The technique of ¹H spin echo n.m.r. has been used for the non-invasive study of enzyme catalysed ¹H/²H equilibrium isotope exchange at the C-2 position of lactate in suspensions of human erythroeytes. The intracellular environment of the enzymes involved in this exchange has been investigated by comparing the exchange properties of the enzymes in the intact cell with the properties they display in vitro. A study of the exchange of the lactate C-2 substituent with solvent, which is catalysed by a coupled system of four glycolytic enzymes, has teen used to examine the kinetic properties of the individual enzymes in vitro. Measurements of the exchange in the intact cell have been used to investigate the in situ kinetic properties of one of these enzymes, glyceraldehydephosphate dehydrogenase. Contrary to the conclusions of previous studies with the isolated enzyme in vitro, these measurements have shown that the enzyme is not rate determining for glycolytic flux in the human erythrocyte and that it is unlikely that it is bound to the cell membrane in situ. A study of ¹H/²H exchange between the C-2 positions of methyl labelled lactate molecules, catalysed by lactate dehydrogenase, has been used to investigate the in situ kinetic properties of this enzyme. Comparison of these properties with those it displays in vitro indicate that the free intracellular NAD(H) concentration in the erythrocyte is only approximately 10% of the total extractable concentration. A considerable fraction of the coenzyme must be bound, therefore, in the intact cell. This type of experiment should be widely applicable to a variety of tissues and possibly to different dehydrogenases. Theoretical aspects of bulk isotope exchange kinetics in multi-enzyme systems are examined and the effects of chemical flux, and of isotope effects, on the measurement of isotopic flux are considered. The advantages of the n.m.r. method over conventional radioactive tracer techniques are described. It is concluded that ¹H n.m.r. studies of ¹H/²H isotope exchange may be used to obtain information about the kinetic properties of enzymes in intact cellular systems. The technique should be a useful complement, therefore, to the currently more widely used n.m.r. methods employing the ³¹P and ¹³C nuclei and to other methods used for the non-invasive study of metabolism.

A técnica de eco de fótons com luz temporalmente incoerente (EFLI) foi utilizada neste trabalho para a medida do tempo de relaxação transversal T2 do Iodeto de 3-3´-Dietiloxadicarbonocianina (DODCI) como função da temperatura. Nestes experimentos foi utilizado um laser de corante de banda larga, bombeado pelo 2&#176 harmônico de um laser de Nd+3 : YAG Q-switched. Este laser operou com os corantes Kiton Red 620 e rodamina 640, cujos máximos do espectro de emissão estão respectivamente em 598 e 610 nm. O tempo de relaxação T2, que é proporcional ao inverso da largura de linha homogênea, segue uma dependência funcional com a temperatura do tipo T-1,9. Encontramos o valor de T2 entre 0 e 30fs para &#955 = 598nm e entre 30 e 590fs para &#955 = 610nm, no intervalo de temperatura entre 300 e 60k. Os perfis das medidas de EFLI podem ser descritos por um modelo baseado num sistema quântico de dois níveis / The photon echo with incoherent light technique (EFLI) has been used in this work for the measurement of the transverse relaxation time T2 in 3-3´-Dietiloxadicarboncyanine Iodide (DODCI) as a function of the temperature. A broad-band dye laser, pumped by the second harmonic of a Q-switched Nd+3 : YAG laser, was used in this experiment. The laser used Kiton Red 620 and rodamine 640 dyes, whose maxima output power are respectively around 598 and 610nm. The relaxation time T2 , which is inversely proportional to the homogeneous linewidth, depends on the temperature according to a T-1,9 Law. We found the value of T2 ranging from 0 to 30fs at 598nm and from 30 to 590fs at 610nm in the temperature range between 300 and 60K. The EFLI profiles can be described by means of a two-level quantum system model

A técnica de eco de fótons com luz temporalmente incoerente (EFLI) foi utilizada neste trabalho para a medida do tempo de relaxação transversal T2 do Iodeto de 3-3´-Dietiloxadicarbonocianina (DODCI) como função da temperatura. Nestes experimentos foi utilizado um laser de corante de banda larga, bombeado pelo 2&#176 harmônico de um laser de Nd+3 : YAG Q-switched. Este laser operou com os corantes Kiton Red 620 e rodamina 640, cujos máximos do espectro de emissão estão respectivamente em 598 e 610 nm. O tempo de relaxação T2, que é proporcional ao inverso da largura de linha homogênea, segue uma dependência funcional com a temperatura do tipo T-1,9. Encontramos o valor de T2 entre 0 e 30fs para &#955 = 598nm e entre 30 e 590fs para &#955 = 610nm, no intervalo de temperatura entre 300 e 60k. Os perfis das medidas de EFLI podem ser descritos por um modelo baseado num sistema quântico de dois níveis / The photon echo with incoherent light technique (EFLI) has been used in this work for the measurement of the transverse relaxation time T2 in 3-3´-Dietiloxadicarboncyanine Iodide (DODCI) as a function of the temperature. A broad-band dye laser, pumped by the second harmonic of a Q-switched Nd+3 : YAG laser, was used in this experiment. The laser used Kiton Red 620 and rodamine 640 dyes, whose maxima output power are respectively around 598 and 610nm. The relaxation time T2 , which is inversely proportional to the homogeneous linewidth, depends on the temperature according to a T-1,9 Law. We found the value of T2 ranging from 0 to 30fs at 598nm and from 30 to 590fs at 610nm in the temperature range between 300 and 60K. The EFLI profiles can be described by means of a two-level quantum system model

Aux basses températures, les matrices dopées aux ions terre-rare sont des systèmes prometteurs pour la réalisation de mémoires quantiques. Parmi elles, le système Er³⁺:Y₂SiO₅ a l'avantage de posséder une transition aux longueurs d'onde Télécom, adaptée aux réseaux de communication actuels. Cependant, aucun stockage quantique n'a pu être réalisé de manière efficace durant un temps suffisamment long dans ce matériau. L'objectif de cette thèse est de mieux comprendre les interactions limitant la cohérence du système aux faibles champs magnétiques. Dans ce cadre là, les interactions dominantes sont les basculements réciproques entre deux spins électroniques opposés des ions erbium et l'interaction super-hyperfine entre ces spins et les spins nucléaires des ligands yttrium. J'ai calculé la force et les caractéristiques de ces deux couplages dipolaires en incluant la grande anisotropie de la matrice Y₂SiO₅. J'ai alors pu vérifier l'effet de cette anisotropie sur les basculements réciproques des spins des ions erbium à l'aide de deux techniques optiques, le creusement de trou spectral et l'excitation transitoire. Le taux de ces basculements est maximisé lorsque le champ magnétique est orienté perpendiculairement à l'axe principal du tenseur caractérisant le spin effectif. Il augmente globalement comme le carré de la concentration en ions dopants et diminue avec le champ magnétique. Enfin, j'ai pu mesurer les caractéristiques des interactions super-hyperfines par le biais des modulations d'une décroissance d'écho de photon qu'elles provoquent. Il existe une configuration particulière où un couplage sélectif intervient entre les ions erbium et un unique yttrium de leurs environnements. Au contraire, le couplage à un nombre important d'ions ligands est responsable de la chute du temps de cohérence pour des champs magnétiques inférieurs à la dizaine de mT. / At low temperatures, rare-earth doped matrices are promising supports for the development of quantum memories. Among them, Er³⁺:Y₂SiO₅ is well adapted to the current communication networks because of its transition at Telecom wavelength. However, quantum storage has a very limited efficiency and a short duration in this material. In this thesis, I study the interactions that hinder the coherence at low magnetic fields. In this regime, the dominant processes are flip-flops between opposite electronic spins of erbium ions and the super-hyperfine interaction with nuclear spins of yttrium ligands. I have included the strong anisotropy of the Y₂SiO₅ matrix in the calculation of these two dipolar interactions. In order to check the anisotropy of the flip-flops between erbium spins, I have used two different optical techniques : spectral hole-burning and transient excitation. I have showed that their rate is maximum when the magnetic field is perpendicular to the principal axis of the effective spin tensor. Moreover, the flip-flop probability globally increases as the square of the doping concentration and as the inverse of the field. Then I have also checked the calculations of super-hyperfine interactions by measuring photon echo modulations. I have found a particular situation where an erbium ion is strongly coupled to a single yttrium. On the contrary, the coupling to several ligands at very low magnetic fields drastically reduces the coherence time.

La réalisation d’une mémoire quantique pour la lumière met en jeu les aspects les plus fondamentaux de l’interaction matière-rayonnement. Pour capturer l’information quantique portée par la lumière, le matériau doit être capable de se maintenir dans un état de superposition quantique. Le temps de stockage est limité par la durée de vie de cet état, caractérisée par le temps de cohérence. Les premières expériences ont été réalisées dans des vapeurs atomiques froides, bien connues. Plus récemment, les ions de terres rares en matrice cristalline (REIC) ont attiré l’attention par leurs long temps de cohérence, associés à de larges bandes passantes d’interaction. Pour exploiter ces bonnes propriétés, des protocoles spécifiques ont été proposés. Nous nous sommes tournés vers un dérivé prometteur de l’écho de photon, le Peigne Atomique de Fréquences (AFC, proposé en 2008), fondé sur la transmission du champ incident à travers un profil d’absorption spectralement périodique. Les premiers chapitres de ce manuscrit présentent ce protocole et les travaux effectués durant cette thèse pour en améliorer l’efficacité (i.e. la probabilité de capter et de restituer l’information incidente), en augmenter la bande passante et la capacité de multiplexage et en mesurer le bruit. Les chapitres suivants présentent un nouveau protocole, proposé dans notre groupe durant cette thèse, et baptisé ROSE (Revival Of Silenced Echo). Ce protocole, très proche de l’écho de photon, a été démontré et caractérisé expérimentalement. Il semble très prometteur en termes d’efficacité, de bande passante et de bruit. / The development of a quantum memory for light involves the most fundamental aspects of the light-matter interaction. To store the quantum information carried by light, the material has to be able to stay in a state of quantum superposition. The storage time is limited by the lifetime of this state, characterized by the coherence time. The first experiments involved the well-known cold atomic vapors. More recently, Rare Earth Ions doped Crystals (REIC) have drawn attention because of their remarkably long coherence time, combined with a large interaction bandwidth. Specific protocols have been proposed to take the most out of these properties. We have opted for a promising spin-off of the well-known photon echo, named the Atomic Frequency Comb (AFC, proposed in 2008), based on the transmission of the incoming field through a spectrally periodic absorption profile. The first chapters of this manuscript present this protocol and our works aimed at improving its efficiency (the probability for capturing and retrieving the incoming information), increasing its bandwidth and its multiplexing capacity and measuring its noise. The following chapters present a new protocol, proposed in our group during this thesis, and called Revival Of Silenced Echo (ROSE). This protocol, similar to the photon echo, have been demonstrated and characterized experimentally. It seems really promising in terms of efficiency, bandwidth and noise.

Les ions de terres rares en matrice cristalline, refroidis à très basse température, offrent des propriétés remarquables pour le traitement analogique du signal sur porteuse optique. L’élargissement inhomogène du spectre d’absorption peut en effet atteindre plusieurs centaines de gigahertz alors que la largeur homogène des raies d’absorption des ions individuels ne dépasse pas quelques kilohertz. Par pompage optique il est alors possible de modifier à volonté le profil du spectre d’absorption. On dispose ainsi d’un filtre programmable présentant à la fois une très grande bande passante, donnée par la largeur inhomogène, et une excellente résolution, fixée par la largeur homogène. Une raie d’absorption étroite correspond à un état de superposition quantique de longue durée de vie. C’est sous cet angle, celui des transitoires cohérents, et spécifiquement celui des échos de photons que nous abordons les propriétés du filtre programmable. Dans la première partie de la thèse, le filtre est programmé comme un élément dispersif. Il permet d’atteindre des taux de dispersion inaccessibles aux dispositifs optiques conventionnels, tels que les fibres optiques. Nous l’utilisons comme un composant de lentille temporelle, en vue de produire des signaux de forme arbitraire. Par rapport à des dispositifs d’optique conventionnels, on gagne plusieurs ordres de grandeurs en termes de produit temps x bande passante. Après avoir exploité l’écho de photon dans un contexte de filtrage linéaire, nous tirons parti de ses propriétés de très forte non-linéarité dans la seconde partie de la thèse. Cette fois nous cherchons à capturer un signal lumineux de très faible intensité, à le convertir en état de superposition atomique, puis à le restituer dans son état lumineux initial. Cela suppose en particulier d’empêcher les effets d’émission spontanée ou stimulé qui nuisent à la fidélité de la restitution. Pour ce faire, nous proposons un nouveau protocole que nous avons appelé « Revival Of Silenced Echo » (ROSE) / Rare earth ions doped crystals, when cooled at very low temperature, exhibit outstanding properties for optically-carried analogical signal processing. The absorption spectral broadening can reach several hundred of Gigahertz, while the homogeneous width of each individual ion does no exceed a few kilohertz. With the help of optical pumping, one may modify the absorption profile at will. The resulting programmable filter simultaneously offers a very large bandwidth, given by the inhomogeneous width, and a very good resolution, fixed by the homogeneous width. Narrow absorption line is related to long lifetime quantum superposition. We contemplate the programmable filter properties, keeping in mind this coherent transient picture, specifically related to photon echoes. In the first part of the dissertation, the programmable filter is programmed as a dispersive element. This gives access to dispersion rate values out of reach of conventional optical devices, such as optical fibers. We use the filter as a temporal lens component, with an eye to generating arbitrary waveforms. Thereby, we gain several orders of magnitude against conventional optical devices in terms of time x bandwidth product. After taking advantage of photon echoes in the linear filtering context, we capitalize on their strongly non-linear properties in the second part of the dissertation. This time we want to capture a very weak optical signal, to convert it into an atomic superposition state, and to restore it in its initial state of light. Faithful retrieval of the incoming signal relies on the elimination of spontaneous and stimulated emission. To this end, we propose a new protocol we have named « Revival Of Silenced Echo » (ROSE).

Methoden der transienten Vierwellenmischung mit Femtosekunden-Zeitauflösung werden angewendet, um die Phasen- und Energierelaxation optisch selektiv erzeugter Anregungszustände im Lichtsammelkomplex II höherer Pflanzen (LHC II) sowie im Halbleiter Cadmiumsulfid (CdS) bei verschiedenen Temperaturen zu untersuchen. Für den LHC II werden die Ergebnisse der Messungen des zeitaufgelösten und integrierten Zweipuls-Photonenechos mit Resultaten aus Pump-Test-Experimenten verglichen, um unter Einbeziehung von Literaturdaten Rückschlüsse über den Charakter der phasenzerstörenden Prozesse zu ziehen und Zusammenhänge zu Strukturdaten des Komplexes aufzudecken. Die vorliegende Arbeit liefert erstmals einen systematischen Überblick über die totalen Phasenrelaxationszeiten T2 im Bereich der Qy-Bande des LHC II von 640 bis 685 nm bei 5 K. Das bei 5 K beobachtete Photonenechosignal am LHC II zeigt in Abhängigkeit von der Verzögerung der beiden Anregungsimpulse ein multiexponentielles Abklingen, das auf die Überlagerung der Einflüsse mehrerer Relaxationsprozesse zurückgeführt wird. Dabei lassen sich drei charakteristische Bereiche der Phasenrelaxationszeit unterscheiden, die verschiedenen phasenzerstörenden Prozessen zugeordnet werden. Ein Vergleich mit Resultaten aus Pump-Test-Experimenten führt zu der Schlußfolgerung, daß die Phasenrelaxation im LHC II bei 5 K für Wellenlängen £ 675 nm im wesentlichen durch den Energietransfer auf einer sub-ps Zeitskala bestimmt wird. Für Wellenlängen > 675 nm steigt die Phasenrelaxationszeit stark an und wird insbesondere im Bereich der tiefsten Anregungszustände um 680 nm durch reine Phasenzerstörung dominiert. Ab 20 K setzt bei dieser Wellenlänge ein zusätzlicher phasenzerstörender Prozeß ein, der mit steigender Temperatur zu einem mäßigen linearen Anstieg der Phasenrelaxationsrate (T2)-1 führt. Die Ursache ist vermutlich ein Aufwärts-Energietransfer. Im Bereich der Chlorophyll a-Absorption vernichten außerdem (physiologisch irrelevante) Multiexzitoneneffekte die Kohärenz der angeregten Zustände, verursacht durch die hohe Anregungsintensität. Zusammenfassend kann festgestellt werden, daß die Erhaltung der Kohärenz für die Funktionalität des LHC II eine untergeordnete Rolle spielt. Die wesentlichen Prozesse sind der schnelle räumliche Energietransfer und die Energierelaxation auf das Niveau des primären Elektrondonators P680 im Reaktionszentrum. Am Halbleiter CdS wird erstmals ein mittels Zwei-Photonen-Absorption angeregtes Photonenecho beschrieben, das in Abhängigkeit von der Wellenlänge charakteristische Quantenbeats mit einer Periode von 700 bis 800 fs zeigt. Das stark gedämpfte periodische Echosignal tritt sowohl für positive als auch für negative Verzögerungszeiten t der Anregungsimpulse auf, wobei die Abklingzeit für t>0 mit 170±10 fs doppelt so groß ist wie für t / Transient four-wave-mixing experiments with femtosecond resolution are performed in order to investigate phase and energy relaxation processes of optically excited states in the light harvesting complex II of higher plants (LHC II) and in the semiconductor cadmium sulfide (CdS) at different wavelengths and temperatures. Extensive studies of the time resolved and integrated two-pulse photon echo on LHC II are combined with pump-probe experiments. Results of both methods together with literature data are used to characterize the nature of dephasing processes and to reveal connections with structural data of the complex. This study gives the first systematic survey of total dephasing times T2 in the spectral region of the Qy-absorption band of LHC II from 640 to 685 nm at 5 K. In the case of LHC II, the photon echo signal at 5 K monitored as a function of delay between both excitation pulses shows a multi-exponential decay which is attributed to the superposition of several relaxation processes. Three characteristic dephasing time domains can be distinguished, ascribed to different dephasing processes. Comparing photon echo and pump-probe results it can be concluded that dephasing in LHC II at 5 K and for wavelengths £ 675 nm is dominated by the fast excitation energy transfer on a sub-ps time scale. At wavelengths > 675 nm the total dephasing time increases drastically. The loss of coherence of the lowest excited states around 680 nm at 5 K is mainly determined by pure dephasing. An additional dephasing process, probably uphill energy transfer, occurs at temperatures higher than 20 K leading to a moderate linear rise of the dephasing rate (T2)-1 with increasing temperature. Furthermore, the dephasing in the spectral region of chlorophyll a absorption is affected by (physiologically irrelevant) multi-excitonic effects caused by the high excitation energy. In summary, it can be concluded that the preservation of coherence plays a minor role in the functionality of LHC II. The main processes are the fast spatial excitation energy transfer and the energy relaxation down to the energetic level of the primary electron donor P680 of the reaction center. Investigations of four-wave mixing signals of the semiconductor CdS resulted in the first description of a two-photon excited photon echo in CdS showing characteristic quantum beats with a period of 700 to 800 fs in dependence on wavelength. The strongly damped periodical echo signal is found for both positive and negative delay times t between the excitation pulses. The decay time for t>0 amounts to 170±10 fs and is twice as large as for t

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