Gotowa bibliografia na temat „Selective refocusing”

A selective variant of the standard INEPT experiment is suggested. The selectivity is achieved by replacing the refocusing proton pulses of the standard INEPT pulse sequence with selective (DANTE) 180° pulses. Since this approach eliminates the undesirable influences of homo- and heteronuclear couplings, the sensitivity of the method is high. In the case of assigning 29Si NMR lines of trimethylsilylated compounds the pulse sequence can be further simplified and a pair of refocusing pulses can be eliminated from the refocusing period. Advantages of the simplified method are demonstrated.

Novel band selective decoupled pure shift selective refocusing experiments allowed simplification of the measurement of all δ¹H, and J_HH couplings with an ultrahigh spectral resolution in peptides.

En Imagerie par Résonance Magnétique (IRM), l’augmentation du champ magnétique statique permet en théorie de fournir un rapport signal sur bruit accru, améliorant la qualité des images. L’objectif de l’IRM à ultra haut champ est d’atteindre une résolution spatiale suffisamment haute pour pouvoir distinguer des structures si fines qu’elles sont actuellement impossibles à visualiser de façon non-invasive. Cependant, à de telles valeurs de champs magnétiques, la longueur d’onde du rayonnement électromagnétique envoyé pour basculer les spins des protons de l’eau est du même ordre de grandeur que l’objet dont on souhaite faire l’image. Des phénomènes d’interférences sont observés, ce qui se traduit par l’inhomogénéité de ce champ radiofréquence (RF) au sein de l’objet. Ces interférences engendrent des artefacts de signal et/ou de contraste dans les images IRM, et rendent ainsi leur exploitation délicate. Il est donc crucial de fournir des solutions pour atténuer la non-uniformité de l’excitation des spins, à défaut de quoi de tels systèmes ne pourront atteindre leurs pleins potentiels. Pour obtenir des diagnostics pertinents à très haut champ, il est donc nécessaire de créer des impulsions RF homogénéisant l'excitation de l'ensemble des spins (ici du cerveau humain), optimisées pour chaque individu. Pour cela, un système de transmission parallèle (pTX) à 8 canaux a été installé au sein de notre imageur à 7 Tesla. Alors que la plupart des systèmes IRM cliniques n’utilisent qu’un seul canal d’émission, l’extension pTX permet de jouer différentes formes d’impulsions RF de concert. La somme résultante de ces interférences doit alors être optimisée pour atténuer la non-uniformité observée classiquement. L’objectif de cette thèse est donc de synthétiser ce type d’impulsions, en utilisant la pTX. Ces impulsions auront pour contrainte supplémentaire le respect des limitations internationales concernant l'exposition à des champs radiofréquence, qui induit une hausse de température dans les tissus. En ce sens, de nombreuses simulations électromagnétiques et de températures ont été réalisées en introduction de cette thèse, afin d’évaluer la relation entre les seuils recommandés d’exposition RF et l’élévation de température prédite dans les tissus. Cette thèse porte plus spécifiquement sur la conception de l’ensemble des impulsions RF refocalisantes utilisées dans des séquences IRM non-sélectives, basées sur l’écho de spin. Dans un premier temps, seule une impulsion RF a été générée, pour une application simple : l’inversion du déphasage des spins dans le plan transverse. Dans un deuxième temps, sont considérées les séquences à long train d’échos de refocalisation appliquées à l’in vivo. Ici, l’opérateur mathématique agissant sur la magnétisation, et non pas son état final comme il est fait classiquement, est optimisé. Le gain en imagerie à très haut champ est clairement visible puisque les opérations mathématiques (la rotation des spins) voulues sont réalisées avec plus de fidélité que dans le cadre des méthodes de l’état de l’art. Pour cela, la génération de ces impulsions RF combine une méthode d’excitation des spins avec navigation dans l’espace de Fourier, les kT-points, et un algorithme d’optimisation, appelé Gradient Ascent Pulse Engineering (GRAPE), utilisant le contrôle optimal. Cette conception est rapide grâce à des calculs analytiques plus directs que des méthodes de différences finies. La prise en compte d’un grand nombre de paramètres nécessite l’usage de GPUs (Graphics Processing Units) pour atteindre des temps de calcul compatibles avec un examen clinique. Cette méthode de conception d’impulsions RF a été validée expérimentalement sur l’imageur 7 Tesla de NeuroSpin, sur une cohorte de volontaires sains
In Magnetic Resonance Imaging (MRI), the increase of the static magnetic field strength is used to provide in theory a higher signal-to-noise ratio, thereby improving the overall image quality. The purpose of ultra-high-field MRI is to achieve a spatial image resolution sufficiently high to be able to distinguish structures so fine that they are currently impossible to view in a non-invasive manner. However, at such static magnetic fields strengths, the wavelength of the electromagnetic waves sent to flip the water proton spins is of the same order of magnitude than the scanned object. Interference wave phenomena are then observed, which are caused by the radiofrequency (RF) field inhomogeneity within the object. These generate signal and/or contrast artifacts in MR images, making their exploitation difficult, if not impossible, in certain areas of the body. It is therefore crucial to provide solutions to mitigate the non-uniformity of the spins excitation. Failing this, these imaging systems with very high fields will not reach their full potential.For relevant high field clinical diagnosis, it is therefore necessary to create RF pulses homogenizing the excitation of all spins (here of the human brain), and optimized for each individual to be imaged. For this, an 8-channel parallel transmission system (pTX) was installed in our 7 Tesla scanner. While most clinical MRI systems only use a single transmission channel, the pTX extension allows to simultaneously playing various forms of RF pulses on all channels. The resulting sum of the interference must be optimized in order to reduce the non-uniformity typically seen.The objective of this thesis is to synthesize this type of tailored RF pulses, using parallel transmission. These pulses will have as an additional constraint the compliance with the international exposure limits for radiofrequency exposure, which induces a temperature rise in the tissue. In this sense, many electromagnetic and temperature simulations were carried out as an introduction of this thesis, in order to assess the relationship between the recommended RF exposure limits and the temperature rise actually predicted in tissues.This thesis focuses specifically on the design of all RF refocusing pulses used in non-selective MRI sequences based on the spin-echo. Initially, only one RF pulse was generated for a simple application: the reversal of spin dephasing in the transverse plane, as part of a classic spin echo sequence. In a second time, sequences with very long refocusing echo train applied to in vivo imaging are considered. In all cases, the mathematical operator acting on the magnetization, and not its final state as is done conventionally, is optimized. The gain in high field imaging is clearly visible, as the necessary mathematical operations (that is to say, the rotation of the spins) are performed with a much greater fidelity than with the methods of the state of the art. For this, the generation of RF pulses is combining a k-space-based spin excitation method, the kT-points, and an optimization algorithm, called Gradient Ascent Pulse Engineering (GRAPE), using optimal control.This design is relatively fast thanks to analytical calculations rather than finite difference methods. The inclusion of a large number of parameters requires the use of GPUs (Graphics Processing Units) to achieve computation times compatible with clinical examinations. This method of designing RF pulses has been experimentally validated successfully on the NeuroSpin 7 Tesla scanner, with a cohort of healthy volunteers. An imaging protocol was developed to assess the image quality improvement using these RF pulses compared to typically used non-optimized RF pulses. All methodological developments made during this thesis have contributed to improve the performance of ultra-high-field MRI in NeuroSpin, while increasing the number of MRI sequences compatible with parallel transmission

The investigations have been carried out in the thesis entitled as “Manipulation of Spin Dynamics and Multifaceted Applications of NMR Spectroscopy to Small Molecules” to address the challenging problems encountered in chemistry, as far as the small organic molecules is concerned, and to underline the importance of NMR spectroscopy by utilizing various one- and two- dimensional techniques. The first part of the thesis discusses the design and utility of a novel experimental technique, cited as, 2D PS-Clean-PE-SERF. The developed methodology is utilized to address the inherent issues of sensitivity of detection, the spectral complexity and the precise measurement of JHH couplings of a selected proton from the complex 1H-NMR spectrum. In addition to enhancement in the sensitivity of detection, the novel experiment results in the complete elimination of the intense uninformative axial peaks and prevents the evolution of undesired couplings arising from the uncoupled partners, which otherwise would have created confusion in the assignment of true coupled partners of the chosen proton. In the second part of the thesis, the investigations have been carried out to probe the weak molecular interactions in the synthesized N-bezoylanthranilamide and its derivatives, especially the participation of organic fluorine in the hydrogen bond (HB) in the fluorine substituted derivative, by the extensive utility of number of one- and two- dimensional NMR techniques. The detection of doublet for an NH proton with significantly large coupling strength (1hJFH) arising due to the polarization transfer between 19F and 1H mediated through HB and a correlated peak in the HOESY established their spatial proximity conducive for HB. The rare and unusual observation of the partial retention of 1hJFH instead of complete nullification in the high polarity solvent DMSO-d6 is interpreted as due to the existence of favorable cis conformers in the investigated molecules. The rivalry between N-H…X and >C=O…H-N types of HBs is perceived as the reason for unusual shielding in the NH resonance frequency and relatively small 1hJFH, contrary to previous reports. NMR experimental findings are further corroborated by the single crystal XRD and DFT studies. In the last part of the thesis, utilization of the residual chemical shift anisotropy as a parameter for the discrimination of enantiomers in the chiral aligning medium is explored. The method is based on the differential alignment tensor components for each diastereomer, and the extent of discrimination is determined by the inter-tensor angle (θ). The robustness and the broad applicability of the method has been demonstrated in the water-compatible polysaccharide alignment medium, which has remained unexplored for the RCSA measurement, and in the versatile PBLG aligning medium which is also demonstrated on the functional group deficient molecule.

Spin selective MQ-SQ correlation has been demonstrated by either selective pulses in homo-nuclear spin systems in isotropic and weakly orienting chiral media or by nonselective pulses in hetero-nuclear spin systems in strongly aligned media. As a consequence of the spin selective correlation, the coherence transfer pathway from MQ to SQ is spin state selective. This two dimensional approach enables the utilization of the passive couplings (remote couplings) to break a complex one dimensional spectrum into many sub spectra. Each sub spectrum contains fewer transitions and hence fewer couplings (active couplings). The role of the passive couplings is to displace the sub spectra and measurement of the displacements taking into account their relative tilt provides the magnitude of the passive couplings along with relative signs. Further possibility of a spin state selective MQ-SQ resolved experiment to determine very small remote couplings otherwise buried within linewidth in one dimensional spectrum has been demonstrated. The resolution of the multiple quantum spectrum in indirect dimension has also been exploited to separate the sub spectra. The technique renders the analysis of complex spectrum in isotropic system much simpler. The potentialities of the technique have also been demonstrated for discrimination of optical enantiomers and derivation of the residual dipolar couplings from very complicated spectrum. The second order spectrum in strongly aligned media restrict selective excitation, however in hetero-nuclear spin system the nonselective pulses on protons do not interact with the hetero-nuclear spins. Thus the weakly coupled part of a strongly coupled spectrum has been exploited for simplifying the second order spectrum and thereby its analysis. Thus several methodologies derived from spin selective correlation has been demonstrated. Enantiopure spectrum has been recorded from a mixture of R and S enantiomers by a novel pulse scheme called Double Quantum Selective Refocusing Experiment. The dipolar coupled methyl protons in weakly orienting media are utilized. The selective excitation of double quantum coherence reduces the three spin system into a two spin system and remote couplings are refocused which otherwise leads to broadening. The sum of passive couplings being different for the enantiomers resolution in the DQ dimension is enhanced and thereby their discrimination. Finally several decoupling schemes has been compared in the indirect dimension of HSQC experiment to resolve 13C satellite spectra otherwise buried within line width for increased confidence in determining hetero-nuclear framework information.

Spin selective MQ-SQ correlation has been demonstrated by either selective pulses in homo-nuclear spin systems in isotropic and weakly orienting chiral media or by nonselective pulses in hetero-nuclear spin systems in strongly aligned media. As a consequence of the spin selective correlation, the coherence transfer pathway from MQ to SQ is spin state selective. This two dimensional approach enables the utilization of the passive couplings (remote couplings) to break a complex one dimensional spectrum into many sub spectra. Each sub spectrum contains fewer transitions and hence fewer couplings (active couplings). The role of the passive couplings is to displace the sub spectra and measurement of the displacements taking into account their relative tilt provides the magnitude of the passive couplings along with relative signs. Further possibility of a spin state selective MQ-SQ resolved experiment to determine very small remote couplings otherwise buried within linewidth in one dimensional spectrum has been demonstrated. The resolution of the multiple quantum spectrum in indirect dimension has also been exploited to separate the sub spectra. The technique renders the analysis of complex spectrum in isotropic system much simpler. The potentialities of the technique have also been demonstrated for discrimination of optical enantiomers and derivation of the residual dipolar couplings from very complicated spectrum. The second order spectrum in strongly aligned media restrict selective excitation, however in hetero-nuclear spin system the nonselective pulses on protons do not interact with the hetero-nuclear spins. Thus the weakly coupled part of a strongly coupled spectrum has been exploited for simplifying the second order spectrum and thereby its analysis. Thus several methodologies derived from spin selective correlation has been demonstrated. Enantiopure spectrum has been recorded from a mixture of R and S enantiomers by a novel pulse scheme called Double Quantum Selective Refocusing Experiment. The dipolar coupled methyl protons in weakly orienting media are utilized. The selective excitation of double quantum coherence reduces the three spin system into a two spin system and remote couplings are refocused which otherwise leads to broadening. The sum of passive couplings being different for the enantiomers resolution in the DQ dimension is enhanced and thereby their discrimination. Finally several decoupling schemes has been compared in the indirect dimension of HSQC experiment to resolve 13C satellite spectra otherwise buried within line width for increased confidence in determining hetero-nuclear framework information.

This chapter defends the thesis that an agent can display more or less rationality in selecting ends, even final ends, against the background of a conception of practical rationality as an excellence in the exercise of cognitive capacities in one’s practical endeavors. It moreover argues that Humeans and anti-Humeans alike should accept this conclusion, while refocusing their disagreement on the question of whether excellence in the exercise of cognitive capacities in one’s practical endeavors invariably yields a configuration of attitudes which precludes that some specific kinds of ends make good sense to the agent, so that having these kinds of ends is a sure sign of irrationality. By way of preliminaries, the chapter also offers a new (partial) account of ends and motivates the cognitive excellence conception of practical rationality in preference to conceptions of practical rationality as responsiveness to normative reasons or as coherence of attitudes and actions.

This chapter introduces the idea of networked learning environments and argues that these environments provide the totality of surrounding conditions for learning in digital networks. It provides illustrative vignettes of the ways that students appropriate networked environments for learning. The chapter then examines the notion of networked learning environments in relation to the idea of infrastructure and infrastructures for learning and sets out some issues arising from this perspective. The chapter suggests that students and teachers selectively constitute their own contexts and that design can only have an indirect effect on learning. The chapter goes on to argue that design needs to be located at the meso level of the institution and that a solution to the problem of indirect design lies in refocusing design at the meso level and on the design of infrastructures for learning.