Chlorophyll Metabolism

Eckhardt, Ulrich; Grimm, Bernhard

doi:10.1002/9780470015902.a0020084

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“…Among tetrapyrroles, chlorophylls are the most abundant natural products on earth . Chlorophyll biosynthesis is believed to take place in two phases. , The processes that take place in darkness in all plants are defined as “dark steps”, whereas a light-dependent step and all subsequent steps are known as “late steps”. At the later steps of biosynthesis, three types of chromophores can be distinguished: (i) porphyrins, (ii) chlorins (in which the pyrrole ring D is hydrogenated), and (iii) bacteriochlorins (in which the rings B and D are hydrogenated) (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Highly Selective Synthesis of the Ring-B Reduced Chlorins by Ferric Chloride-Mediated Oxidation of Bacteriochlorins: Effects of the Fused Imide vs Isocyclic Ring on Photophysical and Electrochemical Properties

et al. 2008

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The oxidation of bacteriopyropheophorbide with ferric chloride hexahydrate or its anhydrous form produced the ring-D oxidized (ring-B reduced) chlorin in >95% yield. Replacing the five-member isocyclic ring in bacteriopyropheophorbide- a with a fused six-member N-butylimide ring system made no difference in regioselective oxidation, and the corresponding ring-B reduced chlorin was isolated in almost quantitative yield. When the oxidant was replaced by 2,3-dichloro-5,6-dicyano-p-benzoquinone, which is frequently used at the oxidizing stage of the porphyrin synthesis, the ring-B oxidized (ring-D reduced) chlorins were obtained. With both ring-B reduced and ring-D reduced chlorins in hand, their photophysical and electrochemical properties were examined and compared for the first time. The ring-B reduced chlorine 20, with a fused six-member N-butylimide ring, exhibits the most red-shifted absorption band (at lambda(max) = 746 nm), the lowest fluorescence quantum yield (4.5%), and the largest quantum yield of singlet oxygen formation (67%) among the reduced ring-B and ring-D chlorins investigated in this study. Measurements of the one-electron oxidation and reduction potentials show that compound 20 is also the easiest to oxidize among the examined compounds and the third easiest to reduce. In addition, the 1.62 eV HOMO-LUMO gap of 20 is the smallest of the examined compounds, and this agrees with values calculated using the DFT method. Spectroelectrochemical measurements afforded UV-visible absorption spectra for both the radical cations and radical anions of the examined chlorins. The ring-B reduced compound 20, with a fused six-member N-butylimide ring, is regarded as the most promising candidate in this study for photodynamic therapy because it has the longest wavelength absorption and the largest quantum yield of singlet oxygen formation among the compounds investigated.

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Section: Introductionmentioning

confidence: 99%