Organinė elektronika pastaruoju metu yra viena sparčiausiai besiplėtojančių puslaidininkių prietaisų krypčių. Ši kryptis labai sparčiai vystoma dėl nuolat kuriamų naujų organinių junginių ir tobulėjančių inžinerijos galimybių. Šiuo metu organinės medžiagos naudojamos organiniuose šviestukuose (OLED), plonasluoksniuose tranzistoriuose, saulės celėse, jutikliuose ir kt. Organinės medžiagos įgalina gaminti didelio ploto bei lanksčius elektronikos prietaisus, gamybai pasitelkiant pigias gaminimo technologijas. Modernios organinės elektronikos medžiagos yra daugiafunkcinės – tai leidžia ne tik pagerinti medžiagos savybes, bet ir supaprastinti technologiją, kur viename sluoksnyje daugiafunkcinė molekulė atlieka keletą funkcijų. Tačiau molekulinės struktūros sudėtingėjimas iškelia naujas problemas susijusias su naujais sudėtingais reiškiniais daugiafunkciniame molekuliniame darinyje, tokiais kaip agregatų formavimas, vidujemolekulinė krūvio pernaša, vidujemolekulinė sąsūka ir kt. Todėl naujų daugiafunkcinių molekulinių darinių savybių optimizavimas yra aktuali nūdienos organinės elektronikos problema. Šiame darbe didžiausias dėmesys skiriamas daugiafunkcinių organinių spinduolių fotofizikinių savybių valdymui. Čia nagrinėjami daugiafunkcinių molekulinių spinduolių agregacijos nulemti reiškiniai ir jų valdymo galimybės, optimizuojant sluoksnio funkcines savybes tokias kaip plėvėdaros savybės, krūvio pernaša, emisijos našumas, sustiprintos savaiminės spinduliuotės slenkstis ir kt. / Currently, organic electronics is one of the most expanding technology of semiconductor devices. This direction is rapidly developing due to the constant synthesis of new organic compounds and sophisticated advances in device engineering. Currently, organic materials are used in organic light-emitting diodes (OLEDs), organic thin-film transistors, solar cells and sensors. Low-cost manufacturing techniques such as wet casting or inkjet printing enable organic materials use in large-area and flexible electronic devices. Modern organic electronic materials are multifunctional – this enables not only to improve the material properties, but also to simplify the device architecture. However, the complexity of the molecular structure brings new problems associated with complex phenomena of the new multifunctional molecules -such as the formation of aggregates, intramolecular charge transfer, intramolecular torsion and others. Therefore, the control of the features of new multifunctional molecules is the main problem of organic electronics today. This work focuses on the control of photophysical characteristics of multifunctional organic emitters. Here we study aggregation induced emission and quenching of multifunctional molecular emitters and the possibilities to control these phenomena by optimizing functional properties of the film such as film forming properties, charge transfer, the emission efficiency, amplified spontaneous emission threshold and others.

Currently, organic electronics is one of the most expanding technology of semiconductor devices. This direction is rapidly developing due to the constant synthesis of new organic compounds and sophisticated advances in device engineering. Currently, organic materials are used in organic light-emitting diodes (OLEDs), organic thin-film transistors, solar cells and sensors. Low-cost manufacturing techniques such as wet casting or inkjet printing enable organic materials use in large-area and flexible electronic devices. Modern organic electronic materials are multifunctional – this enables not only to improve the material properties, but also to simplify the device architecture. However, the complexity of the molecular structure brings new problems associated with complex phenomena of the new multifunctional molecules -such as the formation of aggregates, intramolecular charge transfer, intramolecular torsion and others. Therefore, the control of the features of new multifunctional molecules is the main problem of organic electronics today. This work focuses on the control of photophysical characteristics of multifunctional organic emitters. Here we study aggregation induced emission and quenching of multifunctional molecular emitters and the possibilities to control these phenomena by optimizing functional properties of the film such as film forming properties, charge transfer, the emission efficiency, amplified spontaneous emission threshold and others. / Organinė elektronika pastaruoju metu yra viena sparčiausiai besiplėtojančių puslaidininkių prietaisų krypčių. Ši kryptis labai sparčiai vystoma dėl nuolat kuriamų naujų organinių junginių ir tobulėjančių inžinerijos galimybių. Šiuo metu organinės medžiagos naudojamos organiniuose šviestukuose (OLED), plonasluoksniuose tranzistoriuose, saulės celėse, jutikliuose ir kt. Organinės medžiagos įgalina gaminti didelio ploto bei lanksčius elektronikos prietaisus, gamybai pasitelkiant pigias gaminimo technologijas. Modernios organinės elektronikos medžiagos yra daugiafunkcinės – tai leidžia ne tik pagerinti medžiagos savybes, bet ir supaprastinti technologiją, kur viename sluoksnyje daugiafunkcinė molekulė atlieka keletą funkcijų. Tačiau molekulinės struktūros sudėtingėjimas iškelia naujas problemas susijusias su naujais sudėtingais reiškiniais daugiafunkciniame molekuliniame darinyje, tokiais kaip agregatų formavimas, vidujemolekulinė krūvio pernaša, vidujemolekulinė sąsūka ir kt. Todėl naujų daugiafunkcinių molekulinių darinių savybių optimizavimas yra aktuali nūdienos organinės elektronikos problema. Šiame darbe didžiausias dėmesys skiriamas daugiafunkcinių organinių spinduolių fotofizikinių savybių valdymui. Čia nagrinėjami daugiafunkcinių molekulinių spinduolių agregacijos nulemti reiškiniai ir jų valdymo galimybės, optimizuojant sluoksnio funkcines savybes tokias kaip plėvėdaros savybės, krūvio pernaša, emisijos našumas, sustiprintos savaiminės spinduliuotės slenkstis ir kt.

Orientadora: Prof.ª Dr.ª Karina Passalacqua Morelli Frin / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Quatro compostos polipiridinicos de Re(I), fac-[Re(CO)3(ph2phen)(L)]+ (L = bpa, 4,4¡¦-bpy e, apy) e fac-[{(Ph2phen)(CO)3Re}2(bpa)]+2, foram sintetizados e purificados. Os complexos foram caracterizados por espectroscopia de 1H RMN, IR/ATR e UV-vis em MeCN a 298 K. Foi verificado intensa absortividade (4.104 Lmol-1cm-1) na regiao UVB (£fmax =292 nm) do espectro atribuida a transicao intraligante 1ILPh2phen, e a transicao de transferencia de carga do metal para o ligante 1MLCTRe ¿_ Ph2phen (1.104 Lmol-1cm-1) em aproximadamente £f ~350 nm. As propriedades fotofisicas produzem 3MLCT Re ¿_ Ph2phen que apresentam intensa luminescencia em £fem = 562 nm usando-se excitacao em comprimento de onda monocromatico de 375 nm possuindo rendimento quantico de emissao (¿Öem) da ordem de 0,036-0,360 e tempo de vida de emissao (£n) de £gs, sendo que a luminescencia observada varia em funcao do carater doador e aceptor de densidade eletronica do ligante (L) definindo a basicidade e acidez dos complexos em solucao. As propriedades fotofisicas em pol (metacrilato de metila) PMMA exibiram o efeito rigidocromico observado por meio do deslocamento hipsocromico da emissao sem alteracao na estrutura da banda 3MLCT Re Ph2phen. O estudo de supressao com hidroquinona (H2Q) em solucao desaerada de MeCN a 298 K demonstrou excelente correlacao entre intensidade de emissao (I) e tempo de vida de emissao (£n) dos complexos na metodologia de Stern-Volmer. Para os complexos fac-[R (CO)3(Ph2phen)(bpa)]+, fac-[Re(CO)3(Ph2phen)(4,4¡¦-bpy)]+ e fac-[{(Ph2phen)(CO)3Re}2(bpa)]2+ foram determinadas as constantes Ksv da ordem de 104 Lmol-1 com correspondentes constantes cineticas de supressao bimolecular kq 109 Lmol-1s-1 revelando forte supressao do estado excitado associado ao mecanismo dinamico de transferencia de eletron (ET) por meio de interacoes/empilhamento £k-£k* como sugestao de rota mais eficiente. Enquanto, para o complexo fac-[Re(CO)3(Ph2phen)(apy)]+ a constante Ksv obtida foi de 102 Lmol-1 e, kq 109 Lmol-1s-1, demostrando evidencias de um caminho alternativo para supressao desse composto com H2Q envolvendo um possivel mecanismo dinamico de supressao via transferencia protonica acoplada a transferencia de eletron (EPT) que e menos eficiente, assumindo-se a existencia de intrinseco pre-equilibrio acido-base desse complexo em solucao. / Four polypyridyl Re(I) compounds, fac-[Re(CO)3(ph2phen)(L)]+ (L = bpa, 4,4¡¦-bpy e, apy) and fac-[{(Ph2phen)(CO)3Re}2(bpa)]+2, were synthesized and purified. The complexes have been characterized by 1H NMR, IR/ATR and UV-vis spectroscopies in MeCN at 298 K. Verified intensity absorption (4.104 Lmol-1cm-1) in UVB spectral region (£fmax = 292 nm) assigned to the intraligand 1ILPh2phen transition, and the metal-to-ligand charge transfer 1MLCTRe ¿_ Ph2phen transitions (1.104 Lmol-1cm-1) in about £f ~350 nm. The photophysical properties produces 3MLCT Re ¿_ Ph2phen which account for stronger luminescence in £fem = 562 nm using monochromatic excitation 375 nm resulting in emission quantum yields (¿Öem) in the range of 0,036-0,360 and lifetimes (£n) of the order of £gs, wherein the luminescence observed as a function of the donor or acceptor of electron density of the ligand (L) defining the basicity and acidity of the complexes in solution. The photophysical properties in poly(methyl methacrylate) PMMA exhibited the rigidochromic effect observed by hypsochomic shifts in spectra with no change in the emission band structure 3MLCT Re ¿_ Ph2phen. The quencher studies by hydroquinone (H2Q) in degassed MeCN solution at 298 K demonstrated excellent correlation between emission intensity (I) and lifetime (£n) for the complexes using Stern-Volmer methodology. For fac-[Re(CO)3(Ph2phen)(bpa)]+, fac-[Re(CO)3(Ph2phen)(4,4¡¦-bpy)]+ and fac-[{(Ph2phen)(CO)3Re}2(bpa)]2+ complexes were determined Ksv constant in 104 Lmol-1 order, and the corresponding rate constant for the bimolecular excited state quenching kq 109 Lmol-1s-1 revealed stronger excited-state quenching associated with the dynamic mechanism of the electron transfer (ET) by £k-£k* stacked suggesting a more efficient pathway. While for the fac-[Re(CO)3(Ph2phen)(apy)]+ complex the Ksv obtained constant was 102 Lmol-1 and respective kq = 109 Lmol-1s-1 demonstrated the evidence of an alternate path for quenching that compound by H2Q involving a possible less efficient dynamic mechanism the electron-proton-transfer (EPT) assumed the intrinsic preequilibria acid-base that complexes in solution.

Foram sintetizados, purificados e caracterizados os peróxidos cíclicos: peróxido de difenoíla (1), dimetil-1,2-dioxetanona (2), e spiro-adamantil α-peróxi lactona (3), e determinados seus parâmetros de quimiluminescência. Foram redeterminados os rendimentos quânticos singlete na decomposição catalisada de 1 e 2 em condições análogas as utilizadas anteriormente na literatura, obtendo-se valores várias ordens de grandeza menores que os inicialmente relatados para estes sistemas padrão para a formulação do mecanismo Luminescência Iniciada Quimicamente por Troca de Elétron (Chemically Initiated Electron Exchange Luminescence - CIEEL). O efeito de gaiola de solvente, utilizando-se o sistema binário tolueno/difenilmetano, sobre o rendimento quântico na decomposição de 1 catalisada por rubreno, mostrou-se consideravelmente menor para este sistema intermolecular do que o observado no sistema intramolecular da decomposição induzida de 1,2-dioxetanos fenóxi-substituidos. Foram determinados pela primeira vez os parâmetros de quimiluminescência na decomposição unimolecular e catalisada da spiro-adamantil α-peróxi lactona (3), mostrando que esta é a α-peróxi lactona mais estável sintetizada e estudada até o momento. Este peróxido é sujeito à decomposição catalisada por ativadores adequados, envolvendo transferência de elétron, porém, com eficiência baixa devido a um impedimento estérico exercido pelo substituinte spiro-adamantila sobre a interação do peróxido com o ativador. O rendimento quântico singlete máximo obtido na decomposição catalisada de 3 é de 1%, valor consideravelmente menor que os determinados para sistemas intramoleculares. A decomposição dos peróxidos cíclicos 1 a 3 é catalisada por fenolatos como ativadores, porém, os rendimentos singlete obtidos nesta reação são baixos, entre 10-3 e 10-7 E mol-1. Os resultados obtidos com este sistema modelo intermolecular para a decomposição induzida por transferência intramolecular de elétron de 1,2-dioxetanos fenóxi-substituidos, demonstram claramente que esta última transformação quimiluminescente de alta eficiência deve ocorrer por uma retro-transferência de elétron intramolecular e não intermolecular como proposto na literatura, e como é necessariamente o caso no sistema modelo estudado no presente trabalho. / The cyclic peroxides diphenoyl peroxide (1), dimethyl-1,2-dioxetanone (2) and spiro-adamantyl α-peroxy lactone (3) were synthesized, purified and characterized, as well as its chemiluminescence parameters determined. The singlet quantum yields in the catalyzed decomposition of 1 and 2 were re-determined in experimental conditions equivalent to those formerly utilized in the literature, obtaining values various orders of magnitude lower than the ones initially reported for these model systems for the formulation of the Chemically Initiated Electron Exchange Luminescence\" (CIEEL) mechanism. The solvent-cage effect on the singlet quantum yields in the rubrene catalyzed decomposition of 1, using the binary system toluene / diphenylmethane, showed to be considerably lower for this intermolecular system than the one observed in the intramolecular system of the induced phenoxy-substituted 1,2-dioxetane decomposition. The chemiluminescence parameters in the unimolecular and catalyzed spiro-adamantyl α-peroxylactone (3) decomposition were determined for the first time, showing that 3 is the most stable α-peroxylactone synthesized and studied up to now. This peroxide is subject to catalyzed decomposition by appropriate activators involving electron transfer, however, with low efficiency due to the steric effect of the spiro-adamantyl substituents on the interaction of the peroxide with the activator. The maximum singlet quantum yield obtained in the catalyzed decomposition of 3 is 1 %, a value considerably lower than those determined for intramolecular systems. The decomposition of the cyclic peroxides 1 to 3 is catalyzed by fenolato ions as activators, thus the singlet quantum yields measured for this reaction are low, between 10-3 e 10-7 E mol-1. The results obtained for this intermolecular model system for the induced phenoxy-substituted 1,2-dioxetane decomposition demonstrate clearly that the latter highly efficient chemiluminescent transformation should occur by an intramolecular back-electron transfer and not by an intermolecular one as proposed in the literature, and as is necessarily the case in the model system studied in this work.

This Thesis describes the synthesis, structural, photochemical and photophysical studies of modified retinal protonated Schiff bases in solution. Ultrafast laser spectroscopy, NMR and circular dichroism studies were employed to investigate speed, yield and selectivity of photoisomerisation in these chromophores. <b>Chapter 1</b> introduces relevant biological, photophysical and photochemical aspects of retinal protonated Schiff base photoisomerisation. It includes an overview of synthetic approaches to modified retinal synthesis pertinent to this this work. <b>Chapter 2</b> discuses the investigation of the hypothesis that twisting of the chromophore’s isomerising double bond is responsible for ultrafast photoisomerisation in the protein environment. In these studies it was discovered that addition of a methyl group to the retinal backbone in solution results in protein-like photophysics. <b>Chapter 3</b> presents photopysical and photochemical studies of modified all-trans retinal protonated Schiff bases that culminate in a qualitative model for the influence of electronic factors on photochemical and photophysical behaviour of these chromophores in solution. <b>Chapter 4</b> describes structural and photophysical investigations of 11-cis retinal protonated Schiff bases. NMR studies indicate conformational flexibility of the chromophores. The first synthetic solution-based chromophore to reach rhodopsins’s speed of photoisomerisation is described. <b>Chapter 5</b> presents an attempt to gain conformational information on retinal protonated Schiff bases using circular dichroism spectroscopy. Transfer of stereochemical information from the covalently attached stereogenic centre to the retinal backbone is demonstrated.

In this master thesis I have been dealt with the design and construction of an instrumental platform that used positioning focused laser beam (so-called optical tweezers) for manipulation with living cells without their damage.

Title: Advanced spectroscopic characterization of quantum dot ensembles Author: Michael Greben Department: Department of Chemical Physics and Optics Supervisor of the doctoral thesis: Prof. Jan Valenta, Ph.D. Abstract: Semiconductor quantum dots (QDs) are small crystallites whose sizes (of the order of nm) cause spatial confinement of carriers in all 3 dimensions. As result, QDs often reveal very different physical properties in comparison with their bulk counterparts. From the optical point of view, the broadening of bandgap with QD-size shrinking is particularly interesting. It is a purely quantum mechanical effect that results from quantum confinement (QC), i.e. dimensional limitations of excitons. A strong spatial confinement leads to a relaxation of momentum (Heisenberg uncertainty principle), consequently, larger overlap of the wave-functions of carriers results in significant increase of probability of radiative recombination. Therefore ensembles of QDs are promising candidates for new generations of photonic and photovoltaic devices. This PhD thesis is primary focused on detailed spectroscopic characterization of ensembles of direct (PbS) and indirect (Si) semiconductor QDs in both colloidal (toluene) and matrix-embedded (oxide or oxinitrides multilayers) forms. The oleic- acid capped PbS QDs were...

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The in origin intertidal marine brown alga Fucus vesiculosus L. grow permanently sublittoral in the brackish Bothnian Sea, side by side with the recently discovered F. radicans L. Bergström et L. Kautsky. Environmental conditions like salinity, light and temperature are clearly different between F. vesiculosus growth sites in the Bothnian Sea (4-5 practical salinity units, psu; part of the Baltic Sea) and the tidal Norwegian Sea (34-35 psu; part of the Atlantic Ocean). The general aims of this thesis were to compare physiological aspects between the marine ecotype and the brackish ecotype of F. vesiculosus as well as between the two Bothnian Sea species F. vesiculosus and F. radicans. The result in the study indicates a higher number of water soluble organic compounds in the marine ecotype of F. vesiculosus compared to the brackish ecotype. These compounds are suggested to be compatible solutes and be due to an intertidal and sublittoral adaptation, respectively; where the intertidal ecotype needs the compounds as a protection from oxygen radicals produced during high irradiation at low tide. The sublittoral ecotype might have lost the ability to synthesize these compound/compounds due to its habitat adaptation. The mannitol content is also higher in the marine ecotype compared to the brackish ecotype of F. vesiculosus and this is suggested to be due to both higher level of irradiance and higher salinity at the growth site. 77 K fluorescence emission spectra and immunoblotting of D1 and PsaA proteins indicate that both ecotypes of F. vesiculosus as well as F. radicans have an uneven ratio of photosystem II/photosystem I (PSII/PSI) with an overweight of PSI. The fluorescence emission spectrum of the Bothnian Sea ecotype of F. vesiculosus however, indicates a larger light-harvesting antenna of PSII compared to the marine ecotype of F. vesiculosus and F. radicans. Distinct differences in 77 K fluorescence emission spectra between the Bothnian Sea ecotype of F. vesiculosus and F. radicans confirm that this is a reliable method to use to separate these species. The marine ecotype of F. vesiculosus has a higher photosynthetic maximum (Pmax) compared to the brackish ecotype of F. vesiculosus and F. radicans whereas both the brackish species have similar Pmax. A reason for higher Pmax in the marine ecotype of F. vesiculosus compared to F. radicans is the greater relative amount of ribulose-1.5-bisphosphate carboxylase/oxygenase (Rubisco). The reason for higher Pmax in marine ecotype of F. vesiculosus compare to the brackish ecotype however is not due to the relative amount of Rubisco and further studies of the rate of CO2 fixation by Rubisco is recommended. Treatments of the brackish ecotype of F. vesiculosus in higher salinity than the Bothnian Sea natural water indicate that the most favourable salinity for high Pmax is 10 psu, followed by 20 psu. One part of the explanation to a high Pmax in 10 psu is a greater relative amount of PsaA protein in algae treated in 10 psu. The reason for greater amount of PsaA might be that the algae need to produce more ATP, and are able to have a higher flow of cyclic electron transport around PSI to serve a higher rate of CO2 fixation by Rubisco. However, studies of the rate of CO2 fixation by Rubisco in algae treated in similar salinities as in present study are recommended to confirm this theory. / Fucus vesiculosus L. (Blåstång) är en brunalg som i huvudsak växer i tidvattenzonen i marint vatten men arten klarar också att växa konstant under ytan i det bräckta Bottenhavet. Norska havet och den del av Bottenhavet, där algerna är insamlade i denna studie, har salthalterna 34-35 psu (praktisk salthaltsenhet) respektive 4-5 psu. F. radicans L. Bergström et L. Kautsky (Smaltång) är en nyligen upptäckt art (2005) som har utvecklats i Bottenhavet. F. radicans och Bottenhavets ekotyp av F. vesiculosus växer sida vid sida och har tidigare ansetts vara samma art. Sett till hela Östersjön, så ändras ytans salthalt från 25 till 1-2 psu mellan Östersjöns gräns mot Kattegatt och norra Bottenviken. Den låga salthalten i Östersjön beror på det höga flödet av sötvatten från älvarna och på ett litet inflödet av saltvatten i inloppet vid Kattegatt. Salthaltsgradienten är korrelerad med antalet arter som minskar med minskad salthalt. Östersjön är ett artfattigt hav och de arter som finns är till stor del en blandning av söt- och saltvattenarter. Det finns bara ett fåtal arter som är helt anpassade till bräckt vatten och F. radicans är en av dem. Exempel på miljöskillnader för F. vesiculosus i Norska havet och i Bottenhavet är salthalten, tidvattnet, ljuset och temperaturen. Tidvattnet i Norska havet gör att algerna växlar mellan att vara i vattnet och på land, vilket utsätter algerna för stora ljusskillnader, snabba och stora temperaturväxlingar samt även torka. De alger som växer i Bottenhavet har däremot en jämnare och lägre temperatur, istäcke på vintern och mindre tillgång på ljus eftersom de alltid lever under vattenytan. Skillnaderna i miljön mellan växtplatserna leder till skillnader i fysiologiska anpassningar. Anledningen till att F. vesiculosus och F. radicans valdes som studieobjekt i denna avhandling är att de är viktiga nyckelarter i Bottenhavet. F. vesiculosus och F. radicans är de enda större bältesbildande alger som finns i det artfattiga ekosystemet och de används därför flitigt som mat, gömställe, parningsplats och barnkammare för t.ex. fisk. Att de är nyckelarter gör det angeläget att försöka förstå hur algerna är anpassade och hur de reagerar på miljöförändringar för att få veta hur de kan skyddas och bevaras. F. radicans inkluderades även för att se hur en naturlig art i Bottenhavet är anpassad i jämförelse med den invandrade F. vesiculosus. Marin F. vesiculosus inkluderades för att vara en artreferens från artens naturliga växtplats. Studien visar att det finns fler vattenlösliga organiska substanser (finns vissa organiska substanser som har en proteinskyddande funktion) i den marina ekotypen av of F. vesiculosus än i Bottenhavets ekotyp. Anledningen till detta föreslås vara en anpassning till att växa i tidvattenzonen. Vid lågvatten utsätts F. vesiculosus från Norska havet för starkt ljus, uttorkning, och snabba temperatur- växlingar vilket gör att den kan behöva dessa organiska substanser som skydd mot fria syreradikaler som bildas under lågvattenexponeringarna. F. vesiculosus från Bottenhavet har troligen mist förmågan att syntetisera dessa substanser på grund av anpassning till att hela tiden växa under ytan. Mängden mannitol (socker) är högre i den marina ekotypen av of F. vesiculosus än i Bottenhavets ekotyp. Detta föreslås bero på högre fotosyntetiskt maximum i F. vesiculosus från Norska havet jämfört med ekotypen från Bottenhavet. Skillnaden i fotssyntetiskt maximum är bland annat kopplat till ljus- och salthaltskillnaden på algernas växtplatser. Denna teori styrks av att både fotosyntesen och halten av mannitol ökar i Bottenhavets ekotyp när den behandlas i högre salthalt. Studien visar även att båda ekotyperna av F. vesiculosus samt F. radicans har ett ojämnt förhållande mellan fotosystem II och I (PSII och PSI) med en dominans av PSI. Denna slutsats är baserad på fluorescens emissions mätningar vid 77 K (-196 °C) och mätning av den relativa mängden D1 protein (motsvarar PSII) och PsaA protein (motsvarar PSI). F. vesiculosus från Bottenhavet visar ett emission spektrum som pekar mot en jämnare fördelning av PSII och PSI jämfört med den marina ekotypen och F. radicans. Detta stämmer dock inte med förhållandet mellan D1/PsaA som indikerar att alla tre har mer PSI än PSII. Förklaringen till avvikelsen mellan metoderna antas vara att F. vesiculosus från Bottenhavet har större ljus-infångande antennpigment än marin F. vesiculosus och F. radicans. De tydliga skillnaderna i 77 K fluorescens emission spektra mellan Bottenhavets F. vesiculosus och F. radicans visar att denna metod kan användas som säker artidentifiering. Den marina ekotypen av F. vesiculosus har högre fotosyntetiskt maximum än de båda arterna från Bottenhavet. Mätningar av den relativa mängden av enzymet Rubisco, viktigt för upptaget av koldioxid hos växter och alger, visar att mängden enzym är en sannolik förklaring till skillnaden i fotosyntetiskt maximum mellan den marina ekotypen av F. vesiculosus och F. radicans och detta är troligen en normal artskillnad. Mängden Rubisco kan dock inte förklara skillnaden i fotosyntetiskt maximum mellan de båda ekotyperna av F. vesiculosus. För att undersöka vad skillnaden mellan dessa två beror på så föreslås istället mätningar av Rubisco’s koldioxidfixeringshastighet. Det är en ökning av fotosyntetiskt maximum i Bottenhavets ekotyp av F. vesiculosus när den behandlas i högre salthalt (10, 20 och 35 psu) och det högsta fotosyntetiska maximumet uppmättes i alger som behandlats i 10 psu. Denna ökning beror inte på ökning i den relativa mängden av Rubisco. Ökningen i fotosyntesen speglas dock av en ökning av den relativa mängden PsaA. Detta antas bero på att det behövs mer energi i form av ATP och att en ökning av detta kan ske på grund av att mer PsaA kan driva den cykliska elektrontransporten i fotosyntesreaktionen. Ökat behov av ATP antas bero på en ökning av Rubisco aktiviteten men mätning av aktiviteten krävs för att bekräfta detta.

Colloidal semiconductor nanocrystals (NCs) have attracted a great deal of interest as bright and stable chromophores for a variety of applications. Their superior physicochemical properties depend on characteristics of the inorganic core, as well as on the chemical nature and structure of the stabilizing organic ligand shell. To evaluate the promising material, a thorough knowledge of structure-property relationships is still demanded. The present work addresses this challenge to three water-soluble NC systems, namely thiol-capped CdTe, thiol-capped CdHgTe, and DNA-functionalized CdTe NCs with special emphasis on the investigation of structure, modification, and influence of the ligand shell. Remarkably, CdTe NCs show bright emission in the visible spectral region and can be synthesized in high quality directly in water. It was shown that the aqueous synthesis also facilitates the preparation of strongly near-infrared (NIR) emitting CdHgTe NCs. The current work presents a detailed study on parameters, by which the emission can be tuned, such as the growth time, the initial Cd : Hg ratio, and the choice of ligand. These insights contribute to the knowledge, which is essential for the design of highly emissive and long-term stable NIR emitting NCs. Further variations of the NC/ligand system include the modification of the ligand shell of CdTe NCs with oligonucleotides based on the strong attachment of DNA molecules to the NC. The successful functionalization of NCs with single-stranded DNA molecules is very promising for the precise and programmable assembly of NCs using DNA origami structures as templates. For both, functionality and optical properties, the surface chemistry of the NCs plays a substantial role and was subject to an extensive investigation. As there is no generally applicable technique to determine the amount of stabilizers and the structure of the ligand shell, the presented study is based on a combination of various methods particularly tailored to the analysis of water-soluble CdTe NCs capped by short-chain thiols. CdTe NCs served as a model system for the described analysis of the ligand shell, since they are thoroughly studied regarding synthesis and features of the core. Aiming for the quantification of thiols, a straightforward colorimetric assay, the Ellman\'s test, is for the first time introduced for the analysis of NCs. Accompanied by elemental analysis an approximate number of thiols per NC becomes accessible. Moreover, theoretical calculations were performed to estimate the amount of ligand that would cover the NC in a monolayer of covalently bound molecules. In contrast to these results, the experimental values point to a larger amount of thiols immobilized on the NC. Attempts to remove the ligand indicate the presence of Cd in the ligand shell and thermogravimetric studies show that the ligands are not loosely assembled in the ligand shell. The outstanding conclusion of these findings involves the presence of Cd-thiol complexes in the ligand shell. Further results unambiguously show that the amount of Cd-thiol complexes present in the NC solution strongly influences the concentration-dependent emission yield of the NCs. Additional studies dedicated to the considerable influence of the ligand shell highlight a strong effect of pH, NC concentration, type and purity of the solvent, and the number of precipitation steps on the emission of water-soluble semiconductor NCs. These substantial investigations emphasize the need to carefully control the conditions applied for handling, optical measurements, and application of NCs. In order to gain a deeper insight into the complex structure of the native ligand shell, techniques deliberately chosen for the in situ analysis were applied for thioglycolic acid-capped CdTe NCs. Information from dynamic light scattering (DLS) regarding the stability and the shell thickness are consistent with previous results showing a large ligand network on the NC surface and a decreasing stability of the NCs upon dilution. Importantly, nuclear magnetic resonance (NMR) spectroscopy allows for the distinction of bound and free ligands directly in solution and proves the presence of these species for the NCs studied. In particular, the results indicate that the ligands are not strongly bound to the NC core and that both, free and bound ligand species, consist of modified thiol molecules, such as Cd-thiol complexes. These findings support previous assumptions and allow to establish a distinct picture of the ligand shell of water-soluble semiconductor NCs. Further insights were obtained from small-angle X-ray scattering (SAXS), which facilitates the identification and the determination of the composition of NC core as well as ligand shell. Element-specific SAXS yields the final proof of the presence of Cd in the ligand shell. The model developed for the optimal fitting of the experimental scattering curves additionally confirms the findings from the other methods. In conclusion, the present work contributes to the challenging goal of a comprehensive knowledge of interactions between the NC core and the ligands. The fundamental development of a structural model of water-soluble CdTe NCs including information on stoichiometries is accomplished by the combination of the techniques presented and emphasizes the challenge to assign a clear border between the ligand shell and the Cd-thiol complexes in solution. Altogether, CdTe NCs capped by thioglycolic acid are best described by a crystalline core surrounded by a water-swollen Cd-thiolate shell that considerably affects the optical properties of the system. Notably, the results of the versatile study provide the opportunity to control the overall properties and to evaluate water-soluble semiconductor NCs for particular applications in photonics and optoelectronics.