Au cours de cette thèse nous avons synthétisé et étudié les propriétés d'optique linéaire et non linéaire d'octupôles 2D. Ce type d'assemblage moléculaire est connu pour posséder de bonnes propriétés d'optique non linéaire de troisième ordre, et plus particulièrement de bonnes propriétés d'absorption à deux photons (ADP). Dans ce travail, nous nous sommes plus particulièrement intéressés aux octupôles 2D à cœur isocyanurate et triazine. Les isocyanurates ont été peu étudiés pour leurs propriétés d'optique non linéaire, bien que des premiers résultats les placent comme des structures très prometteuses, tandis que les triazines sont plus reconnues pour leurs bonnes propriétés d'absorption à deux photons. Dans une première partie, une série de composés organiques à cœur isocyanurate a été synthétisé et leurs propriétés d'optique linéaire et non linéaire ont été étudiées. Ayant pu établir des relations structure/propriétés à partir de ces premières séries de molécules nous avons ensuite synthétisé une nouvelle famille d'analogues à cœur triazine possédant les mêmes groupements électro-donneurs que ceux de la série isocyanurate, afin de pouvoir comparer l'effet de cœur entre ces deux familles. Cette étude comparative nous a permis de sélectionner deux chromophores candidats pour une des applications de l'absorption à deux photons, la thérapie photodynamique à deux photons (2PPDT). Dans une deuxième partie, nous nous sommes attachés à la synthèse de dérivés hydrosolubles pour la thérapie photodynamique à deux photons. Les propriétés de photosensibilisation et biocompatibilité de ces composés ont pu être testées in vitro et in vivo grâce à une collaboration avec le groupe de Magali Gary-Bobo et Marcel Garcia (UMR 6247, Montpellier). Enfin, dans une troisième partie, nous avons tiré parti des relations structure/propriétés mises en évidence dans notre étude sur les isocyanurates organiques pour concevoir une série d'octupôles contenant des unités platine cyclométallées. Nous avons ainsi synthétisé et caractérisé une nouvelle série de complexes de platine à cœur isocyanurate, triazine ou triphénylbenzène. / During this Ph.D work, we were able to synthesize a series of 2D octupoles as well as study their linear and nonlinear optical properties. These molecular architectures are known for their good NLO properties, especially their two-photon absorption properties (TPA). In this thesis, we focused most of our work on isocyanurate and triazine cored octupoles. Isocyanurates are quite understudied even though they have recently proven to be promising for TPA applications, whereas triazines were already known for their good TPA properties. In this respect we started out by the synthesis and characterization of a series of organic isocyanurates. These compounds allowed us to derive useful structure/property relationships. We also synthesized a series of analogous triazines possessing the same donor groups than the isocyanurate series, in order to be able to compare the effect of the core in these two series. This study allowed us to select two candidate chromophores for one of the applications of TPA, twophoton photodynamic therapy (2PPDT). We then focused our efforts on making hydrosoluble version of our model compounds for 2PPDT. Thanks to a collaboration with the group of Magali Gary-Bobo and Manuel Garcia (UMR 6247, Montpellier), photosensitization and biocompatibility results have been obtained in vitro and in vivo. In the last part of this work, the structure/property relationships derived on organic molecules have been used to design a new series of cyclometalated platinum complexes arranged on isocyanurate, triazine or triphenylbenzene cores.

<p>U radu su prvi put za proveru teorija nastajanja i gumolike elastičnosti polimernih mreža primenjeni modelni poliuretanski sistemi čiji su čvorovi veoma stabilni izocijanurat(heksahidro-1,3,5-triazin- 2,4,6-trion) prstenovi. Rad obuhvata: (1) Sintetezu nekoliko serija homogenih poli(uretan-izocijanuratnih) mreža, na bazi 2.4-TDI i poli(oksipropilen)diola, dvoetapnim postupkom u masi, tj. ciklotrimerizacijom teleheličnih diizocijanata uz katalizator Polycat 41. (2) Sintezu manje savr&scaron;enih mreža sa nekom definisanom koncentracijom visećih lanaca koja je postignuta uvodenjem monoola dietilenglikol- monometiletra u toku pripreme prepolimera. (3) Odredivanje povoljnih reakcionih uslove svih etapa sinteze uz primenu i modifikaciju postojećih analitičkih postupaka za karakterizaciju svojstava reakcionih komponenti i praćenja reakcija umrežavanja. (4) Procenu mogućih bočnih reakcija u toku nastajanja mreža jer one mogu značajno uticati na raspodelu različitih fragmenata u mrežama praćenjem koncentracija reakcionih proizvoda kod modelnih reakcija u rastvoru uz isti diol i isti katalizator i odgovarajuće mono-funkcionalne izocijanatne komponente. (5) Karakterizaciju svojstava i strukturnih parametara modelnih mreža i to primenom postupaka ekstrakcije i bubrenja, diferencijalne skanirajuće kalorimetrije, fotoelastičnih merenja, dinamičko-mehaničke spektroskopije i merenja napon-istezanje. Izborom nominalne Mn diola od 400 do 4000 postigne gustina umreženja 0.1x10^-4mol/cm³ do 10x10^-4mol/cm³ sa rasponom temperatura staklastog prelaza od -60&deg;C do +30&deg;C. Za procenu strukturnih parametara mreža primenjena je teorija granajućih procesa sa kaskadnom zamenom za slučaj nastajanja mreža ciklotrimerizacijom i dvoetapni postupak. U zavisnosti od konverzije NCO grupa u mrežama izračunate su masa po monomernoj jedinici, maseni udeo, broj po monomernoj jedinici, koncentracija po jedinici zapremine, Mn, Mw, Mz i Mw/Mn kako za elastično aktivne, osnovne i viseće lance tako i zamolekule sola. Ključni ekspehmentalni podaci koji su kori&scaron;ćeni za proveru teorija nastajanja bio sadržaj gela dobijen vi&scaron;estrukim ekstrakcijama, a za teorije gumolike elastičnosti ravnotežni modul dobijen iz fotoelastičnih merenja. Provera teorija gumolike elastičnosti se zasnivala se u nalaženje vrednosti pred- faktora 3 (tzv. faktora pamćenja) u jednačini koja daje vezu ravnotežnog modula elastičnosti i koncentracije elastično aktivnih lanaca mreže koji ukazuje na način fluktuacije cvorova mreže. Fotoelastična merenja su omogućila da se preko njih parameter pred-faktor 3 proceni pri malim deformacijama. Potvrden je koncept stvarnih mreža sa delimično potisnutim fluktuacijama čvorova uz aditivni doprinos zapletenosti lanaca modulu elastičnosti prema Langley-Graesley konceptu zarobljenih prepletaja.</p> / <p>In this thesis polymer network formation theories and rubber elasticity of polymer networks on model polyurethane systems having as a junction very stable isocyanurate(hexahidro-1,3,5-tгiazin-2,4,6- trion) rings are for the first time investigated. The work contains: (1) Synthesis of homogenious series of several poly(urethane-isocyanurate) networks based on poly(oxypropylene)diol and 2.4-TDI by two stages procedures in bulk i.e. cyclotrimerization of telechelic diisoicyanates with Polycat 41 as catalyst. (2) Synthesis of less perfect networks with some concentration of dangling chains obtained by introduction of monofunctional component diethyleneglycolmonomethylether during prepolymer formation. (3) Determination of optimal reaction conditions for both stages of the synthesis. (4) Estimation of possible side reaction during network formation because of theirs important influence on nework fragment distribution. (5) Caracterization of networks structure and properties by swelling and multiply extraction, differential scanning calorimetry, photoelastical measurements, dynamic-mechanical spectroscopy and stress-strain measurements. By using the different Mn of diols (400 - 4000) the network density from<br />0.1x10^-4mol/cm³ to 10x10^-4mol/cm³ and glass transition temperatures from -60&deg;C to +30&deg;C was achieved. For network structure determinations the theory of branching processes with cascade substitution was used. Mass per monomer unit, mass fraction, number per monomer unit, concentration per unit volume, Mn, Mw, Mz and Mw/Mn for elastically active network chains, backbone chains, dangling chains and sol molecules In the dependence on NCO groups conversion are calculated. Crucial experimental data for examination of network formation theories was the gel content and for rubber<br />elasticity theories the equilibrium modulus received from photoelastical measurement. The estimation of rubber elasticity theories was based on the analysis of the front factor 3 in the equation which gives the relation between the equilibrium modulus and concentration of elastically active network chains. It is estimated the additive contribution of chain entanglements to the equilibrium modulus, especially in the case of high networks density according to Langley-Graesley theory of trapped entanglements.</p>

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Monolithische Phasen werden seit ca. 20 Jahren entwickelt und sind in den letzten Jahren eine attraktive Alternative zu etablierten mit Partikeln gefüllten Säulen geworden. Sie werden in anorganische Phasen und organische Polymermonolithe unterteilt. Monolithe bestehen aus einem einzigen, durchgehenden Stück. Charakteristisch ist das sie durchziehende Porennetzwerk, durch das der Eluent mit geringerem hydraulischen Widerstand fließen kann und das somit schnellere Flussraten ermöglicht. Polymermonolithe werden vorwiegend für die Separation großer Biomoleküle aufgrund eines durch Konvektion beschleunigten Massentransfers eingesetzt. Zudem sind sie über einen breiten pH-Wert-Bereich stabil und können direkt (in situ) im gewünschten Format polymerisiert werden. In der vorliegenden Arbeit gelang die Herstellung neuartiger epoxidbasierter Phasen nach einem von Weller et al. entwickelten Konzept, die im Affinitätsexperiment angewendet wurden. Die Herstellung erfolgte durch Autopolymerisation polyfunktioneller Glycidylether. Für die Funktionalisierung wurden nicht polymerisierte Epoxide genutzt. Als Monomere dienten TEPIC, GE 100 sowie GE 500. Die Arbeiten konzentrierten sich vor allem auf die bei Raumtemperatur durchführbaren Synthesen mit dem höher funktionellen GE 500. Die Polymerisationsbedingungen wurden hinsichtlich Porogenmischung und -anteil optimiert. Eine mit 75 Vol.-% Porogen (Dioxan/ MTBE (2:3)) hergestellte und mit rProtein A funktionalisierte Kapillarsäule (66 %, 12 µm, 7m2/g) ergab im Affinitätsexperiment eine Kapazität von 0,44 mg/mL aus Kaninchenserum isolierbarem IgG. Durch Beimischung von 60 % BDE konnte der Epoxidgehalt vervierfacht und die Porengröße auf 400 nm bei 59 % Porosität reduziert werden. Die spezifische Oberfläche wurde verdreifacht und die Kapazität präparierter Disks auf 0,90 mg/mL etwa verdoppelt. Die in dieser Arbeit entwickelten Disks können zur Isolierung von IgG aus einer komplexen Probe, wie beispielsweise Blutserum, eingesetzt werden. / Monolithic supports have been developed since 20 years and have become an attractive alternative to well-established columns packed with particles over the past years. They are classified into inorganic media and organic polymer monoliths. Monoliths consist of a single, continuous piece with an integrated characteristic porous network through which the eluent can flow with lower hydraulic resistance and which consequently offers higher flow rates. Due to an accelerated mass transfer caused by convection polymer monoliths are mainly used for separation of large biomolecules. In addition, they are stable over a wide pH range and can be polymerized directly (in situ) in the desired format. In the present work the successful preparation of new epoxide-based supports according to a concept introduced by Weller et al. as well as their application in affinity chromatography are reported. Their preparation was carried out by self-polymerization of polyfunctional glycidyl ethers and for functionalization non-polymerized epoxide groups were used. As monomers TEPIC, GE 100 and GE 500 were utilized. The work has focused especially on the polymerization of the higher functional GE 500, which can be perfomed at room temperature and was optimized in terms of both composition and amount of porogen. The extraction of IgG from rabbit serum with a capillary column (66 %, 12 µm, 7m2/g) prepared by 75 vol.-% porogen (dioxane/ MTBE (2:3)) and functionalized with rprotein A resulted in a capacity of 0,44 mg/mL. By addition of 60 % BDE the epoxide content was quadrupled and the pore size reduced to 400 nm while maintaining consistently high porosity of 59 %. The specific surface area was tripled and the capacity of prepared disks approximately doubled to 0,90 mg/mL. The disks developed in this work can be applied for the isolation of IgG from complex samples such as serum.