Nous étudions les aspects spatiaux de l’intrication, d’une part dans le cadre de la génération d’états intriqués de haute dimensionnalité par amplification paramétrique optique, et d’autre part dans le cadre des expériences dites de Hong- Ou- Mandel. La première partie de cette étude s’attache à démontrer l’existence d’un paradoxe Einstein-Podolsky-Rosen (EPR) dans le comportement de la lumière de fluorescence générée par un amplificateur paramétrique optique. Le paradoxe EPR estétudié dans le contexte de sa formulation originelle, c’est-à-dire dans le domaine des positions et impulsions. La détection des photons intriqués est assurée à l’aide de caméras particulières,appelées caméras EMCCD, qui présentent la propriété de pouvoir atteindre un régime de comptage de photons. En prenant des images des faisceaux de fluorescence, nous montrons l’existence d’un paradoxe EPR de haut degré. La seconde partie de cette étude concerne les expérience sde Hong- Ou- Mandel et cherche à démontrer, par l’utilisation de simulations, la possibilité d’obtenir une coalescence complète des paires de photons sur toute l’extension spatiale de faisceaux de fluorescence paramétrique. Partant du constat du comportement non-local qui apparaît clairement au cours de cette étude, nous démontrons la possibilité d’ établir une inégalité de Bell pour ce phénomène d’interférence à deux photons. Nous montrons par ailleurs que le formalisme quantique prévoit la violation de cette inégalité de Bell par un état construit en filtrant l’ état intriqué écrit par EPR en 1935. / Spatial aspects of entanglement in parametric amplification : Einstein-Podolsky-Rosen paradox intwin images and Hong-Ou-Mandel experiment.We study spatial aspects of entanglement, first in the context of spontaneous down converted lightexhibiting high dimensional entanglement, and in a second step through a simulated Hong-Ou-Mandel experiment. The first part of this study demonstrate an Einstein-Podolsky-Rosen paradox inits original formulation, e.g. in the context of position and momentum correlations. We detect photonsby mean of special cameras including a gain register, called EMCCD cameras, able to count photonarrival on each pixel. By taking direct images of the fluorescence beams, we demonstrate a strongdegree of EPR paradox. The second part of this study aim to demonstrate, by mean of simulations,the possibility to obtain a full field coalescence of fluorescence photons, due to the Hong-Ou-Mandeleffect. Starting from the observation that the HOM effect exhibits a nonlocal behaviour, we establisha Bell inequality on the two photons interference phenomenon itself. We then show that the original1935 EPR state is able to violate this Bell inequality

La construction de nouvelles architectures d'aimant moléculaire basé sur l'approche métal-radical repose sur la conception de nouvelles molécules radicalaires. Dans cette optique, notre stratégie s'est concentrée sur la synthèse de porphyrins incorporant des composés radicaux libres. En effet, les porphyrines sont des composés π conjugués qui devraient favoriser la délocalisation de spin et la transmission des interactions magnétiques sur l'entier macrocycle et de plus sur l'ensemble du composé obtenu. A cause de leur excellente stabilité dans une grande diversité d'environnements chimiques et leur capacité à coordonner avec des métaux de transitions, notre choix s'est porté sur les radicaux nitroxides. Dans cette thèse, une série de porphyrines contenant des tBUNO, nitronyl and imino nitroxide directement liés sur le squelette de la molécule ont été synthétisées. Les macrocycles obtenus ont été caractérisés par UV-Vis, Masse et RPE spectroscopie. De plus, durant ce travail, des intermédiaires réactionnaires intéressant ont été obtenus et caractérisés pour la première fois. Ce fut le cas pour la meso-tetrakis(4-formylphenyl)porphyrin et ses équivalents métallés pa le Cu(II) et le Mn(II). Ainsi que pour quelques précurseurs prometteurs de macrocycle tetrapyrroliques comme 2-(3,4-dicyanophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1oxyl, 2-(3,4-dicyanophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and 2-(4-benzaldehyde)-4,4,5,5-tetramethylimidazoline-1-oxyl. D'après ce que nous savons, ces composés représentent le premier exemple de porphyrines substituées par des nitronyl et imino nitroxide radical, ayant été caractérisées sans ambiguïté par des méthodes spectroscopiques / The preparation of Molecule-Based Magnets is based on the assembling carriers of magnetic moment. These may be the metal ions only with diamagnetic linkers or the metal ions connected through open-shell organic molecule. The building of novel Molecule-Based Magnets architectures following the metal-radical approach relies on the design of innovative open-shell organic molecular blocks. In this regard, we focus our strategy on the synthesis of porphyrins incorporating free radicals. Indeed, porphyrins compounds are π-conjugated systems which should favor spin delocalization and the transmission of the magnetic interactions on the overall macrocycle and further over the all architecture. Due to their excellent stability in a wide variety of chemical environments, and their abilities to coordinate with transition metal we focus our attention on nitroxide radicals. In this dissertation a series of porpyrin macrocycles were synthesized, bearing tBuNO, nitronyl and imino nitroxide covalently linked to the skeleton. Characterization was done by UV-Vis, Mass and EPR spectroscopy. Moreover during this work some interesting synthetic intermediates were obtained with good yield and characterize for the first time. This was the case for meso-tetrakis(4-formylphenyl)porphyrin and its corresponding metallated derivatives by Cu(II) and Mn(II). Some novel promising tetrapyrrolic macrocycle precursors bearing nitronyl and imino nitroxides free radicals as 2-(3,4- dicyanophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, 2-(3,4- dicyanophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and 2-(4-benzaldehyde)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl. To the best of our knowledge, these compounds represent the first example of nitronyl and imino nitroxide substituted porphyrin derivatives that have been unambiguously characterized by spectroscopic techniques

Tato práce popisuje historicky první multi-frekvenční rapid-scan EPR. Při zavedení mikrovlnného záření z oblasti 200 GHz a následnou sinusovou modulací bylo dosaženo rychlostí změn frekvence až 61 500 THz/s a zkreslení spekter, známé jako ”wiggles”, bylo pozorováno u obou studovaných vzorků organických radikálů – BDPA v polystyrenové matici a LiPc. Tato práce představuje flexibilní metodu provádění rapid-scan EPR experimentů za použití napětím ovládaného oscilátoru (Voltage Controlled Oscillator; VCO) jako zdroje a zero-bias detektoru (ZBD) pro detekci, čímž se otevírá možnost postupu dále do oblastí vyšších polí / vyšších frekvencí. Dále je popsán postup získání ustáleného spektra z rapid-scan výsledků, známý jako Fourierovská dekonvoluce, a dále je zjistěn spinový dekoherenční čas vzorků pomocí srovnání experimentálních spekter s výsledky numericky vyřešených Blochových rovnic. Výsledné hodnoty jsou 50 ns pro BDPA a 12 ns pro LiPc.

Diploma thesis deals with the characterization of chokeberry (Aronia melanocarpa) and saskatoon berry (Amelanchier alnifolia) fruits. The theoretical part focuses on the botanical classification, chemical composition, curative effects and the use of chokeberry and saskatoon berry in the food industry. Further, the attention is also devoted to a review of methods for the determination of important antioxidants, specialized on the determination of polyphenols, anthocyanins, ascorbic acid and total antioxidant activity. The experimental part of the work deals with the determination of selected parameters in different varieties of chokeberry and serviceberry, harvested in 2012 and 2013 using spectroscopic and chromatographic techniques with an emphasis on effect of solvent (50% ethanol, destilled water, DMSO). Specifically total content of polyphenols and anthocyanins, color characteristics using the CIE L*a*b* system and the ability of the sample to reduce the iron are determined using the UV-VIS-NIR spectroscopy. Further ascorbic acid concentration in individual extracts is quantified by High performance liquid chromatography coupled with a diode array detector and the total antioxidant activity is characterized by electron paramagnetic resonance involving •DPPH and ABTS•+ assays.

The Ph.D. thesis was focused on EPR study of redox reactions of selected types of phenols, secondary amines and diperoxy coumpounds. Within the study some redox agents were employed in nonpolar, in some special cases also in polar solvents. EPR spectra of generated radical products were interpreted using spectral simulation. Study of radical reactions under participation of phenols was preferentially concentrated on the behavior of para methyl substituted phenols, where the instability of this substituent in relation to the applied redox agents was evaluated. The tendency towards the abstraction of hydrogen from methyl group, representing the paralell mechanism to the hydrogen abstaction from phenolic OH group was proved. The generated benzyl radicals were undirectly detected in the form of adducts with aromatic nitroso compounds. These adducts undergo the consecutive transformations, leading to the formation of new types of phenoxy radicals. The study of the decomposition of NH bonds was performed with substituted N,N´-paraphenylenediamines, 1-anilino-1-phenylpentane-3-ones and amino substituted 1,3-dimethyluracils. By the oxidation with 3-chloroperbenzoic acid the corresponding nitroxyl radicals were prepared. In the case of 1-anilino-1-phenylpentane-3-ones the aminyl radicals were prepared by the oxidation with PbO2, which existence was evidenced by spin trapping method with nitrosobenzene. In the framework of the investigation of the decomposition of -O-O- bonds the oxygen centred radicals, generated from peroxidic compounds of Luperox type using selected redox agents were detected by spin trapping method. The analysis of EPR spectra documented that primary alkoxyl radicals undergo the consecutive fragmentation, which leads in the presence of oxygen to the formation of secondary alkoxyl radicals. The generation of oxygen centred radicals during the decomposition was indirectly proved in the presence of model phenolic compounds, where due to the abstraction of hydrogen from phenolic OH group the phenoxyl radicals are formed.

Metal-organic framework (MOF) compounds as a new class of porous coordination polymers consists of metal ions or clusters linked by organic molecules. They have gained recent interest because of their large surface areas and huge variety of the porous network structures. They exhibit interesting adsorption properties and therefore are potential candidates for various technical applications. In this work, continuous wave (cw) and pulsed electron paramagnetic resonance (EPR) methods such as pulsed electron-nuclear double resonance (ENDOR) and hyperfine sublevel correlation (HYSCORE) spectroscopy are applied to study metal-organic frameworks with respect to different aspects of their properties: The host-guest interactions between Cu2+ ions in [Cu3(btc)2]n (HKUST-1; btc: 1,3,5-benzenetricaboxylate) with adsorbed methanol (CH3OH), 13C enriched carbon monoxide and dioxide (13CO, 13CO2), hydrogen (H2), deuterium (D2) and mixed isotopic HD. In [Cu3(btc)2]n, the Cu2+ ions are connected to binuclear Cu/Cu paddle wheel units. Since the Cu2+ ions in the [Cu3(btc)2]n are antiferromagnetically coupled, the new compound [Cu2.97Zn0.03(btc)2]n is synthesized by isomorphous substitution containing about 1 % paramagnetic Cu/Zn paddle wheel units. The modified Cu/Zn paddle wheel units prove to be a very sensitive probe for the interactions with the adsorbed molecules. Secondly, the exchange interactions of antiferromagnetically coupled Cu/Cu paddle wheel units as well as additional inter-paddle wheel exchange interactions between the Cu/Cu pairs are studied in [Cu2(bdc)2(dabco)]n, a layered MOF with 1,4-benzenedicaboxylate (bdc) as linker and 1,4-diazabicyclo[2.2.2]octane (dabco) acting as pillars between the layers. In comparison to [Cu3(btc)2]n, the additional inter-paddle wheel exchange interactions are much easier disturbed by incorporation of Zn2+ ions into the framework structure. Third, the structural dynamics of the framework is investigated in the compound [Al(OH)(bdc)]n (MIL-53) which was isomorphously substituted by V(III)/V(IV) species. The 51V hyperfine structure revealed to be sensitive to the so-called breathing effect, a flexible structural behaviour upon guest adsorption/desorption or upon thermal treatment. It is shown that the aluminum ions can be substituted by vanadium but the octahedral coordination environment changes slightly to a pseudo-octahedral or a square-pyramidal coordination. Based on the hyperfine interactions between the electron spin and the nuclear spins of the surrounding atoms, structural models can be derived from orientation-selective measurements. In such a way, structural information of materials like powder samples and adsorbate complexes can be obtained which are hardly or even not accessible by other methods.:1 Introduction 1.1 Electron paramagnetic resonance spectroscopy for investigation of porous materials 1.2 Metal-organic frameworks 1.3 Implementation of paramagnetism by isomorphous substitution 1.4 EPR spectroscopic methods 1.4.1 Spin Hamiltonian 1.4.2 cw EPR spectroscopy 1.4.3 Pulsed EPR spectroscopy 1.5 Description of the project 2 [Cu2.97Zn0.03(btc)2]n 2.1 Introduction: Monometallic [Cu3(btc)2]n (1) 2.1.1 Spin coupling 2.1.2 Adsorption of H2O 2.1.3 Adsorption of DTBN 2.2 Isomorphous substitution of Cu2+ by Zn2+ in [Cu3(btc)2]n 2.2.1 Synthesis and characterisation of [Cu2.97Zn0.03(btc)2]n (2) 2.2.2 cw EPR spectroscopy of 2 2.2.3 Pulsed EPR spectroscopy of 2 2.2.4 Summary: Zn2+ substitution 2.3 Adsorption of methanol (MeOH) on [Cu2.97Zn0.03(btc)2]n (2_MeOH) 2.3.1 cw EPR spectroscopy of 2_MeOH 2.3.2 Pulsed EPR spectroscopy of 2_MeOH 2.3.3 Discussion 2.3.4 Summary: adsorption of MeOH 2.4 Adsorption of 13CO2 and 13CO on [Cu2.97Zn0.03(btc)2]n (2_CO2, 2_CO) 2.4.1 cw EPR spectroscopy of 2_CO2 and 2_CO 2.4.2 Pulsed EPR spectroscopy of 2_CO2 and 2_CO 2.4.3 Discussion 2.4.4 Summary: adsorption of 13CO2 and 13CO 2.5 Adsorption of H2, D2 and HD on [Cu2.97Zn0.03(btc)2]n (2_HH, 2_DD and 2_HD) 2.5.1 cw EPR spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2 Pulsed EPR spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2.1 3p ESEEM spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2.2 Davies-ENDOR spectroscopy of 2_HH 2.5.2.3 Davies-ENDOR spectroscopy of 2_HD 2.5.2.4 Davies-ENDOR spectroscopy of 2_DD 2.5.3 Discussion 2.5.4 Summary: adsorption of H2, D2 and HD 2.6 Conclusion: [Cu2.97Zn0.03(btc)2]n 3 [Cu2(bdc)2(dabco)]n (3) and [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_x) 3.1 [Cu2(bdc)2(dabco)]n (3) 3.2 [Cu1.9Zn0.1(bdc)2(dabco)]n (3_0.1) 3.3 [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_0.5, 3_1.0, 3_1.5 and 3_1.9) 3.4 Determination of the exchange coupling constant J 3.5 Discussion 3.6 Conclusions: [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_x) 4 [(AlOH)1-x(VO)x(bdc)]n (4) and [(AlOH)1-x(VO)x(ndc)]n (5) 4.1 Introduction 4.2 EPR spectroscopic investigations of mixed-metal bdc compounds 4.3 EPR spectroscopic investigations of mixed-metal ndc compounds 4.4: Conclucions: V(III)/V(IV) substitution in [Al(OH)(bdc)]n and [Al(OH)(ndc)]n 5 Summary and Conclusion 5.1 Host-guest interactions 5.2 Exchange couplings of Cu/Cu pairs 5.3 Structural dynamics of the bdc and the ndc framework 5.4 Conclusion 6 Appendix 6.1 Experimental details and additional spectra 6.2 Instrumental details 6.3 Curriculum vitae and publications

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Den höga textilkonsumtionen i Sverige har resulterat i stora mängder textilavfall, vilket har en negativ påverkan på miljön. Denna kandidatuppsats, författad på° svenska, behandlar hur svenska textilföretag anpassar sig vid ett införande av utökat producentansvar (EPR) för textilier som miljöreglering. Genom att ge producenter ansvar för att hantera sina egna produkter genom hela livscykeln, syftar lagförslaget att främja hållbarhet och cirkulär ekonomi i den textila värdekedjan. Detta är avsett att minska miljöpåverkan och öka återanvändningen av material. Denna studie identifierar de möjligheter och utmaningar som svenska textilföretag möter vid ett införande av EPR för textilier samt undersöker på vilket sätt textilföretagen anpassar sig efter dessa. Studien ämnar att skapa fördjupad förståelse för hur textilsektorn kan navigera genom dessa förändringar för en effektiv implementering av lagen. Studien har samlat empiri genom semistrukturerade intervjuer samt data genom en litteraturstudie. Den kvalitativa metodologin återspeglar ett bekvämlighetsurval på fem respondenter som besitter arbetsroller inom hållbarhet. Insikter från intervjuer, kombinerat med en tematisk analys, identifierar återkommande mönster som presenteras i resultat. Dessa mönster kopplas sedan till litteraturen i analysen och presenteras i diskussionen. Bland möjligheterna som identifierades framhålls ökade incitament för cirkularitet och främjande av samarbetsstrukturer. Vidare möjligheter tyder på åtgärder som främjar cirkulära processer, såsom design för återvinning och användning av återvunnet material. Utmaningarna identifieras ekonomiskt olönsamma strategier, upplevd osäkerhet där otydliga krav presenteras samt bristfällig innovation, där mycket teknologisk utveckling saknas. Utöver dessa möjligheter och utmaningar pekar studien på att företag upplever en viss osäkerhet kring EPR för textilier och därför anpassar sig olika. Bristen på detaljerade tillvägagångssätt hindrar företagen från att förbereda sig fullt ut. Därav väljer vissa att jobba proaktivt och förbereda sig inför vad som komma skall medan andra väntar genom att jobba mer reaktivt för att se hur andra företag agerar. / The high consumption of textiles in Sweden has resulted in large amounts of textile waste, which has a negative impact on the environment. This bachelor's thesis, written in Swedish, addresses how Swedish textile companies adapt to the introduction of extended producer responsibility (EPR) for textiles as an environmental regulation. By assigning producers responsibility for managing their own products throughout their entire lifecycle, the proposed legislation aims to promote sustainability and a circular economy in the textile value chain. This is intended to reduce environmental impact and increase the reuse of materials. This study identifies the opportunities and challenges faced by Swedish textile companies with the introduction of EPR for textiles and examines how these companies adapt to these changes. The study aims to create an in-depth understanding of how the textile sector can navigate these changes for effective implementation of the law. The study collected empirical data through semi-structured interviews and additional data through a literature review. The qualitative methodology reflects a convenience sample of five respondents who hold roles in sustainability. Insights from the interviews, combined with a thematic analysis, identify recurring patterns that are presented in the results. These patterns are then connected to the literature in the analysis and discussed in the discussion section. Among the identified opportunities are increased incentives for circularity and the promotion of collaborative structures. Further opportunities include measures that promote circular processes, such as design for recycling and the use of recycled materials. The challenges identified include economically unfeasible strategies, perceived uncertainty due to unclear requirements, and inadequate innovation, where much technological development is lacking. In addition to these opportunities and challenges, the study indicates that companies experience some uncertainty regarding EPR for textiles and therefore adapt differently. The lack of detailed procedures prevents companies from fully preparing. As a result, some choose to work proactively and prepare for what is to come, while others adopt a more reactive approach, waiting to see how other companies act.

Multidrug resistance (MDR) is a major obstacle limiting chemotherapeutic efficacy. The purpose of these studies was to investigate the potential application of injectable paclitaxel (PX) and doxorubicin (Dox)-loaded nanoparticles (NPs) engineered from oil-in-water microemulsion precursors for overcoming P-glycoprotein (P-gp)- mediated drug resistance in solid tumors. An in-vitro study was performed to test whether the oil (stearyl alcohol and cetyl alcohol) used to make lipid nanoparticles could be metabolized. The results showed that the concentrations of the fatty alcohols within nanoparticles, which were quantitatively determined over time by gas chromatography, decreased to only 10-20% of the initial concentration after 15-24 h of incubation with horse liver dehydrogenase (HLADH) and NAD+ at 37ºC. Moreover, the surfactant Brij 78 (polyoxyethylene 20-sterayl ether) in the nanoparticles influenced the activity of the enzyme. Novel Cremophor EL-free paclitaxel-loaded nanoparticles were developed using experimental design combining Taguchi array and sequential simplex optimization. The resulting PX G78 and PX BTM NPs were stable at 4ºC over five months and in PBS at 37ºC over 102 h. Release of PX from PX NPs was slow and sustained without initial burst release. Interestingly, PX BTM NPs could be lyophilized without cryoprotectants and without changing any physiochemical properties and bioactivities. Cytotoxicity studies in breast cancer MDA-MB-231 cells showed that PX NPs have similar anti-cancer activities compared to Taxol. Optimized Dox-loaded NPs were prepared using an ion-pair agent, sodium tetradecyl sulfate (STS), to mask Dox charge and to enhance its entrapment in NPs. In-vitro cytotoxicity studies were carried out in both sensitive and resistant human cancer cells treated with PX and Dox-loaded NPs. All of drug-loaded NPs decreased IC50 values by 6-13-fold in resistant cells compared to free drugs. A series of in-vitro assays were used to understand the underlying mechanisms. The results, in part, showed that the NPs inhibited P-gp and transiently depleted ATP, leading to enhanced uptake and prolonged retention of the drugs in P-gp-overexpressing cancer cells. Finally, in-vivo anti-cancer efficacy studies were performed using pegylated PX BTM NPs after intravenous (i.v.) injection and showed marked anti-cancer efficacy in nude mice bearing resistant NCI/ADR-RES tumors versus all control groups. These results suggest that NPs may be used to both target drug and biological mechanisms to overcome MDR.

The photosynthetic process has the unique ability to capture energy from sunlight and accumulate that energy in sugars and starch. This thesis deals with the light driven part of photosynthesis. The aim has been to investigate how the light-absorbing protein complexes Photosystem I (PS I) and Photosystem II (PS II), react upon illumination of light with lower energy (far-red light; 700-850 nm) than the absorption peak at respective primary donor, P700 and P680.  The results were unexpected. At 295 K, we showed that both PS I and PS II were able to perform photochemistry with light up to 130 nm above its respective primary donor absorption maxima. As such, it was found that the primary donors’ action spectra extended approximately 80 nm further out into the red-region of the spectrum than previously reported.  The ability to perform photochemistry with far-red light was conserved at cryogenic temperatures (< 77 K) in both photosystems. By performing EPR measurements on various photosystem preparations, under different illumination conditions the origin of the effect was localized to their respective reaction center. It is also likely that underlying mechanism is analogous for PS I and PS II, given the similarities in spatial coordination of the reaction center pigments. For PS II, the results obtained allowed us to suggest a model involving a previously unknown electron transfer pathway. This model is based upon the conclusion that the primary cation from primary charge separation induced by far-red light resides primarily on ChlD1 in P680. This is in contrast to the cation being located on PD1, as has been suggested as for visible light illumination. The property to drive photochemistry with far-red wavelengths implies a hither to unknown absorption band, probably originating from the pigments that compose P700 and P680. The results presented here might clarify how the pigments inside P680 are coupled and also how the complex charge separation processes within the first picoseconds that initiate photosynthetic reactions occur.