1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.9 Potential Strategies for the Development of Novel Photosensitizers 3.2.9.1 Concepts in Focus With 92, a sensitizer was obtained having outstanding characteristics: 124 • Fully synthetic accessibility in high yields (∼ 46 % overall from parental porphyrin hν system 88) as pure and well-defined substance. • High stability towards light and oxygen. 104 • Good to excellent solubility in organic solvents including alcohols and ethers without any tendency to self-aggregation. • High quantum yields for the generation of cytotoxic singlet oxygen. Together with the amino group, providing the ability to couple that system to any (carboxylic) acid moiety, 92 can be regarded as potential photoactive dye for the implementation into 3 rd generation sensitizers like it has already been shown in Scheme 16 (p. 20). As 92 showed up highly effective as monomer, a huge multiplier could be possibly unnecessary. Furthermore, it provides the possibility to study novel approaches to photosensitization. An innovative concept thereto is the utilization of the so-called FÖRSTER resonance energy transfer (FRET) 107c describing non-radiative energy transfer mechanisms between different dye molecules. In the two-dye case, the donor chromophore is excited by light and transferring energy to a proximately situated acceptor chromophore by long-range dipole- dipole coupling. Since the distance between these two dyes is very small (typically < 10 nm) it is much smaller than the wavelength of light used so that the process can be regarded as the emission and absorption of a virtual photon like it is depicted in Scheme 58. FRET (addressable) linkage Scheme 58. Excitation of an acceptor dye by FRET where hν stands for photons capable to excite the donor dye. The linker is bringing both dyes into the correct orientation towards each other and could be further used to attach the dye-pair to an organic substrate or a functional surface.
O N NH HN N Discussion and Results 3 This process would allow the utilization of light of different wavelengths since the excitation could then be accomplished indirectly via the donor dye and FRET and still directly via the acceptor itself. This would not only broaden the “active window” for excitation but also provide the possibility to tune the wavelength for excitation without the need to change the sensitizer (=acceptor) in structure but by selection of an appropriate donor. This can lead to an improved performance of PDT systems and also to applications in detoxification devices for purification of air or water. To clarify, whether the concept could be working, a model compound has to be designed in which two photoactive dyes are brought into close proximity by a covalent linkage. As the two different photosensitizer classes used within this thesis represent a carboxylic acid derivative (pyropheophorbide a 33) and an amine (cycloketo-porphyrin 92) it seemed obvious to simply try to couple both to obtain a conjugate. 3.2.9.2 Approaching a Novel Photosensitizing Systems by Conjugation of Amino O N NH HN N Cycloketo-Porphyrin 92 and Pyropheophorbide a 33 The coupling reaction to obtain the desired two-dye conjugate was conducted under standard condition utilizing the carbodiimide method. Both dyes were reacted with 1-ethyl- 3-(3-dimethylaminopropyl)-carbodiimide (EDC) assisted by N-hydroxysuccinimid (NHS) and N,N-4-dimethylaminopyridine (DMAP) in DMF like it is shown in Scheme 59. + NH 2 HO O N O N H N H N 92 33 94 HN O N O N H N H N Scheme 59. Formation of two-dye conjugate 94 from monomeric photosensitizers 33 and 92. Applied conditions: 1. EDC, NHS, DMAP (catalytic) in DMF, rt, 24 h, 2. add. EDC and 92, rt, 24 h. The reaction proceeded well to give conjugate 94 in good isolated yield (69 % based on 33) as pure and stable compound with a molecular weight of 1368.75 g·mol -1 providing a single 125
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Semi-Natural and Synthetic Chiral C
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Die vorliegende Arbeit entstand in
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Table of Contents 1 Introduction 1
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n J j-coupling (constant) with n in
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1 Introduction characteristics. For
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1 Introduction 1.1 Porphyrins - A G
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1 Introduction Especially interesti
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1 Introduction 8 [H] 4 + 4 O H O H
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1 Introduction complexes are usuall
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1 Introduction transitions as it is
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1 Introduction 1.2 Photodynamic The
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1 Introduction Certainly, Photofrin
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1 Introduction intact membranes bei
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1 Introduction components, the limi
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2 State of The Art & Aims They were
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2 State of The Art & Aims 2.2 Aim o
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3 Discussion and Results encapsulat
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3 Discussion and Results diastereot
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3 Discussion and Results 30 E ½ Re
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3 Discussion and Results irradiatio
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3 Discussion and Results 34 R 1 O N
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3 Discussion and Results 3.2.2.1.2
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3 Discussion and Results Table 4. S
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3 Discussion and Results 3.2.2.2 FR
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3 Discussion and Results 3.2.2.3 Ac
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3 Discussion and Results 3.2.3.1 IR
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3 Discussion and Results 3.2.3.2 NM
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3 Discussion and Results 3.2.3.3 Va
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3 Discussion and Results 3.2.3.3.2
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3 Discussion and Results Obviously,
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3 Discussion and Results Like Figur
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3 Discussion and Results utilizatio
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3 Discussion and Results has been d
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3 Discussion and Results other TPP
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3 Discussion and Results (being sup
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3 Discussion and Results other band
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
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6 Experimental Section 6.2.5.13 α
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6 Experimental Section 6.2.5.15 5 4
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6 Experimental Section 6.2.6 AB2C-T
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section broad signal
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7 References 16 H. Fischer, K. Zeil
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7 References 57 S. Schwartz, K. Abs
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7 References 89 (a) R. C. Fuson, J.
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7 References 131 (a) J. Perdew, Phy
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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