1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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2 State of The Art & Aims 2.2 Aim of the Work Within the course of this thesis, novel cycloketo-porphyrin systems shall be established and thoroughly investigated. As they are related to pyropheophorbides, being active photosensitizers suited for applications in photodynamic therapy, both substance classes shall be compared and finally, trials are to be conducted to synergize both approaches to photosensitization – the fully synthetic and the nature based one – to gain the ability of developing novel photosensitizing systems with improved characteristics. Concerning the porphyrin building blocks, which represent the basis for the development of cycloketo-porphyrins, it seems worth to revisit the used synthetic protocols to rationalize their formation to be able to access those systems in multi-gram quantities. Then novel synthetic protocols shall be established leading to systems like M-53 (see Scheme 19) as rational as possible and to free base systems. Furthermore, it is to be investigated, whether those protocols are also applicable to obtain bis- or even higher annulated analogs of specific symmetries. All obtained systems shall then be characterized and thoroughly investigated concerning their general behavior and especially their photophysical and electrochemical properties. Dependent on those findings, it is to be studied, if thereof arise potential candidates for PDT applications and if those could be directly implemented into a 3 rd generation sensitizer concept or whether further structural modifications have to be performed. Also, those adapted compounds are then to be subjected to detailed studies. Additionally, the assumption that some of those compounds appear as mixtures of atropisomers, and thus are considered to be inherently chiral, shall be further investigated and, if possible, a pathway shall be figured out to finally be able to resolve the racemic mixtures. Meanwhile, also the isolation and transformation protocols to access pyropheophorbide a derivatives shall be worked over, since the isolation from higher plants (e.g. spinach and stinging nettles) or chlorella algae involves the very laborious separation of chlorophylls a and b. The use of spirulina algae can offer a good alternative therefore, which is to be verified. The obtained derivatives will furthermore serve as reference compounds for investigations on the synthesized cycloketo-porphyrin systems being regarded as artificial structural analogs. 24
N N NH HN NH HN N O N O CO2Me CO2Me O OH O O 3 Discussion and Results 3 3 Discussion and Results 3.1 Semi-Natural Cycloketo-<strong>Porphyrins</strong> That substance class covers the whole family of the chlorophylls and their derivatives. Thereby chlorophyll a 1 is of the utmost significance, since it is the most wide-spread one being found in plants, algae and even some bacteria. 79 Primary degradation comprises demetallation (→ pheophytin a 31) and the loss of the phytyl side chain leading to pheophorbide a 32 existing as equilibrium mixture of two diastereomers. As that fact seriously hampers photophysical measurements and as it could give rise to ring-opening side-reactions leading to chlorin e6 derivatives, further degradation by pyrolysis is performed destroying the allomeric center to give pyropheophorbide a 33. N NH HN N 31 32 33 Scheme 20. Products from chemical modification (degradation) of chlorophyll a 1. 3.<strong>1.1</strong> Accessing Pyropheophorbide a To successfully generate pyropheophorbide a 33, chlorophyll a 1 had to be isolated. Initially applied protocols used mixtures of leaf spinach and stinging nettles or dried chlorella algae as natural source. But both, they were laborious due to time-consuming processing of the organic starting materials (e.g. grinding) and as the separation from unwanted chlorophyll b turned out to be difficult. 80 Thus, switching the starting material to spirulina algae seemed more promising since it exclusively contains chlorophyll a 1 and as that is not being O O OH 25
Page 1 and 2: Semi-Natural and Synthetic Chiral C
Page 3 and 4: Die vorliegende Arbeit entstand in
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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3 Discussion and Results 3.2.6.4 Sy
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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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3 Discussion and Results 3.2.6.5.4
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3 Discussion and Results 90 5 μA -
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3 Discussion and Results 3.2.7 Appr
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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3 Discussion and Results of rotatio
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3 Discussion and Results Thus, the
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3 Discussion and Results Time-resol
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3 Discussion and Results first redu
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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3 Discussion and Results With all t
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3 Discussion and Results The interm
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3 Discussion and Results 116 HO 2 C
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3 Discussion and Results nitro comp
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3 Discussion and Results The effect
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3 Discussion and Results 3.2.8.2.7
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3 Discussion and Results 3.2.9 Pote
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3 Discussion and Results peak at m/
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3 Discussion and Results Table 25.
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3 Discussion and Results 130
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4 Summary As the characterization d
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5 Zusammenfassung 5 Zusammenfassung
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5 Zusammenfassung Da in guten Ausbe
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6 Experimental Section UV/Vis spect
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6 Experimental Section 6.2 Studied
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6 Experimental Section 13 C NMR (10
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6 Experimental Section (cyanomethyl
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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.4.3 5 4
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6 Experimental Section 6.2.4.11 10
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6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.4.15 10
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6 Experimental Section 6.2.5 A2B2-T
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6 Experimental Section 6.2.5.5 αβ
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6 Experimental Section 6.2.5.7 αβ
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6 Experimental Section 6.2.5.9 αα
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6 Experimental Section 6.2.5.11 α
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6 Experimental Section 6.2.5.13 α
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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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