Porphyrin studies. XXXVI. Deoxophylloerythroetioporphyrin

Baker, Earl W.; Corwin, Alsoph H.; Klesper, E.; Wei, Pan

doi:10.1021/jo01272a026

Cited by 53 publications

(12 citation statements)

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“…2) was assigned as C 32 Ni deoxophylloerythroetioporphyrin (DPEP, Fig. A1; Baker et al, 1968) based on the interpretation of mass spectrum and comparison of absorption spectrum with previous results (Baker and Louda, 1986;Figs. 3a and 3b).…”

Section: Geoporphyrins In Bonarelli Black Shalementioning

confidence: 60%

The importance of diazotrophic cyanobacteria as primary producers during Cretaceous Oceanic Anoxic Event 2

et al. 2006

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Abstract. In Livello Bonarelli black shale deposited during Cretaceous Oceanic Anoxic Event 2 (OAE-2, ca. 94 Ma), nitrogen isotopic compositions of bulk sediments are mostly in a narrow range from -2.7 to -0.7‰. We also determined molecular distribution and nitrogen isotopic compositions of geoporphyrins extracted from the black shale. The nitrogen isotopic compositions of C 32 Ni deoxophylloerythroetioporphyrin (DPEP) and total Ni porphyrins are -3.5 and -3.3‰, respectively, leading us to the estimation that the mean nitrogen isotopic composition of photoautotrophic cells were around +1‰ during the formation of Bonarelli black shale. This value is suggestive of N 2 -fixation, a dominant process for these photoautotrophs when assimilating nitrogen. Furthermore, Ni-chelated C 32 DPEP, derived mainly from chlorophyll a had the highest concentration. Based on this evidence, we conclude that diazotrophic cyanobacteria were major primary producers during that time. Cyanobacteria may be key photoautotrophs during the formation of black shale type sediments intermittently observed throughout the later half of the Earth's history, and hence may have played a crucial role in the evolution of geochemical cycles even in the later half of the Earth's history.

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Section: Geoporphyrins In Bonarelli Black Shalementioning

confidence: 60%

The importance of diazotrophic cyanobacteria as primary producers during Cretaceous Oceanic Anoxic Event 2

et al. 2006

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“…Authentic tetrapyrrole pigments were formed from pheophytin-a (ex Spinacea oleracea chlorophyll-a, or purchased from Roth Laboratories, West Germany) according to published methods (Baker et al, 1968;Fischer and Stern, 1940;Fuhrhop and Smith, 1975).…”

Section: Methodsmentioning

confidence: 99%

Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Baker¹,

Louda²

1982

Initial Reports of the Deep Sea Drilling Project

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Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene.Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter.Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature).Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p 6 .The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected.Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial.Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants.Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene.The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

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“…An a/ß ratio of 2.3 is indicative of a DPEP/etio ratio of ca. 2, based on a/ß ratios of nickel deoxophylloerythroetioporphyrin and nickel etioporphyrin III of 2.0 and 3.0, respectively (Baker et al, 1968). ' A linear change of the a/ß ratio from 2.3 at a distance to 4.4 in close proximity to the sill is indicative of partial to total conversion to the etio series coincident with increasing dealkylation.…”

Section: Etio Series Generationmentioning

confidence: 99%

Porphyrin studies. XXXVI. Deoxophylloerythroetioporphyrin

Cited by 53 publications

References 0 publications

The importance of diazotrophic cyanobacteria as primary producers during Cretaceous Oceanic Anoxic Event 2

The importance of diazotrophic cyanobacteria as primary producers during Cretaceous Oceanic Anoxic Event 2

Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Intermediate and Late Diagenetic Tetrapyrrole Pigments, Leg 41: Cape Verde Rise and Basin

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