POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical properties

Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction. Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère. Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie.

Electrospinning and characterization of supramolecular poly(4-vinyl pyridine)-small molecule complexes

La chimie supramoléculaire est basée sur l'assemblage non covalent de blocs simples, des petites molécules aux polymères, pour synthétiser des matériaux fonctionnels ou complexes. La poly(4-vinylpyridine) (P4VP) est l'une des composantes supramoléculaires les plus utilisées en raison de sa chaîne latérale composée d’une pyridine pouvant interagir avec de nombreuses espèces, telles que les petites molécules monofonctionnelles et bifonctionnelles, grâce à divers types d'interactions. Dans cette thèse, des assemblages supramoléculaires de P4VP interagissant par liaisons hydrogène avec de petites molécules sont étudiés, en ayant comme objectifs de faciliter l'électrofilage de polymères et de mieux comprendre et d'optimiser la photoréponse des matériaux contenant des dérivés d'azobenzène. Une nouvelle approche est proposée afin d'élargir l'applicabilité de l'électrofilage, une technique courante pour produire des nanofibres. À cet effet, un complexe entre la P4VP et un agent de réticulation bifonctionnel capable de former deux liaisons hydrogène, le 4,4'-biphénol (BiOH), a été préparé pour faciliter le processus d’électrofilage des solutions de P4VP. Pour mieux comprendre ce complexe, une nouvelle méthode de spectroscopie infrarouge (IR) a d'abord été développée pour quantifier l'étendue de la complexation. Elle permet de déterminer un paramètre clé, le rapport du coefficient d'absorption d'une paire de bandes attribuées aux groupements pyridines libres et liées par liaisons hydrogène, en utilisant la 4-éthylpyridine comme composé modèle à l’état liquide. Cette méthode a été appliquée à de nombreux complexes de P4VP impliquant des liaisons hydrogène et devrait être généralement applicable à d'autres complexes polymères. La microscopie électronique à balayage (SEM) a révélé l'effet significatif du BiOH sur la facilité du processus d’électrofilage de P4VP de masses molaires élevées et faibles. La concentration minimale pour former des fibres présentant des perles diminue dans le N, N'-diméthylformamide (DMF) et diminue encore plus lorsque le nitrométhane, un mauvais solvant pour la P4VP et un non-solvant pour le BiOH, est ajouté pour diminuer l'effet de rupture des liaisons hydrogène causé par le DMF. Les liaisons hydrogène dans les solutions et les fibres de P4VP-BiOH ont été quantifiées par spectroscopie IR et les résultats de rhéologie ont démontré la capacité de points de réticulation effectifs, analogues aux enchevêtrements physiques, à augmenter la viscoélasticité de solutions de P4VP pour mieux résister à la formation de gouttelettes. Cette réticulation effective fonctionne en raison d'interactions entre le BiOH bifonctionnel et deux chaînes de P4VP, et entre les groupements hydroxyles du BiOH complexé de manière monofonctionnelle. Des études sur d’autres agents de réticulation de faible masse molaire ont montré que la plus forte réticulation effective est introduite par des groupes d’acide carboxylique et des ions de zinc (II) qui facilitent le processus d’électrofilage par rapport aux groupements hydroxyles du BiOH. De plus, la sublimation est efficace pour éliminer le BiOH contenu dans les fibres sans affecter leur morphologie, fournissant ainsi une méthode élégante pour préparer des fibres de polymères purs dont le processus d’électrofilage est habituellement difficile. Deux complexes entre la P4VP et des azobenzènes photoactifs portant le même groupement tête hydroxyle et différents groupes queue, soit cyano (ACN) ou hydrogène (AH), ont été étudiés par spectroscopie infrarouge d’absorbance structurale par modulation de la polarisation (PM-IRSAS) pour évaluer l'impact des groupements queue sur leur performance lors de l'irradiation avec de la lumière polarisée linéairement. Nous avons constaté que ACN mène à la photo-orientation des chaînes latérales de la P4VP et des azobenzènes, tandis que AH mène seulement à une orientation plus faible des chromophores. La photo-orientation des azobenzènes diminue pour les complexes avec une teneur croissante en chromophore, mais l'orientation de la P4VP augmente. D'autre part, l'orientation résiduelle après la relaxation thermique augmente avec la teneur en ACN, à la fois pour le ACN et la P4VP, mais la tendance opposée est constatée pour AH. Ces différences suggèrent que le moment dipolaire a un impact sur la diffusion rotationnelle des chromophores. Ces résultats contribueront à orienter la conception de matériaux polymères contenant des azobenzène efficaces.

Patient-specific anisotropic model of human trunk based on MR data

There are many ways to generate geometrical models for numerical simulation, and most of them start with a segmentation step to extract the boundaries of the regions of interest. This paper presents an algorithm to generate a patient-specific three-dimensional geometric model, based on a tetrahedral mesh, without an initial extraction of contours from the volumetric data. Using the information directly available in the data, such as gray levels, we built a metric to drive a mesh adaptation process. The metric is used to specify the size and orientation of the tetrahedral elements everywhere in the mesh. Our method, which produces anisotropic meshes, gives good results with synthetic and real MRI data. The resulting model quality has been evaluated qualitatively and quantitatively by comparing it with an analytical solution and with a segmentation made by an expert. Results show that our method gives, in 90% of the cases, as good or better meshes as a similar isotropic method, based on the accuracy of the volume reconstruction for a given mesh size. Moreover, a comparison of the Hausdorff distances between adapted meshes of both methods and ground-truth volumes shows that our method decreases reconstruction errors faster. Copyright © 2015 John Wiley & Sons, Ltd.

Scanning Electron Microscopy Studies on Tear and Wear Failure of Short Kevlar Fiber-Thermoplastic- Polyurethane Composite

Tear and wear properties of short kevlar fiber, thermoplastic polcurethane (TPU) composite with respect to fiber loading-and fiber onentation has been studied and the fracture surfaces were examined under scanning electron microscope (SEM). Tear strength first decreased up to 20 phr fiber loading and then gradually increased with increasing fiber loading. Anisotropy in tear strength was evident beyond a fiber loading of 20 phr. Tear fracture surface of unfilled TPU showed sinusoidal folding characteristics of high strength matrix. At low fiber loading the tear failure was mainly due to fibermatrix failure whereas at higher fiber loading the failure occurred by fiber breakage. Abrasion loss shows a continuous rise with increasing fiber loading, the loss in the transverse orientation of fibers being higher than that in the longitudinal orientation. The abraded surface showed lone cracks and ridges parallel to the direction of abrasion indicating an abrasive wear mechanism. In the presence of fber the abrasion loss was mainly due to fiber low.

Characteristics of a Microstrip-Excited High-Permittivity Tectangular Dielectric Resonator Antenna

The radiation characteristics of a microstrip-line-excited rectangular dielectric resonator antenna (DRA) are studied experimentally.The radiation charactristics and excitation of different modes are highly influenced by the orientation of the DR,feed line parameters ,and finite size of the ground plane

Studies on the dynamics and rheology of dilute suspensions of Brownian particles in simple shear flow under the action of an external force

We present a novel approach to computing the orientation moments and rheological properties of a dilute suspension of spheroids in a simple shear flow at arbitrary Peclct number based on a generalised Langevin equation method. This method differs from the diffusion equation method which is commonly used to model similar systems in that the actual equations of motion for the orientations of the individual particles are used in the computations, instead of a solution of the diffusion equation of the system. It also differs from the method of 'Brownian dynamics simulations' in that the equations used for the simulations are deterministic differential equations even in the presence of noise, and not stochastic differential equations as in Brownian dynamics simulations. One advantage of the present approach over the Fokker-Planck equation formalism is that it employs a common strategy that can be applied across a wide range of shear and diffusion parameters. Also, since deterministic differential equations are easier to simulate than stochastic differential equations, the Langevin equation method presented in this work is more efficient and less computationally intensive than Brownian dynamics simulations.We derive the Langevin equations governing the orientations of the particles in the suspension and evolve a procedure for obtaining the equation of motion for any orientation moment. A computational technique is described for simulating the orientation moments dynamically from a set of time-averaged Langevin equations, which can be used to obtain the moments when the governing equations are harder to solve analytically. The results obtained using this method are in good agreement with those available in the literature.The above computational method is also used to investigate the effect of rotational Brownian motion on the rheology of the suspension under the action of an external force field. The force field is assumed to be either constant or periodic. In the case of con- I stant external fields earlier results in the literature are reproduced, while for the case of periodic forcing certain parametric regimes corresponding to weak Brownian diffusion are identified where the rheological parameters evolve chaotically and settle onto a low dimensional attractor. The response of the system to variations in the magnitude and orientation of the force field and strength of diffusion is also analyzed through numerical experiments. It is also demonstrated that the aperiodic behaviour exhibited by the system could not have been picked up by the diffusion equation approach as presently used in the literature.The main contributions of this work include the preparation of the basic framework for applying the Langevin method to standard flow problems, quantification of rotary Brownian effects by using the new method, the paired-moment scheme for computing the moments and its use in solving an otherwise intractable problem especially in the limit of small Brownian motion where the problem becomes singular, and a demonstration of how systems governed by a Fokker-Planck equation can be explored for possible chaotic behaviour.

Investigations on Structural response of Water Backed Perforated plates

The study envisaged herein contains the numerical investigations on Perforated Plate (PP) as well as numerical and experimental investigations on Perforated Plate with Lining (PPL) which has a variety of applications in underwater engineering especially related to defence applications. Finite element method has been adopted as the tool for analysis of PP and PPL. The commercial software ANSYS has been used for static and free vibration response evaluation, whereas ANSYS LS-DYNA has been used for shock analysis. SHELL63, SHELL93, SOLID45, SOLSH190, BEAM188 and FLUID30 finite elements available in the ANSYS library as well as SHELL193 and SOLID194 available in the ANSYS LS-DYNA library have been made use of. Unit cell of the PP and PPL which is a miniature of the original plate with 16 perforations have been used. Based upon the convergence characteristics, the utility of SHELL63 element for the analysis of PP and PPL, and the required mesh density are brought out. The effect of perforation, geometry and orientation of perforation, boundary conditions and lining plate are investigated for various configurations. Stress concentration and deflection factor are also studied. Based on these investigations, stadium geometry perforation with horizontal orientation is recommended for further analysis.Linear and nonlinear static analysis of PP and PPL subjected to unit normal pressure has been carried out besides the free vibration analysis. Shock analysis has also been carried out on these structural components. The analytical model measures 0.9m x 0.9m with stiffener of 0.3m interval. The influence of finite element, boundary conditions, and lining plate on linear static response has been estimated and presented. Comparison of behavior of PP and PPL in the nonlinear strain regime has been made using geometric nonlinear analysis. Free vibration analysis of the PP and PPL has been carried out ‘in vacuum’ condition and in water backed condition, and the influence of water backed condition and effect of perforation on natural frequency have been investigated.Based upon the studies on the vibration characteristics of NPP, PP and PPL in water backed condition and ‘in vacuum’ condition, the reduction in the natural frequency of the plate in immersed condition has been rightly brought out. The necessity to introduce the effect of water medium in the analysis of water backed underwater structure has been highlighted.Shock analysis of PP and PPL for three explosives viz., PEK, TNT and C4 has been carried out and deflection and stresses on plate as well as free field pressure have been estimated using ANSYS LS-DYNA. The effect of perforations and the effect of lining plate have been predicted. Experimental investigations of the measurement of free field pressure using PPL have been conducted in a shock tank. Free field pressure has been measured and has been validated with finite element analysis results. Besides, an experiment has been carried out on PPL, for the comparison of the static deflection predicted by finite element analysis.The distribution of the free field pressure and the estimation of differential pressure from experimentation and the provision for treating the differential pressure as the resistance, as a part of the design load for PPL, has been brought out.

Effect of Gender-role Orientations and Communication Styles on Executive Performance

Biosocial profile can produce variations in Gender-role Orientation of executives. Biosocial variables are not responsible for the development of Communication Style except in cases of number of children, dual career family and fathers occupation. Gender-role orientation is a function of Communication Style. Executive performance is a function of Communication Style.Gender- role orientation can have a decisive influence on executive performance. The cumulative effect of Communication Style and gender role orientation can produce variations in executive performance. Open Communication Style is predominantly responsible for the creation of a higher level executive performance than other Communication Styles.

Market Orientation in Indian Seafood Processing Firms

This thesis studied the impact of market orietnation on business performance, in the seafood industry, which is a unique situation wherein the firms were all 100% export oriented. The study was able to prove that in the context of the seafood indsutry, implementation of market orientation principles will lead to increase in business performance. The business performance variables were measured under two heads, namely economic performance and non-economic performance. Market orientation in Indian seafood firms was significantly and postiively related to both the performance measures. Under the non-economic performance, were the customer and employee consequences.Again market orientation was positively and significantly related to both the consequences.Thus, the implication arising from the study is this: market orientation in Indian seafood processing firms increases their business performance. The implementation of market orientation will help the seafood firms in gaining competitve advantages in exporting. This in turn will result in increased exports and the position of Indian seafood in the global market will be strengthened. It will thus become a leading player in the global fish trade. Next, the focus was on the effect of the antecedents on the market orientation of a firm. It was seen that several factors were antecedents to the adoption of market orientation principles. They include top management emphasis, conflict, centralization and reward system. It is noted that top management emphasis and support is vital to the market orientation programme. The top management needs to adopt market oriented behaviour and reinforce the need for being market oriented, for it to percolate down the line.Interdepartmental conflict is seen to affect market orientation positively. A large percent of the Indian seafood firms are traditionally family-owned companies, rather than professionally managed firms. This would result in promulgation of old ideas of management whereby, conflict was seen as a healthy exercise, which helped to build up each department's efficiency. But, this view in the long run proves to be detrimental to the firm's performance and must therefore be kept to a bare minimum, if any.Decentralisation of decision making facilitates the participation of the lower level employees and builds up their motivational levels and commitment to the firm. Thus employees are encouraged to make their own decisions, so that they can deal with customers faster and more efficiently. Reward systems help improve an employee's morale, provide encouragement and helps inculcate commitment and loyalty. It improves the employee's self worth and fulfills his need for achievement. A satisfied employee works better, produces more output and needs less supervision, and is happy, thereby reducing costs to the company for replacement and retraining, if the employee quits.Competitive intensity plays a moderating role on the market orientation business performance. Thus in times of greater competition, the relationship between market orientation and business performance grows stronger. Thus, this thesis was successful in investigating a positive relationship between business performance and market orientation.

Studies on the, Physical Aspects of the Mud Banks along the Kerala Coast

A detailed survey of the present knowledge on the physical aspects of the mud banks has been presented in chapter 1.The physical geographical and geological aspects of the kerala coast, the shore-line and the sea bed and the various views on the formation,movements and dissipation of the mud banks have been discussed.The scope of the present work and a description of the area of study have also been given in this chapter. The horizontal and vertical distribution and the seasonal variations of the concentration of suspended matter in the mud bank region are discussed in chapter 3.it is seen that the mud bank reses above the bottom in the form of a ridged ,irregular,solid come with a flat top. Chapter vi deals with waves and currents in the region of the mud bank. The orientation of the breakers on either side of the mud bank suggests the possibility of formation of opposing alongshore currents and convergence of energy caused by wave refraction.The distribution of currents during the formative nature and dissipating stages of the mud bank show that the converging alongshore currents give rise to offshore flows

Investigations on the Radiation Characteristics of Broadband Strip Loaded Slotted Microstrip Antennas

With the recent progress and rapid increase in mobile terminals, the design of antennas for small mobile terminals is acquiring great importance. In view of this situation, several design concepts are already been addressed by the scientists and engineers. Compactness and efficiency are the major criteria for mobile terminal antennas. The challenging task of the microwave scientists and engineers is to device compact printed radiating systems having broadband behavior, together with good efficiency. Printed antenna technology has received popularity among antenna scientists after the introduction of microstrip antenna in 1970s. The successors in this kind such as printed monopoles and planar inverted F are also equally important. Scientists and Engineers are trying to explore this technology as a viable coast effective solution for forthcoming microwave revolution. The transmission line perspectives of antennas are very interesting. The concept behind any electromagnetic radiator is simple. Any electromagnetic system with a discontinuity is radiating electromagnetic energy. The size, shape and the orientation of the discontinuities controls the radiation characteristics of the system such as radiation pattern, gain, polarization etc. It can be either resonant or non resonant structure. Microstrip antennas are suitable for wireless applications due to their low cost, high gain and ease of fabrication. But the major disadvantage of micro strip antennas is their inherent narrow bandwidth. A lot of techniques are introduced by the researchers all over the world to enhance the bandwidth of micro strip patch antennas. The thesis addresses an attempt to enhance the bandwidth of micro strip patch antennas by incorporating impedance matching strip as a part of the micro strip patch antenna. The first part of the thesis deals with the broadband operation of the tilted square slot and polygonal slot loaded square micro strip patch antennas. The resonant mechanisms are clearly mentioned using the simulation and experimental studies. The bandwidth of the polygonal slotted broadband patch antenna is again enhanced by implementing an Lstrip feed mechanism. In the second major part of the thesis, a novel gain enhancement technique for single band and broadband square micro strip patch antennas is achieved by implementing offset stacked configurations.

“Design and Development of Coplanar Strip Fed Planar Antennas”

With the recent progress and rapid increase in the field of communication, the designs of antennas for small mobile terminals with enhanced radiation characteristics are acquiring great importance. Compactness, efficiency, high data rate capacity etc. are the major criteria for the new generation antennas. The challenging task of the microwave scientists and engineers is to design a compact printed radiating structure having broadband behavior along with good efficiency and enhanced gain. Printed antenna technology has received popularity among antenna scientists after the introduction of planar transmission lines in mid-seventies. When we view the antenna through a transmission line concept, the mechanism behind any electromagnetic radiator is quite simple and interesting. Any electromagnetic system with a discontinuity is radiating electromagnetic energy. The size, shape and orientation of the discontinuities control the radiation characteristics of the system such as radiation pattern, gain, polarization etc. It can be either resonant or non-resonant. This thesis deals with antennas that are developed from a class of transmission lines known as coplanar strip-CPS, a planar analogy of parallel pair transmission line. The specialty of CPS is its symmetric structure compared to other transmission lines, which makes the antenna structures developed from CPS quite simple for design and fabrication. The structural modifications on either metallic strip of CPS results in different antennas. The first part of the thesis discusses a single band and dual band design derived from open ended slot lines which are very much suitable for 2.4 and 5.2 GHz WLAN applications. The second section of the study is vectored into the development of enhanced gain dipoles. A single band dipole and a wide band enhanced gain dipole suitable for 5.2/5.8 GHZ band and imaging applications are developed and discussed. Last part of the thesis discusses the development of directional UWBs. Three different types of ultra-compact UWBs are developed and almost all the frequency domain and time domain analysis of the structures are discussed.

Structural And Surface Morphological Investigation Of Formation Stages Of Highly (002) Oriented Zno Films On Glass Substrates By Spray Pyrolysis Method

ZnO thin films were coated on amorphous glass substrate at various temperatures in the range 160-500 0C by spray pyrolysis method. The as deposited films were characterised by using XRD and SEM. Wurtzite phase of ZnO was formed at a substrate temperature of 400 0C, highly oriented (002) phase was developed with respect to increase of substrate temperature from 450 to 500 0C. Morphological and growth mode of these films were analyzed with respect to structural orientation of films from wurtzite to highly (002) oriented phase. Present study reveals that substrate temperature was one of the important parameters which determine the crystalline quality, population of defects, grain size, orientation and morphology of the films

Prediction of the azimuth angle dependence of the quasimolecular anisotropy in heavy ion collisions

Within the quasimolecular (MO) kinematic dipole model we predict a strong dependence of the anisotropy of the MO radiation on the orientation of the heavy ion scattering plane relative to the direction of the photon detection plane.

Constructing a ‘moment of crisis’ and its adequate solution

The rejection of the European Constitution marks an important crystallization point for debate about the European Union (EU) and the integration process. The European Constitution was envisaged as the founding document of a renewed and enlarged European Union and thus it was rather assumed to find wide public support. Its rejection was not anticipated. The negative referenda in France and the Netherlands therefore led to a controversial debate about the more fundamental meaning and the consequences of the rejection both for the immediate state of affairs as well as for the further integration process. The rejection of the Constitution and the controversy about its correct interpretation therefore present an intriguing puzzle for political analysis. Although the treaty rejection was taken up widely in the field of European Studies, the focus of existing analyses has predominantly been on explaining why the current situation occurred. Underlying these approaches is the premise that by establishing the reasons for the rejection it is possible to derive the ‘true’ meaning of the event for the EU integration process. In my paper I rely on an alternative, discourse theoretical approach which aims to overcome the positivist perspective dominating the existing analyses. I argue that the meaning of the event ‘treaty rejection’ is not fixed or inherent to it but discursively constructed. The critical assessment of this concrete meaning-production is of high relevance as the specific meaning attributed to the treaty rejection effectively constrains the scope for supposedly ‘reasonable’ options for action, both in the concrete situation and in the further European integration process more generally. I will argue that the overall framing suggests a fundamental technocratic approach to governance from part of the Commission. Political struggle and public deliberation is no longer foreseen as the concrete solutions to the citizens’ general concerns are designed by supposedly apolitical experts. Through the communicative diffusion and the active implementation of this particular model of governance the Commission shapes the future integration process in a more substantial way than is obvious from its seemingly limited immediate problem-solving orientation of overcoming the ‘constitutional crisis’. As the European Commission is a central actor in the discourse production my analysis focuses on the specific interpretation of the situation put forward by the Commission. In order to work out the Commission’s particular take on the event I conducted a frame analysis (according to Benford/Snow) on a body of key sources produced in the context of coping with the treaty rejection.