In dieser Arbeit werden die Synthese eines 286-Reste-langen Proteins, der γ-Untereinheit der ATP-Synthase, seine Rückfaltung und Rekonstitution zum aktiven Proteinkomplex gezeigt.

Les plasmons-polaritons de surface (PPS) font figure de plateforme polyvalente très promet- teuse pour le guidage des ondes électromagnétiques à l’échelle nanométrique. Dans ce contexte, le contrôle dynamique de la propagation PPS est d’une importance capitale. Le contrôle actif des dispositifs plasmoniques a souvent été réalisé jusqu’à présent par le biais d’un effet thermo-optique (TO). Toutefois dans la majorité des cas considérés, l’effet thermo-optique résulte d’une modification des propriétés d’un matériaux diélectrique en contact avec le métal supportant le mode plasmon. Ainsi, le rôle des propriétés thermo-optiques du métal lui-même a rarement été analysé aux fréquences télécom dans le cadre d’applications plasmoniques. L’objectif principal de cette thèse est donc d’analyser en détail l’impact des propriétés thermo- optiques des métaux sur différents modes PPS aux longueurs d’ondes télécom. En premier lieu, nous considérons la modulation photo-thermique d’un mode plasmon supporté par un film mince d’or se propageant à l’interface "or/air". Nous démontrons tout d’abord la modulation de la propagation des modes PPS induite par la dépendance des pertes ohmiques de l’or à la température du film mince. Le contrôle de la température du film est obtenu par un effet photo-thermique en régime continu modulé. Les mesures expérimentales de la pro- fondeur de modulation de l’intensité des modes PPS combinées à la simulation numérique de la distribution de température le long du film d’or nous permettent de remonter aux coefficients thermo-optiques de l’or aux fréquences télécoms. Dans un second temps, nous considérons le contrôle thermo-optique de modes plasmons dont le confinement spatial (et donc l’indice effectif) est supérieur à ceux des modes de films. Les modes considérés dans cette seconde étude sont connus sous le nom de "polymer- loaded surface plasmon waveguides (PLSPPWs)". Ces modes présentent un confinement latéral induit par l’indice de réfraction du ruban de polymère déposés sur le film métallique et un confinement vertical résultant de leur nature plasmonique. L’excitation photo-thermique de ces guides plasmoniques dans un régime nano-seconde nous permet de mettre en évidence la dynamique thermo-optique du métal aux temps courts (<1ns) et du polymère aux temps plus longs (<1µs). La même démarche appliquée à un micro-résonateur plasmonique en anneau révèle les temps caractéristiques de la dynamique de diffusion de la chaleur dans le polymère à l’échelle de quelques dizaines de nanomètres. Sur la base de ces expériences, nous suggérons un design de dispositifs plasmoniques thermo-optique dont la bande passante est de l’ordre du megahertz, un ordre de grandeur au-dessus des systèmes thermo-optiques traditionnels. Enfin, nous présentons la modulation photo-thermique de la propagation PPS le long de nanofils d’or fabriqués par lithographie électronique supportant des modes plasmons très confinés aux longueurs d’onde télécom. La transmission d’un signal télécom à 10 Gbit/s est tout d’abord démontrée afin d’établir sans ambiguïté la pertinence de tels guides d’ondes miniatures pour la transmission d’informations à très courtes échelles. Enfin, nous mettons en évidence la modulation photo-thermique de la propagation de tels modes. En particulier, nous investiguons l’influence sur la profondeur de modulation de la polarisation du faisceau pompe relativement à l’orientation des nanofils. Cet effet de polarisation s’explique par une absorption exaltée si la polarisation du faisceau pompe est orientée perpendiculairement à l’axe du nanofil. L’exaltation résulte de l’excitation d’un mode plasmon local selon l’axe transverse du nanofil. / Surface plasmon polaritons (SPPs) is the promising versatile platform proposed for guiding electromagnetic waves at nanoscale dimensions. In this context dynamic control of SPPs prop- agation is of paramount importance. Thermo-optical (TO) effect is considered as an efficient technique for performing active control of plasmonic devices. Among the thermo-optical based plasmonic devices demonstrated so far TO coefficient is dominantly provided by a dielectric material on top of the metal sustaining the SPP mode, however, the role of TO properties of the metal has been rarely investigated for plasmonic applications especially at the telecom frequency ranges. Therefore, the aim of this thesis is to investigate in detail the impact of thermo-optical properties of metals onto various SPP modes at telecom wavelengths.First, we report on photo-thermal modulation of thin film SPP mode traveling at gold/air interface excited at telecom wavelengths. We start by investigating the photo-thermally in- duced modulation of SPPs propagation mediated by the temperature dependent ohmic losses in the gold film. Then we extract the thermo-plasmonic coefficient of the SPP mode from the accurately measured SPPs signal depth of modulation by which we could compute the thermo-optical coefficients (TOCs) of gold at telecom wavelength. Lastly, we demonstrate a pulsed photo-thermal excitation of the SPPs in the nanosecond regime.Secondly, we investigate the thermo-optical dynamics of polymer loaded surface plasmon waveguide (PLSPPW) based devices photo-thermally excited in the nanosecond regime. First, we demonstrate thermo-absorption of PLSPPW modes mediated by the temperature-dependent ohmic losses of the metal and the thermally controlled field distribution of the plasmon mode within the metal. Next, we consider the thermo-optical response of a PLSPPW based racetrack shaped resonator coupled to a straight bus waveguide and evaluate the photo-thermal activation through heating and cooling times. We conclude that nanosecond excitation combined to high thermal diffusivity materials opens the way to high speed thermo-optical plasmonic devices.Finally, we report on the photo-thermal modulation of SPPs propagation along litho- graphically fabricated gold nanowires sustaining highly confined plasmonic mode at telecom wavelengths. First, we investigate telecommunication characterization of the nanowires by ap- plying high bit rate signal transmission, 10 Gbit/s, through fiber-to-fiber confocal detection setup. Next, we demonstrate and evaluate the photo-thermal modulation of SPPs propagation along the nanowires where we discuss qualitatively TO effects due to light-induced modula- tions on nanowires and show the impact of the incident beam polarization on the photo-thermal modulation.

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We have developed a general theory of the plasmonic enhancement of many-body phenomena resulting in a closed expression for the surface plasmon-dressed Coulomb interaction. It is shown that this interaction has a resonant nature. We have also demonstrated that renormalized interaction is a long-ranged interaction whose intensity is considerably increased compared to bare Coulomb interaction over the entire region near the plasmonic nanostructure. We illustrate this theory by re-deriving the mirror charge potential near a metal sphere as well as the quasistatic potential behind the so-called perfect lens at the surface plasmon (SP) frequency. The dressed interaction for an important example of a metal–dielectric nanoshell is also explicitly calculated and analyzed. The renormalization and plasmonic enhancement of the Coulomb interaction is a universal effect, which affects a wide range of many-body phenomena in the vicinity of metal nanostructures: chemical reactions, scattering between charge carriers, exciton formation, Auger recombination, carrier multiplication, etc. We have described the nanoplasmonic-enhanced Förster resonant energy transfer (FRET) between quantum dots near a metal nanoshell. It is shown that this process is very efficient near high-aspect-ratio nanoshells. We have also obtained a general expression for the force exerted by an electromagnetic field on an extended polarizable object. This expression is applicable to a wide range of situations important for nanotechnology. Most importantly, this result is of fundamental importance for processes involving interaction of nanoplasmonic fields with metal electrons. Using the obtained expression for the force, we have described a giant surface-plasmoninduced drag-effect rectification (SPIDER), which exists under conditions of the extreme nanoplasmonic confinement. Under realistic conditions in nanowires, this giant SPIDER generates rectified THz potential differences up to 10 V and extremely strong electric fields up to 10^5-10^6 V/cm. It can serve as a powerful nanoscale source of THz radiation. The giant SPIDER opens up a new field of ultraintense THz nanooptics with wide potential applications in nanotechnology and nanoscience, including microelectronics, nanoplasmonics, and biomedicine. Additionally, the SPIDER is an ultrafast effect whose bandwidth for nanometric wires is 20 THz, which allows for detection of femtosecond pulses on the nanoscale.

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Obwohl die methodische Entwicklung der Peptidsynthese gewöhnlich eine automatisierte Herstellung erlaubt, sind für die Herstellung einer Reihe von Peptiden auch gegenwärtig Grenzen gesetzt. Einerseits kann eine im Verlauf der Kettenverlängerung auftretende Bildung intra- und /oder intermolekularer Wasserstoffbrücken zu einer begrenzten Solvatation und damit Zugänglichkeit der zu acylierenden Aminokomponente am Syntheseharz führen, andererseits kommt es beim Einbau sterisch anspruchsvoller Aminosäuren zu ungenügenden Acylierungsausbeuten. Urethangeschützte Aminosäurefluoride haben sich für den Einbau von alpha, alpha-Dialkylaminosäuren als geeignet erwiesen. Die reaktiveren urethangeschützten Aminosäurechloride sind zwar herstellbar, besitzen aber in Gegenwart einer Hilfsbase, die zum Abfangen der während ihrer Reaktion gebildeten HCl notwendig ist, eine zu geringe Stabilität (Oxazolonbildung, Abspaltung der Schutzgruppen). Erst die Verwendung von N(alpha)-Schutzgruppen, die keinen reaktionsfähigen Carbonylkohlenstoff enthalten, wie Arensulfonyl- Schutzgruppen, ermöglichen die volle Ausschöpfung der hohen Reaktivität der Aminosäurechloride. Mit Hilfe dieser Schutzgruppen gelang ein erster Vergleich der Reaktivität der Aminosäurechloride und -fluoride. Bei den durchgeführten Reaktionen wurde keine Stereomutation beobachtet. Unter Verwendung von Arensulfonylschutzgruppen war es erstmals möglich, zwei aufeinanderfolgende N-Alkyl-alpha, alpha-dialkylaminosäuren in Peptide einzubauen. Weiterhin konnten wir zeigen, daß derart geschützte Aminosäuren sich für in situ Aktivierungen mit Thionylchlorid eignen. Als Fänger für überschüssiges Aktivierungsreagenz wurden tertiäre Alkohole bzw. Amine eingesetzt. Arensulfonyl-geschützte Aminosäurechloride haben wir darüber hinaus erfolgreich in der Festphasenpeptidsynthese verwendet. In Kombination von Arensylfonyl-Schutz mit der Standard-Fmoc-Strategie gelang die Synthese eines biologisch aktiven Analogen des CRF, eines 41-mer Peptides mit einer eingefügten Tetrapeptidsequenz -Ala-MeAib-MeAib-Aib-. / Despite its wide field of application automatic peptide synthesis is still limited in certain cases. One of the limiting factors is the possibility of intra- or intermolecular hydrogen bond formation during the elongation of the peptide chain. This causes decreased solvation and thus reduced accessibility to the resin-bound amino component. Another limitation is the incorporation of sterically hindered amino acids that usually give rise to insufficient yields of acylation. Urethane protected amino acid fluorides have been shown suitable for the incorporation of alpha,alpha-dialkyl amino acids. Though the more reactive urethane protected amino acid chlorides can be readily synthesized, they do not possess the necessary stability in the presence of an auxiliary base that must be used for trapping of the hydrochloric acid formed during the reaction. Formation of oxazolons and deprotection of formerly protected functional groups would occur. Only the advent of protecting groups for the amino acid N-alpha that do not have a reactive carbonyl function - like arene sulfonyl groups - allowed to take full advantage of the high reactivity of the amino acid chlorides. These protecting groups enabled us to compare the reactivities of amino acid chlorides and fluorides for the first time. We didn't observe any stereo mutation in our experiments. The use of arene sulfonyl protecting groups permitted the consecutive incorporation of two N-alkyl-alpha,alpha-dialkyl amino acids into a peptide for the first time. Furthermore we could show, that amino acids protected in this way, are suitable for in situ activation with thionyl chloride. Tertiary alcohols and amines were used as scavenger for excessive activating reagent. Arene sulfonyl protected amino acids were also successfully used in solid phase peptide synthesis. By combining this protecting concept with the standard Fmoc approach we were able to synthesize a biologically active analogue of CRF, a peptide containing 41 residues into which we inserted the tetrapeptide Ala-MeAib-MeAib-Aib.

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In recent years a significant research focus has been on the development of biomimicking three-dimensional substrates for cell culturing. Hydrogels mimicking the extracellular matrix is a well-suited scaffold for this purpose and there are many different ways these can be cross-linked to retain their shape. The group of Molecular Materials at IFM, Linköping University, is focusing on the development of physical hydrogels hybridized through peptide-peptide interactions but all peptides used for this today are created using rational design and on top of this very large, making them time-consuming and expensive to fabricate. The aim of this project was to evaluate if One Bead One Compound (OBOC) libraries could be used as an alternative to rational design in the finding of cyclic peptide binding partners used in the hybridization of hydrogels. The results were not very promising though since only seven peptides passed all screening steps and of these only two could be sequenced. Of these two, only one was water soluble enough to enable binding interactions analysis but was then found to be a false hit. Nevertheless, it should be noticed that only a fraction of all possible combinations was screened and the results cannot exclude OBOC libraries as an approach in the quest of finding new cyclic peptide binding partners.