matrix. As PtCl₄, the Zeise salt is soluble in matrixes giving rise to homogeneous and transparent samples. Raman spectroscopy and EXAFS show that if the Pt-Cl bonds of the hybrid are identical to those found in the Zeise salt,Pt-C₂H₄ vibrations are only identified in the samples after a ageing period. For PEO1900 hybrid matrix loaded with Zeise salt, the formation of metallic platinum was observed during the release essays.The correlation of the structural results gained on the matrices incorporating different platinum molecules with the results of the release assays evidences that the weak interaction of neutral molecules with the matrix is responsible to the fact that the release of CisPt is mainly controlled by the swelling properties of the matrix. The incorporation of anionic Pt species, as (PtCl₄)²⁻ or Zeise salt, gives rise to samples for which the amount of released Pt species are significantly lower than the one obtained for hybrids loaded with CisPt. The strong interactions between the matrix and the anionic species are responsible for the fact that the anionic species is not easily released in solution
Guadri, Ahmed. „Architecture pour la reconfiguration en temps réel des systèmes complexes“. Phd thesis, Ecole Centrale de Lille, 2009. http://tel.archives-ouvertes.fr/tel-00579518.
Der volle Inhalt der QuelleAtoini, Youssef. „New luminescent hybrid materials : synthesis and properties“. Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF004/document.
Der volle Inhalt der QuelleThe aim of this thesis is the synthesis, characterization and investigation of luminescent metalcomplexes, and in particular of Pt(II) compounds, their aggregation properties in solution but inconfined space as well. The incorporation of transition metal complexes in porous structure, and inparticular in a metal-organic framework (MOF), by post-synthesis grafting, have been investigated.Luminescence properties of amphiphilic Pt(II) complexes were enhanced inside mesoporous silicananoparticles by the creation of a confined space. Similar effect is observed by deposition offunctionalized Pt(II) complexes on gold nanoparticles surface. Luminescence of metal organicframework was tuned by post-synthetic grafting of Ir(III) and Pt(II) complexes
Cosson, Marjorie. „Stabilité du réseau électrique de distribution. Analyse du point de vue automatique d'un système complexe“. Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLC065/document.
Der volle Inhalt der QuelleTo maintain the voltage within specified limits, local control laws of distributed generators (DGs) reactive power (Q) with respect to their voltage (U) have been considered. This work studies the impact of Q(U) control laws on distribution feeders’voltage stability. An empirical study confirms the risk of voltage instability and highlights its dependence on control law parameters. To help distribution grid operators to choose these parameters, three methods assessing stability are formulated.First, a formal method based on discrete abstraction and bisimulation calculation is developed. The proposed approach yields precise results but with a high computational load. Then, to overcome this issue, an analytical criterion adapting Q(U) control laws response time with respect to grid parameters is formulated. Finally, a general criterion, valid in any cases, is established in order to be included in the grid codes. To conclude this work, extension to more complex cases is discussed
Carrara, Serena. „Towards new efficient nanostructured hybrid materials for ECL applications“. Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF016/document.
Der volle Inhalt der QuelleThis doctoral dissertation aim to develop new hybrid materials for ECL applications. In the field of metal complexes, the electrochemiluminescent properties of new Pt(II) and Ir(III) complexes were investigated as alternative of existing complexes. Passing to nanomaterials, the combination of labels and NCNDs bearing primary or tertiary groups on the surface as alternative co-reactant species resulted an interesting strategy to eliminate the toxic TPrA. In particular, NCNDs in covalently linked system with metal complexes is not only an innocent carrier for ECL active species, but act also as co-reactant in the ECL process, revealing itself an ECL self-enhancing platform. Finally, a real immunoassay for cardiac marker detection has been built with enhanced sensitivity and stability, which is of fundamental importance for biological and bio-medical detection applications. The same technology can be applied to a variety of other analytes opening the venue to other assays
Kamath, Amarjit. „Hydrothermal Synthesis and Structural Characterization of Single Crystals of Metal-Organic Hybrid Complexes“. Thesis, University of North Bengal, 2018. http://ir.nbu.ac.in/handle/123456789/2791.
Der volle Inhalt der QuelleMillan, Laurine. „Caractérisation d’inhibiteurs de complexes CDK‐cycline chez Arabidopsis thaliana“. Thesis, Paris 11, 2011. http://www.theses.fr/2011PA112149.
Der volle Inhalt der QuelleAs in all multicellular organisms, growth and development in plants require the coordination of cell production by division and cell differentiation. Progression through cell cycle is controlled by the kinase activity of CDK/cyclin complexes. Inhibitors of these complexes, CKIs, represent excellent candidates to regulate the balance between proliferation and differentiation processes during development. To get insight in the potential integrator role of CKIs, floral development was chosen as a developmental model. Using a real time quantitative PCR approach, we bring to light that during floral development of Arabidopsis thaliana, a restricted subset of CKIs was preferentially expressed. It was decided to focus our work on the two major expressed CKIs, KRP6 and KRP7. A better characterization of their expression patterns of during development was undertaken using complementary approaches such as promoter activity analysis, mRNA dynamics, protein expression and post-translational regulation analysis. Because until now ‘gain of function’ approaches have been largely applied to unravel the role of plant CKIs, our challenge was to detect a floral phenotype for KRP6 and KRP7 loss of function mutants, either using knock-out mutants or RNAi lines. We generated krp6-krp7, krp3-krp6, krp3-krp7 double mutants and krp3-krp6-krp7 triple mutant and also several RNAi lines with specifics promoters. Despite the study of these numerous lines, we were not able to highlight phenotypic effects associated with the absence of CKI function during floral development. All these results emphasis functional redundancy which appears to exist between all KRPs, thus quadruple mutant might be needed to provoke some developmental modification.In order to better understand the integrative function of KRPs during floral development, partners of KRP6 and KRP7 were assessed. Two-hybrid screens were performed to identify cDNAs from a “floral-buds-development” library encoding proteins that are able to interact with KRP6 and KRP7. Interestingly, apart from D-type cyclins, we brought to light a new type of interaction. Indeed, a sub-class of the remorin protein family was able to interact with KRP6 or KRP7 in yeast two-hybrid. Remorins are plant specific plasma membrane associated proteins with unknown function. A BiFC approach in BY-2 protoplasts allowed us to confirm remorins/KRP6-7 interactions. Furthermore, the influence of the presence of remorin proteins on KRP6/7 localisation was assessed. KRP7 is able to adopt a nucleo-cytoplasmic localisation in presence of its new partners.Finally, recent results have shown that AMPK is phosphorylating p27KIP1, KRPs functional counterpart in mammals. These phosphorylation events lead to changes in its cellular localisation and its inhibitory activity toward CDK-cyclin complexes. After in silico analysis aiming to predict potential AMPK Arabidopsis homologue SnRK1 phosphorylation sites within some KRPs protein sequences, recombinant KRP6 was used in order to perform in vitro kinase assays. Phosphorylation occurs efficiently on KRP6 when activated SnRK1 catalytic subunit is present. Furthermore, unlike in mammals, this phosphorylation event leads to an alteration of KRP6 inhibitory activity without modification of its cellular localisation. This abolition of KRP6 activity was confirmed by in planta analysis. Indeed, KRP6 overexpression phenotype can be attenuated by simultaneous SnRK1 catalytic subunit overexpression. The existence of this link between KRP6 and SnRK1 underscores a direct relationship between energy homeostasis and cell proliferation
Hoarau, Marie. „Towards new bioinorganic hybrid catalysts based on amyloid fibres“. Thesis, Toulouse 3, 2016. http://www.theses.fr/2016TOU30346/document.
Der volle Inhalt der QuelleDeveloping sustainable alternatives to catalytic systems developed to date is a key point of the Green Chemistry Principles. Among the different existing approaches, the artificial metalloenzyme strategy aims at combining the efficiency of enzymes with the versatility of chemical catalysts. In this context, we turned our interest in developing a new type of bioinorganic hybrid catalysts through incorporation of coordination complexes in amyloid fibres. These protein aggregates display unique mechanical properties that make them good candidates for applications in catalysis. In a first part, our work consisted in overexpressing amyloid-βpeptides in Escherichia coli. A new purification procedure was set up that allowed to obtain peptides in a few steps. A series of organic ligands was synthesized, as well as the corresponding Cu(II), Fe(II) and Ru(II) complexes. The interaction between amyloid fibres and metal complexes was assessed, using a set of techniques (UV-Visible, Fluorescence, NMR...). Docking studies were also conducted by molecular modelling to acquire further insights in the interaction. Finally, catalytic experiments were performed with Fe(II) complexes, showing high conversion rates for styrene oxidation reaction. Preliminary results on the final hybrid systems show that the catalytic activity of metal complexes is maintained upon incorporation within fibres. This constitutes a proof of concept for the elaboration of hybrid catalysts based on amyloid fibres
Laureau, Raphaëlle. „Genomic diversity of hybrid yeast cells upon meiosis and return to growth“. Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066684.
Der volle Inhalt der QuelleIn somatic cells, recombination between the homologous chromosomes, followed by equational segregation, leads to loss of heterozygosity events (LOH), allowing the expression of recessive alleles and the production of novel allele combinations that are potentially beneficial upon Darwinian selection. However, inter-homolog recombination in somatic cells is rare, thus reducing the potential to generate recombinants. Here, we explored the property of S. cerevisiae to enter the meiotic developmental program, induce meiotic Spo11-dependent double-strand breaks genome-wide and return to mitotic growth, a process known as Return To Growth (RTG). Whole genome sequencing of 36 RTG strains derived from the hybrid S288c/SK1 diploid strain demonstrates that the RTGs are bona fide diploids with mosaic recombined genome. Individual RTG genotypes comprised 5 to 87 homozygous regions due to loss of heterozygous (LOH) events of various lengths, varying between a few nucleotides up to several hundred kilobases. Furthermore, we show that the iteration of the RTG process orderly increments the percentage of homozygosity. Phenotype/genotype analysis of the RTG strains for the auxotrophic and arsenate resistance traits validates the potential of this procedure of genome diversification to rapidly map complex traits loci (QTLs) in diploid strains, without going through sexual reproduction
El, Beji Imen. „Caractérisation biochimique et moléculaire du complexe SCF (SKP1-CULLIN-FBOX) chez le blé tendre“. Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2011. http://tel.archives-ouvertes.fr/tel-00999477.
Der volle Inhalt der QuelleJustaud, Frédéric. „Complexes binucléaires organofers électro-actifs à pont fonctionnel pour l'électronique moléculaire“. Thesis, Rennes 1, 2013. http://www.theses.fr/2013REN1S030.
Der volle Inhalt der QuelleThis thesis highlights the conception, synthesis and studies of redox-active organoiron complexes in which the two termini Cp*(dppe)FeII/III are linked by a functional bridge. In chapter I, an original and efficient synthetic Pd(0) catalysed homocoupling procedure is reported involving mononuclear organoiron(II) intermediates allowing us to isolate [5,5’-{Cp*(dppe)Fe–C≡C}2-(μ-2,2’-bipy)]. In chapter II, a rapid and efficient synthetic access to the redox-active metallo-ligand [6,6’-{cp*(dppe)Fe–C≡C}2-(μ-2,2’-bipy)] is described. In chapter III, the synthesis and properties of a series of complexes containing bis(ethynyl)biferrocene as a bridge between different redoxactive groups is pointed out. The redox bridge acts as a molecular relay for the electronic exchange between the termini via an electron hopping pathway. In order to tune the redox potential compared with those of biferrocene, one or two organoiron groups have been substituted by the Cp(PPh3)2M (M = Ru, Os) groups. In chapter IV, works are dedicated to the hybrid system Cp*(dppe)Fe-C≡C-TTMe3. In this molecule, electronic interactions take place between the Cp*(dppe)FeII/III center and the tetrathiafulvalene core through the ethynyl bridge. The new molecule is stable under three redox states. The mono-oxidized species behaves as a mixed valence species with an electronic coupling Hab = 320 cm-1 between the two electrophores. In the fifth and final chapter, the discovery of a CH bond activation of a methyl group located on the same cycle of the TTF core and the iron acetylide for the compound [Cp*(dppe)Fe-C≡C-TTMe3](PF6)3 is reported. This new reaction allows the synthesis of the multicomponent molecule [Cp*(dppe)Fe=C=C=TTFMe2=CH-CH=TTFMe2=C=C=Fe(dppe)Cp*][PF6]2 in good yield. The resulting device displays specific properties analysed with the support of the quantum chemistry
Kaloun, Adham. „Conception de chaînes de traction hybrides et électriques par optimisation sur cycles routiers“. Thesis, Ecole centrale de Lille, 2020. http://www.theses.fr/2020ECLI0019.
Der volle Inhalt der QuelleDesigning hybrid powertrains is a complex task, which calls for experts from various fields. In addition to this, finding the optimal solution requires a system overview. This can be, depending on the granularity of the models at the component level, highly time-consuming. This is even more true when the system’s performance is determined by its control, as it is the case of the hybrid powertrain. In fact, various possibilities can be selected to deliver the required torque to the wheels during the driving cycle. Hence, the main obstacle is to achieve optimality while keeping the methodology fast and robust. In this work, novel approaches to exploit the full potential of hybridization are proposed and compared. The first strategy is a bi-level approach consisting of two nested optimization blocks: an external design optimization process that calculates the best fuel consumption value at each iteration, found through control optimization using an improved version of dynamic programming. Two different systemic design strategies based on the iterative scheme are proposed as well. The first approach is based on model reduction while the second approach relies on precise cycle reduction techniques. The latter enables the use of high precision models without penalizing the calculation time. A co-optimization approach is implemented afterwards which adjusts both the design variables and parameters of a new efficient rule-based strategy. This allows for faster optimization as opposed to an all-at-once approach. Finally, a meta-model based technique is explored
Staniland, Paul M. „Synthesis and characterisation of new complexes with soft donor hybrid ligands“. Thesis, Loughborough University, 2007. https://dspace.lboro.ac.uk/2134/10803.
Der volle Inhalt der QuelleShen, Yuwei. „Metal-Organic Frameworks - Spin Crossover Complexes Hybrid Architectures for VOCs Sensing“. Electronic Thesis or Diss., Université Paris sciences et lettres, 2022. http://www.theses.fr/2022UPSLS038.
Der volle Inhalt der QuelleChapter I:The first part of this chapter is dedicated to a general introduction of VOCs including their emission sources, the exposure-related health risk and the state of the art of current VOC sensing techniques. The second part explains the basics of the spin-crossover phenomenon with a special focus on the guest-induced spin crossover. The third part is devoted to a brief description of MOFs featuring their general properties and typical synthetic strategies. Lastly, the fourth section is composed of a review stating the recent progress in MOF-based optical sensors for VOCs sensing.Chapter II:This chapter involves the design of porous materials with magnetic bistability based on the impregnation of a FeIII SCO complex into a chemically robust MOF (MOF-808-Zr), denoted as SCO⊂MOF. This work contains the synthesis of the hybrid compounds with tunable SCO loading, the investigation of their switching properties and of the origin of such bistability through the perspective of molecular simulations. Additional results relating to the impact of the functionalization of the FeIII spin crossover (SCO) complex on the switching properties of the hybrid compounds, as well as the shaping process of the compounds are also detailed in this chapter.Chapter III:This chapter presents the impact of MOF topology on the switching properties of the SCO⊂MOF material. The same series of the FeIII complexes is inserted into robust Zr-based MOFs (MIP-206s). Different synthetic strategies are tested for this MOF in order to regulate its particle size. The SCO⊂MOF thin film fabrication also is finally described.Chapter IV:In the last chapter, the sensing capacities for certain VOCs of the porous switchable thin films developed in Chapters II and III are evaluated. The influence of the properties of thin films on the sensing performance is also studied.In the end, the general conclusion and perspectives are discussed. In summary, this project describes a novel strategy to construct porous switchable material based on FeIII SCO complexes and different Zr(IV)-based MOFs. The solids display promising switching properties. Fabrication of optical-active thin film using these materials has been achieved, and subsequently, their sensing capacities have also been evaluated and optimized
Vo, Tan Phuoc. „Théorie du contrôle et systèmes hybrides dans un contexte cryptographique“. Electronic Thesis or Diss., Vandoeuvre-les-Nancy, INPL, 2009. http://www.theses.fr/2009INPL079N.
Der volle Inhalt der QuelleThis manuscript deals with a specific engineering application involving hybrid dynamical systems : secure communications and cryptography. The work is motivated by the following facts. The considerable progress in communication technology during the last decades has led to an increasing need for security in information exchanges. In this context, cryptography plays a major role as information is mostly conveyed through public networks. Among a wide variety of cryptographic techniques, stream ciphers are of special interest for high speed encryption. They are mainly based on generators of complex sequences in the form of dynamical systems, which must be synchronized at the transmitter and receiver sides. The aim of this work is threefold. First, the interest of resorting to hybrid dynamical systems for the design of cryptographic primitives is motivated. Secondly, a connection between chaotic and conventional cryptography is brought out by comparing the respective algorithms proposed in the open literature. The investigation focuses on structural consideration. Control theoretical concepts, in particular left invertibility and flatness, are the central tools to this end. It is shown that the so-called message-embedding technique, consisting in injecting the information to be concealed into a dynamical system, is the most relevant technique. Furthermore, it is shown that, under the flatness condition, the resulting cipher acts as a self-synchronizing stream cipher. Finally, cryptanalytic methodologies for assessing the security of the message-embedded cryptosystem involving a special class of hybrid systems, namely the switched linear systems, are proposed. Again concepts borrowed from control theory, namely identifiability and identification, are considered. Specificities related to the context are taken into account. The variables describing the dynamical systems do not take values in a continuum unlike what usually happens in automatic control when physical models are considered. They rather take values in finite cardinality sets, especially finite fields, since an implementation in finite state machines, say computers or digital electronic devices, is expected
Bouyon, Yenda Tracy Christ. „Synthèses, analyses et applications de systèmes à base de nanoparticules hybrides Or/Thiol“. Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4761.
Der volle Inhalt der QuelleThis Ph.D. work developed the controlled synthesis and purification of hybrid gold nanoparticles AuNPs, stabilized by organic thiols that are tuning their surface properties. The targeted applications are the catalysis and in the biomedical field, requiring a thorough control of the introduced nanoobjects. Syntheses of the organic AuNPs were developed from the Brust method, using 4-hydroxymercaptophenol or 4-methylmercaptophenol, leading to stable hybrid gold nanoparticles of size 2 nm. Purified fractions were characterized using TEM, UV-visible, NMR and TG analysis, issuing key data about the gold core, the organic layer and their interactions. Among the different fractions of AuNPs, the organic thiol ligands appeared to be assembled either as a monolayer or a multilayer pattern. A new direct route for synthesis of aqueous AuNPs of size 4 nm, stabilized by 4-hydroxymercaptophenol, has been developed. The AuNPs were purified using dialysis and characterized by TEM, UV-visible, NMR and TG analysis. Organic AuNPs, exhibiting different surface properties, were impregnated into SBA-15 mesoporous silica. Adsorption isotherms and nitrogen adsorption/desorption studies were in good agreement with the homogeneous distribution of AuNPs and the significant incorporation into the porosity. Finally, exploration of the targeted applications was started. The use of organic AuNPs for alkene oxidation tends to improve the selectivity of manganese salt catalyst. In the biomedical field, the aqueous AuNPs exhibited good dispersibility into biocompatible aqueous solvents. First in-vitro assays involving human sarcoma cells line showed limited cytotoxicity and good cellular uptake
Laureau, Raphaëlle. „Genomic diversity of hybrid yeast cells upon meiosis and return to growth“. Electronic Thesis or Diss., Paris 6, 2015. http://www.theses.fr/2015PA066684.
Der volle Inhalt der QuelleIn somatic cells, recombination between the homologous chromosomes, followed by equational segregation, leads to loss of heterozygosity events (LOH), allowing the expression of recessive alleles and the production of novel allele combinations that are potentially beneficial upon Darwinian selection. However, inter-homolog recombination in somatic cells is rare, thus reducing the potential to generate recombinants. Here, we explored the property of S. cerevisiae to enter the meiotic developmental program, induce meiotic Spo11-dependent double-strand breaks genome-wide and return to mitotic growth, a process known as Return To Growth (RTG). Whole genome sequencing of 36 RTG strains derived from the hybrid S288c/SK1 diploid strain demonstrates that the RTGs are bona fide diploids with mosaic recombined genome. Individual RTG genotypes comprised 5 to 87 homozygous regions due to loss of heterozygous (LOH) events of various lengths, varying between a few nucleotides up to several hundred kilobases. Furthermore, we show that the iteration of the RTG process orderly increments the percentage of homozygosity. Phenotype/genotype analysis of the RTG strains for the auxotrophic and arsenate resistance traits validates the potential of this procedure of genome diversification to rapidly map complex traits loci (QTLs) in diploid strains, without going through sexual reproduction
Magri, Andrea. „Multifunctional complexes for molecular devices“. Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAE036/document.
Der volle Inhalt der QuelleAluminum-based organic semiconductors (OSCs) were systematically synthesized and studied by photophysical and electrochemical methods to identify a relationship between their chemical structure and electronic properties, using Alq3 as benchmark. Experimental HOMO and LUMO were compared to those computed. In addition, newly developed methods were implemented to generate morphologies and calculate charge carrier mobilities. The hole mobility of Al(Op)3 was measured in thin film transistors: 0.6-2.1×10−6 cm2V−1s−1. By photoemission spectroscopy techniques, the Co/Al(Op)3 hybrid interface was probed. Two hybrid interface states (HISs) were unraveled; the SP (spin polarization) of HIS1 is 8% higher than bare cobalt, whereas the SP of HIS2 is 4% lowered. At last, phenalenyl-based dysprosium SMMs (single-molecule magnet) were investigated. [Dy(Op)2Cl(HOp)(EtOH)] showed an energy gap of 43.8K and a quantum relaxation time of 5x10-4s
Kaloun, Adham. „Conception de chaînes de traction hybrides et électriques par optimisation sur cycles routiers“. Thesis, Centrale Lille Institut, 2020. http://www.theses.fr/2020CLIL0019.
Der volle Inhalt der QuelleDesigning hybrid powertrains is a complex task, which calls for experts from various fields. In addition to this, finding the optimal solution requires a system overview. This can be, depending on the granularity of the models at the component level, highly time-consuming. This is even more true when the system’s performance is determined by its control, as it is the case of the hybrid powertrain. In fact, various possibilities can be selected to deliver the required torque to the wheels during the driving cycle. Hence, the main obstacle is to achieve optimality while keeping the methodology fast and robust. In this work, novel approaches to exploit the full potential of hybridization are proposed and compared. The first strategy is a bi-level approach consisting of two nested optimization blocks: an external design optimization process that calculates the best fuel consumption value at each iteration, found through control optimization using an improved version of dynamic programming. Two different systemic design strategies based on the iterative scheme are proposed as well. The first approach is based on model reduction while the second approach relies on precise cycle reduction techniques. The latter enables the use of high precision models without penalizing the calculation time. A co-optimization approach is implemented afterwards which adjusts both the design variables and parameters of a new efficient rule-based strategy. This allows for faster optimization as opposed to an all-at-once approach. Finally, a meta-model based technique is explored
Kahloul, Senda. „Analyse structurale et fonctionnelle de la sous-unité SKP1 du complexe SCF (Skp1-Cullin-Fbox) chez le riz (Oryza sativa)“. Thesis, Clermont-Ferrand 2, 2012. http://www.theses.fr/2012CLF22326/document.
Der volle Inhalt der QuelleIn eukaryotes, the ubiquitin Ub/26S proteasome pathway is responsible for the selective degradation of most intracellular proteins. This cellular process is initiated by protein polyubiquitination mediated by a three-step cascade involving: an ubiquitin-activating enzyme (E1), an ubiquitin-conjugating enzyme (E2) and an ubiquitin-protein ligase (E3). The E3 ubiquitin ligases contain several classes, among which the best-known are Skp1-Cullin-F-box (SCF) complexes. The SKP1 protein binds both Cullin and F-box which recognizes specifically the target proteins. Whereas protists, fungi and some vertebrates have a single functional SKP1 gene, many animal and plant species possess multiple SKP1 homologues. Twenty one and thirty-two SKP1-related genes have been described respectively in the Arabidopsis and Oryza sativa genome. Despite the importance of the SCF complex, there have been a few reports of systematic surveys of interactions between the dozens of SKP1-like proteins and the hundreds of F-box proteins in rice. In a first step, we retrieved and analyzed 288 SKP1-like genes belonging to 17 species including the moss Physcomitrella patens, five monocots and 11 eudicots. Structural and phylogenetic analysis of rice OSK genes and other plant SKP1-like genes have indicated that the different members of the plant SKP1 can be split into different subfamily. Our analyses indicated that OSK1 and OSK20 belong to a class of SKP1 genes that contain one intron at a conserved position. In a second step, we studied expression profiles of the rice Skp1-like genes. Our EST survey indicated that OSK1 and OSK20 are the most widely represented genes in public EST databases. Meta-analysis of the expression of rice SKP1-like genes indicated that OSK genes exhibit an expression profile that was heterogeneous in terms of tissues, conditions and overall intensity. Yeast two-hybrid results revealed that OSK proteins display a differing ability to interact with F-box proteins. However, OSK1 and OSK20 seemed to interact with most F-box proteins tested. Subcellular localization studies indicated that OSK1 and OSK20 are nuclear and cytosolic proteins. Based on the results obtained in this study, we can suggest that rice OSK1 and OSK20 are likely to have similar functions as do the Arabidopsis ASK1 and ASK2 genes. Similarly, we suggest a list of functional equivalent in the other sequenced plant genomes
Réal, Eléonore. „Etude du complexe de transcription et réplication des lyssavirus“. Paris 7, 2004. http://www.theses.fr/2004PA077223.
Der volle Inhalt der QuelleLl, Yanfen. „Synthesis, Structure, and Characterization of Hybrid Solids Containing Polyoxometalates and Ruthenium Polypyridyl Complexes“. TopSCHOLAR®, 2012. http://digitalcommons.wku.edu/theses/1163.
Der volle Inhalt der QuelleRampazzi, Vincent. „Chimie de coordination du phosphore aux métaux du groupe 11 : progrès en catalyse de couplage C-N au Cu(I) et nouveaux complexes polyphosphines de l'Au(I)“. Thesis, Dijon, 2014. http://www.theses.fr/2014DIJOS025/document.
Der volle Inhalt der QuelleNowadays, sustainable development encourages chemists to develop new economic and ecologic synthesis, because natural ressources are reducing. Most exploited ressources are gas and petroleum, but precious metals are also essential. This thesis is focusing on the enhancement of gold and copper complexes, obtained in our laboratory from phosphorous-based ligands. In the first part, we will develop a new system for the N-arylation of pyrazoles from a copper complexe coordinated by a new hybrid phosphinoalkene ligand. In the second part, coordination properties of gold to different ferrocenic polyphosphine will be studied. Several new innovative complexes will be isolated, and could be used in future catalytic or luminescent studies
Oddon, Frédéric. „Les oxygénases artificielles : nouveaux outils pour la catalyse asymétrique d'oxydation d'alcènes et de thioéthers dans le cadre de la "chimie verte"“. Phd thesis, Grenoble, 2010. http://www.theses.fr/2010GRENV076.
Der volle Inhalt der QuelleMy thesis works have consisted in elaborating new catalysts, in agreement with the “green chemistry” principles, to promote the catalysis of asymmetric oxygenation of thioethers and alkenes. These new catalysts are bio-inorganic hybrids which result from the association of a protein and an iron catalyst. Our choice for the protein have consisted of the bacterial protein NikA which is able to bind the Fe(EDTA) complex. Then, we have synthesized iron complexes containing N2Py2 ligands (two amine and two pyridine moieties), a favorable environment for metal-based chemistry. On the amino moieties, were added one or two carboxyle groups to allow the recognition with NikA. The catalytic studies of these complexes in alkenes and thioethers oxidation have shown that the presence of one carboxyle moiety alter slightly the reactivity of the catalyst, but two carboxyle groups poisoned totally the catalyst. The obtention of the structure of one complex and several spectroscopic analyses have shown uncommon features for theses complexes, such as the coordination of carboxyle groups by the carbonyl moiety to the iron center, and the formation of the species Fe(II)Cl42-, as counter-ion, when the complexes are prepared with Fe(II)Cl2. The NikA/Fe(N2Py2) hybrids were tested in sulfoxidation catalysis showing an enhanced activity without (or very few) sulfone production, opposite to the corresponding complexes alone which afford both sulfoxide and sulfone. Besides, we have determined cristallographic structure of some hybrids and some novel configurations for this type of complexes have been observed. Unfortunately, we have obtained poor enantioselectivities (ee = 11%). To solve this problem, directed mutagenesis experiences, based on cristallographic structure of the hybrids and on docking studies, are envisaged. To conclude, new artificial metalloenzymes have been designed. They will serve as basis for new more optimized systems
Triger, Aurelien. „Procédé hybride cristallisation et séparation membranaire pour le traitement d'un fluide complexe (urine)“. Thesis, Toulouse, INSA, 2012. http://www.theses.fr/2012ISAT0045/document.
Der volle Inhalt der QuelleThe development of decentralized and specific sanitation system is an issue that concerns both the improvement of sanitary conditions in the poorest area of the world and the development of renewable sources of nutrients for agriculture. This study aims to provide some elements about a treatment line including crystallization and membrane separation for the treatment and valorization of urine. Crystallization allows to recover phosphorus and part of nitrogen contained in urine. Membrane separation is used in order to remove bacteria and viruses from urine. To check the potentialities of these processes some tests were performed at labscale with synthetic and real human urines.It was shown that the struvite crystallization by magnesium addition with a ratio Mg:P=1,3:1 allows recovering most of the phosphorus from urine with a very rapid kinetics (about 20s). Influence of mixing conditions, urine storage, organic matter and initial crystals in urine was studied in batch and continuous reactor. Ultrafiltrations of different pretreated urines (no pretreatment, stored urine, stored and crystallized urine) were performed with PES, PAN and PVDF membranes. Mechanisms responsible for an important flux decline during urine flitration were studied. Specific influence of particular, colloidal and soluble fraction on the flux decline was also evidenced. On these basis different possible treatment lines of urines are proposed and discussed
Irvoas, Joris. „Synthèse et assemblage de molécules hybrides complexe de ruthénium-ADN“. Toulouse 3, 2013. http://thesesups.ups-tlse.fr/2062/.
Der volle Inhalt der QuelleThe present work describe the synthesis of novel hybrid supramolecules composed of ruthenium complexes and DNA, together with their assembly. The goal was to precisely situate ruthenium trisbipyridines complexes through space, controlling their exact positions and distances by use of nucleotidic sequences. The ruthenium complex geometry put together with the possible bipyridine substitutions gave rise to the idea of three-dimensional assemblies. Two coupling strategies between the ruthenium complexes and the oligonucleotides were conceptualized : an amidation coupling and a click chemistry one. On one hand, carboxylic acid, azide or alkyne functionalized ruthenium complexes were synthesized. On the other hand, alkyne or azide modified oligonucleotides were used. From both those specific entities (i. E. Modified ruthenium complexes and modified oligonucleotides) hybrid supramolecules were synthesized using both click chemistry and amidation couplings, linking one ruthenium complex to one, two identical or two different oligonucleotides. The specific hybridization DNA property permitted the assembly of such supramolecules. Linear assemblies were made to position 1 to 7 ruthenium complexes all along a DNA duplex. The chosen oligonucleotide length and sequence allow to modulate the space between two consecutive ruthenium complexes. A star-shaped structure based on three half-complementary oligonucleotides was formed. Adding sticky ends to that peculiar structure permitted the assembly of two stars linked with an hybrid ruthenium complex-DNA molecule previously obtained. It also permitted the placement of ruthenium complexes on the periphery of such structures. Through this work, the integration and free placement of ruthenium complexes on oligonucleotidic structures was demonstrated
Gajan, David. „Sites de surface de systèmes complexes : monosites, particules supportées vs. matériaux hybrides : structure, réactivité et mécanisme de formation : un point de vue RMN“. Thesis, Lyon 1, 2010. http://www.theses.fr/2010LYO10221.
Der volle Inhalt der QuelleIn order to optimize heterogeneous catalysts through a molecular approach, whether based on single-sites or supported nanoparticles, it is necessary to access to a detailed understanding of its structures and formation mechanism. To reach this goal, classical characterization techniques (adsorption, IR, EXAFS, TEM…) have been combined with solid state NMR in order to access to the detailed structure and the dynamics of surface species. Here, we showed that the formation of well-dispersed Au(I) surface species (0.35/nm2) surrounded by hydrophobic groups (OSiMe3) by the controlled grafting of {AuN(SiMe3)2}4 and its conversion into 1.8nm gold nanoparticles supported on fully passivated silica upon a mild reduction under H2 (300°C). This system displays good activity and selectivity in air oxidation and hydrogenation reactions and provides new information on the activation of O2 on gold nanoparticles. By a similar approach, supported ruthenium nanoparticles have been prepared and characterized. Reactivity of Au and Ru nanoparticles with probe molecules (H2, phosphines, ethylene and CO) has been studied, in particular by NMR. However, the low density of these surface species, especially for supported nanoparticles is still one of the main problems, making difficult to obtain high quality NMR spectra in a reasonable time. Therefore, we have developed a method based on the enhancement of NMR signals of surface species via dipolar nuclear polarization (DNP). This very promising approach has first been applied very successfully to hybrid materials and silica; this opens new avenues in the characterization of surface species of materials and particularly heterogeneous catalysts
Rico, Santacruz Marisa. „Band gap control in hybrid titania photocatalysts“. Doctoral thesis, Universidad de Alicante, 2014. http://hdl.handle.net/10045/42201.
Der volle Inhalt der QuelleLi, Xiang. „Un modèle hybride statistique-déterministe du canal LMS en environnements complexes“. Poitiers, 2010. http://theses.edel.univ-poitiers.fr/theses/2010/Li-Xiang/2010-Li-Xiang-These.pdf.
Der volle Inhalt der QuelleThis PhD research focuses on the modeling and simulation of mobile satellite radio propagation channels in constrained areas, e. G. , build-up, urban and suburban areas. More precisely, the aim of the work is to develop a high performance model to predict the received signal behavior, in particular, the slow-fading and fast-fading. Based on a hybrid concept, we propose a novel channel model combining a deterministic approach (raytracing) and two statistical models : Nakagami-m and lognormal. The model was developed at L-band but is easily extensible to S-band. The context of this study and a state of art of the existing channel models are first introduced in chapter 1 of this thesis. After describing their advantages and drawbacks, we present the hybrid concept of our channel model. The work of chapter 2 aims at the selection of the fast-fading model. We use the Kolmogorov–Smirnov test and Kullback–Leibler test (with optimal histograms base on information theory) to compare the goodness of fit of different statistical models regarding to simulated sample signals. The third chapter is divided into two complementary studies as LOS and NLOS areas need to be modeled using optimum statistical laws. Based on deterministic simulations in Toulouse city areas using geosynchronous satellites, the channel behavior is studied from which we deduce our semi-deterministic model. It takes into account of the receiving site’s specificities and leads to dynamic statistical parameter setup. Finally, the use of the hybrid model is presented in chapter 4. We show the interest of our model by comparing the hybrid simulated signals to purely deterministically simulated ones in terms of precision and simulation time. In addition, the extensibility of our model is studied in order to use non-geosynchronous satellites
Bournez, Olivier. „Complexite algorithmique des systemes dynamiques continus et hybrides“. Lyon, École normale supérieure (sciences), 1999. http://www.theses.fr/1999ENSL0109.
Der volle Inhalt der QuelleCrivoi, Dana Georgiana. „Hybrid materials: discovering properties and mechanisms“. Doctoral thesis, Universitat Rovira i Virgili, 2016. http://hdl.handle.net/10803/386445.
Der volle Inhalt der QuelleTodo lo que nos rodea es quiral, por lo tanto, una de las propiedades más importantes que subyace en la disposición y la acción de fármacos está dada por la quiralidad de la sustancia activa. En consecuencia, la estereoquímica representa un campo activo, cambiante y desafiante que combina diferentes disciplinas de las ciencias naturales que conducen a los resultados más espectaculares. En este contexto, la presente tesis se centra en: i) el desarrollo de nuevos sistemas catalíticos para la producción de sustancias quirales, ii) la comprensión de los mecanismos de reacción posteriores, y iii) el diseño de procesos más ecológicos sostenibles. Bio-nanohíbridos con una alta variedad de propiedades se obtuvieron mediante la inmovilización de L-leucina y poli-L-leucina en el espacio entre capas de materiales del tipo hidrotalcita. Estos catalizadores son ecológicos, fáciles de sintetizar y no requieren pre-activación. Sustancias con una aplicación potencial en la industria química y farmacéutica se obtuvieron utilizando estos nanohíbridos como catalizadores, empleando un único reactor, en la reacción de adición aldólica y la reacción de condensación de Claisen-Schmidt /epoxidación Juliá-Colonna. La cooperación entre la ciencia de superficies y la catálisis permitió revelar al verdadero mecanismo de Juliá-Colonna mediante el análisis con micro-balanza de cristal de cuarzo con disipación (QCM-D). Por último, pero no menos importante, los reactores híbridos de membrana catalítica se pueden emplear en la transformación de reacciones complejas en otras más triviales, como la producción de peróxido de hidrógeno in-situ y posterior epoxidación de la calcona.
Everything around us is chiral, thus, one of the most important properties which underlies the drug disposition and action is given by the chirality of the active substance. Consequently, stereochemistry represents an active, changing, and challenging field which combines different disciplines of natural sciences that lead to the most spectacular findings. In this context, the present thesis focuses on: i) the development of new catalytic systems for the production of chiral substances, ii) the understanding of the subsequent reaction mechanisms, and iii) the design of greener sustainable processes. Bio-nanohybrid materials with a high variety of properties were obtained by immobilizing L-leucine and poly-L-leucine in the interlayer space of hydrotalcite-type materials. These catalysts are eco-friendly, are facile to synthesize, and no pre-activation is required. Substances with potential application in pharmaceutical or fine chemical industries were obtained using these nanohybrids as catalysts in the aldol addition reaction and the one-pot Claisen-Schmidt condensation / Juliá-Colonna epoxidation reaction. Cooperation between surface science and catalysis revealed the real Juliá-Colonna mechanism by using quartz crystal microbalance with dissipation (QCM-D) analysis. Last but not the least, hybrid catalytic membrane reactors can be employed in transforming complex reactions into simpler ones, like the production of hydrogen peroxide in-situ and subsequent epoxidation of chalcone.
Reynaud, Sébastien. „Modélisation hybride du canal radiomobile en environnement indoor complexe : application aux systèmes sans fil“. Limoges, 2006. http://aurore.unilim.fr/theses/nxfile/default/b4f6d9b0-26aa-432b-96fa-753d42ce5000/blobholder:0/2006LIMO0020.pdf.
Der volle Inhalt der QuelleNowadays, an increasing interest is devoted to wide-band applications like Wireless Local Area Networks (WLANs), because the present multimedia services require more high bit rate and thus large bandwidth. These needs in bandwidth involve important rise in frequency. At such frequencies and in an indoor propagation context, several objects neglicted in the channel modelisation (objects of wavelength size or with complex shapes), can disturb signal transmission. Recently, ray tracing techniques (RT), associated to the Uniform Theory of Diffraction (UTD), have emerged as the dominant techniques to predict the wide-band channel behaviour. Indeed, these asymptotic methods are fast and not limited in frequency. However, dealing with INDOOR propagation, this classical approach is not sufficient to model object of wavelength size or with complex shapes. For these structures, rigorous methods like the FDTD, consisting in solving Maxwell's equations in discrete time domain, are well-suitable. This subject deals with the elaboration of a hybrid method, combining the advantages of the UTD and the FDTD methods. On the one hand, the RT technique is used to model the wave propagation in rooms and buildings including large objects compared to wavelength. On the other hand, the furniture with small size or complex shape will be modeled by FDTD. The final goal is to determine which accuracy level of description of the environment we have to choose to get a good electromagnetic representation of the studied scene. In global terms, this subject deals with the bringing of a deterministic channel modelisation in systems' simulations
Saccucci, Laurent. „Intérêt thérapeutique de la protéine A20 des orthopoxvirus comme cible pertinente d'apatamères peptidiques et de compsés chimiques bloquant ses intéractions essentielles à l'intérieur du complexe de réplication virale“. Grenoble 1, 2009. http://www.theses.fr/2009GRE10338.
Der volle Inhalt der QuelleVariola virus (VARV), the etiologic agent of smallpox was responsible of the most devastating infectious disease. Because of successful preventive measures by immunization, the World Health Organization (WHO) declared global eradication of smallpox in 1980. The subsequent discontinuation of vaccination has rendered all children and many adults virtually susceptible to smallpox infection. If variola virus was used in an act of terrorism or warfare it could cause a real catastrophe. So it is essential to develop new antiviral molecules with different mechanisms of action and usable immediately in case of terrorist attack. Here we report the use of two original strategies to identify new effective anti-orthopoxvirus agents targeting specifically the viral replication complex of vaccinia virus (VACV), a valuable surrogate for the smallpox virus. First, through a yeast two-hybrid assay, we have selected peptide aptamers directed against the VACV A20 protein, a central component of the replication complex and shown to form, with the D4 protein, a processivity factor for the viral DNA polymerase. Peptide aptamers are combinatorial protein molecules designed to inhibit the function of target proteins in living cells. We have proved that one selected aptamer interacting with a central region of A20 was able to significantly inhibit viral DNA synthesis and viral production in cell culture. Second, we have performed a high-throughput screening of small molecules to isolate compounds capable of disrupting A20 interaction with either D4, an uracil DNA glycosylase or D5, a DNA-independent nucleoside triphosphatase (NTPase) that contains a helicase domain. The screen is based on an automated dual-luciferase yeast two-hybrid assay, performed in 384-well plates. Among a collection of 27,600 compounds from diverse commercial chemical libraries we have identified two potential inhibitors that exhibit antipoxvirus effect on infected cell culture. These compounds were also found to specifically inhibit DNA replication. Thus, the screening for inhibitors of protein-protein interactions within viral replication complex remains to be a promising strategy for identifying new compounds active against orthopoxvirus infections
Kekatos, Nikolaos. „Vérification formelle des systèmes cyber-physiques dans le processus industriel de la conception basée sur modèle“. Thesis, Université Grenoble Alpes (ComUE), 2018. http://www.theses.fr/2018GREAM081/document.
Der volle Inhalt der QuelleCyber-Physical Systems form a class of complex, large-scale systems of frequently safety-critical nature in various industrial applications. Formal verification approaches can provide performance and safety guarantees for these systems. They require three elements: a formal model, a formal verification method, and a set of formal specifications. However, industrial models are typically non-formal, they are analyzed in non-formal simulation environments, and their specifications are described in non-formal natural language. In this thesis, we aim to facilitate the integration of formal verification into the industrial model-based design process.Our first key contribution is a model transformation methodology. Starting with a standard simulation model, we transform it into an equivalent verification model, particularly a network of hybrid automata. The transformation process addresses differences in syntax, semantics, and other aspects of modeling. For this class of formal models, so-called reachability algorithms can be applied to verify safety properties. An obstacle is that scalable algorithms exist for piecewise affine (PWA) models, but not for nonlinear ones. To obtain PWA over-approximations of nonlinear dynamics, we propose a compositional syntactic hybridization technique. The result is a highly compact model that retains the modular structure of the original simulation model and largely avoids an explosion in the number of partitions.The second key contribution is an approach to encode rich formal specifications so that they can be interpreted by tools for reachability. Herein, we consider specifications expressed by pattern templates since they are close to natural language and can be easily understood by non-expert users. We provide (i) formal definitions for select patterns that respect the semantics of hybrid automata, and (ii) monitors which encode the properties as the reachability of an error state. By composing these monitors with the formal model under study, the properties can be checked by off-the-shelf fully automated verification tools.Furthermore, we provide a semi-automated toolchain and present results from case studies conducted in collaboration with industrial partners
Łomzik, Michał Pawel. „Synthesis and characterization of hybrid drugs based on ruthenium complex moiety and biologically active organic compounds“. Thesis, Université de Lorraine, 2016. http://www.theses.fr/2016LORR0338/document.
Der volle Inhalt der QuelleThe main goal of this thesis was synthesis and preliminary characterization of novel ruthenium(II) polypyridyl complexes bearing biologically active molecules as potential theranostic agents. Luminescence for the diagnostic applications, and cytotoxicity for the anticancer, therapeutic applications are considered as the theranostic properties. Four new ligands containing biologically active moieties - 5-(4-4’-methyl-[2,2’-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) were synthesized and characterized. The ligands were used to obtain nine novel ruthenium(II) polypyridyl complexes. Six complexes were synthesized with ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) and three with ligands L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2’-bipyridine, Mebpy = 4,4’-dimethyl-2,2-bipyridine, tBubpy = 4,4’-tert-butyl-2,2’-bipyridine, Phbpy = 4,4’-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). The spectroscopic and photophysical properties of those complexes were determined. The presence of ligands L1-L4 in the structure of the complex decreased luminescence quantum yield and luminescence lifetime in comparison with unmodified [Ru(bpy)3]2+ complex. The theoretical calculations have shown that ligands L1-L4 do not have influence on ruthenium core geometry. However, they increased the energy of the HOMO that resulted in a shorter band gap. The simulated electronic absorption spectra were in a good agreement with the experimental data. The interactions between the studied ruthenium complexes and human serum albumin (HSA) were investigated. All studied Ru(II) complexes exhibited strong affinity to HSA with the association constant 105 M-1s-1, which suggests formation of Ru complex-HSA adducts. It was also determined that ruthenium complexes most likely bind to the hydrophobic pocket of protein, located in Sudlow’s site I in the subdomain II A. Preliminary cytotoxicity evaluation for the studied ruthenium complexes showed their cytotoxic activity towards cancer cell lines. Those results, together with good luminescence properties of the studied ruthenium complexes (luminescence lifetimes and luminescence quantum yield) make them interesting candidates for potential theranostic applications
Ben, beldi Nesrine. „Modélisation et optimisation des systèmes complexes en conception innovante : application aux chaines de transmission hybrides“. Thesis, Paris, ENSAM, 2015. http://www.theses.fr/2015ENAM0028.
Der volle Inhalt der QuelleIn an industrial context that is continuously evolving and changing, automotive constructors find themselves obliged to develop their products by taking into account the requirements of an international market and the imposed regulations in this field. Hybrid powertrain systems fits into this constructor will to propose to customers efficient products that respects the regulation regarding gas emissions and presents a profitable low cost. Through the work done in this PhD, we propose a design approach that allow the modeling of a complex technical system in its different systemic levels during the design process, the local optimization done from professional expertise, the modeling of collaborative data exchanged between expert models and the optimization of the design space in order to converge towards an optimal design solution in innovative context.The aim of our work is to propose a new way of dealing with design problems related to complex systems that can be adapted to an innovative design context. This will allow companies such as PSA Peugeot Citroen to be able to diversify their products and integrated even the latest technology in it. This work has been illustrated and validated through the results obtained on the MTI project for the design of hybrid powertrain
TROMA, LAURENT. „Surveillance et diagnostic de systemes industriels complexes : une approche hybride numerique/symbolique“. Rennes 1, 2000. http://www.theses.fr/2000REN10009.
Der volle Inhalt der QuelleOddon, Frédéric. „Les oxygénases artificielles : nouveaux outils pour la catalyse asymétrique d'oxydation d'alcènes et de thioéthers dans le cadre de la “chimie verte”“. Phd thesis, Grenoble, 2010. http://tel.archives-ouvertes.fr/tel-00558081.
Der volle Inhalt der QuelleFerré, Romeu Meritxell. „Hybrid silica materials derived from proline sulfonamides, imidazolium salts and (NHC)AuX complexes as supported catalysts“. Doctoral thesis, Universitat Autònoma de Barcelona, 2015. http://hdl.handle.net/10803/297699.
Der volle Inhalt der QuelleLa búsqueda de reacciones orgánicas que procedan con eficiencia, selectividad y economía atómica se ha convertido en un objetivo importante para la química sintética. Además de la concienciación sobre la sostenibilidad de los procesos químicos, el uso de catalizadores soportados en química sintética ha aumentado considerablemente en los últimos años. De esta manera, la inmovilización covalente de especies catalíticas ofrece ventajas importantes. Sin embargo, la actividad catalítica de las especies soportadas se encuentra fuertemente determinada por la accesibilidad de los reactivos al centro activo. Por lo tanto, la elección del soporte es una cuestión esencial debido a que su estructura y propiedades pueden influir de forma importante en el curso de las reacciones químicas mediadas por catalizadores inmovilizados en este soporte. Los materiales híbridos orgánico-inorgánicos derivados de sílice son geles de sílice modificados con componentes orgánicos, que se han aplicado como soportes versátiles para una gran variedad de sistemas catalíticos. En el presente trabajo, varias organosílicas derivadas de prolinsulfonamidas, de sales de imidazolio y de imidazolinio y de un complejo [(NHC)AuCl] han sido preparados mediante el proceso sol-gel así como por el método de grafting. Estos materiales han sido ensayados como catalizadores soportados en diversos procesos orgánicos. Concretamente, la organocatálisis asimétrica ha sido abordada por prolinsulfonamidas soportadas, que han mostrado buenos resultados en la reacción aldólica asimétrica directa en condiciones suaves (en agua a temperatura ambiente) y han permitido su reciclaje hasta 5 ciclos consecutivos. La inmovilización de sales de imidazolio y de imidazolinio no ha permitido la generación de especies NHC para catalizar la condensación benzoínica o la reacción de anelación de un enal con una vinil-cetona. Sin embargo, la sal de imidazolio soportada se ha utilizado como organocatalizador reciclable para la protección quimioselectiva con Boc de aminas aromáticas. Por último, un complejo soportado de [(NHC)AuCl] representa el primer ejemplo de material de sílice derivado de un complejo de [(NHC)-Au(I)] que ha sido preparado mediante el proceso sol-gel. Se ha aplicado con éxito como catalizador [(NHC)Au]+, facilitando transformaciones tales como la transposición de ésteres alílicos o la cicloisomerización de ácidos γ-alquinoicos para dar lugar a enol-lactonas de 5 miembros, permitiendo su reutilización hasta 6 ciclos consecutivos en la última reacción. Además, el material híbrido derivado de sílice muestra un mejor comportamiento catalítico que el análogo homogéneo correspondiente.