Syntheses of oxygen analogues of sulfhemes-A and -C

Iakovides, Panos; Smith, Kevin M.

doi:10.1016/0040-4020(95)00953-1

Cited by 17 publications

(23 citation statements)

References 55 publications

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“…Absorption spectra in dichloromethane of dihydrofuran-annulated chlorin 11-H 2 31 (red line) and chlorin–epoxide 11-H 2 33 (orange line). The absorption spectrum of 11-H 2 33 is displayed on the basis of the data listed in the published experimental section …”

Section: Cycloadditions With β-Vinylporphyrinsmentioning

confidence: 99%

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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Chlorophylls make Earth green, are the central constituents in the engine of photosynthesis, and not surprisingly have garnered immense attention. A chlorin, the core chromophore of a chlorophyll, is a dihydroporphyrin macrocycle that contains one pyrroline ring and three pyrrole rings. The dominant method for the synthesis of chlorins has entailed the derivatization of porphyrins. The present review covers the ostensibly simple conversion of porphyrins, regardless of synthetic or biological origin, to chlorins. The period covered encompasses the entire history since the beginnings of chlorin synthetic chemistry in the early 20th century through 2015. Representative transformations include hydrogenation, cycloaddition, annulation, and diverse "breaking and mending" approaches. Altogether, the synthesis of >1000 chlorins or chlorin-like compounds (containing >50 distinct pyrroline motifs) is described. Such diversity animates the question "what structural features are essential for a chlorin to resemble chlorophyll?" To begin to address the structure-spectrum relationship, > 250 absorption spectra are provided for representative structures. The synthesis and spectral properties of the vast collection of compounds described herein are expected to illuminate the scope to which synthetic chlorins can serve as surrogates for chlorophylls and be exploited in diverse ways.

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Section: Cycloadditions With β-Vinylporphyrinsmentioning

confidence: 99%

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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“…Platinum(II) octaethylporphine ketone (PtOEPK) was synthesized according to a method in the literature. 20,21 The chemicals for synthesis of PtOEPK including osmium tetroxide (very toxic), perchloric acid, FeS, and hydrochloric acid, anhydrous ether, dichloromethane (99% HPLC), pyridine, benzonitrile, anhydrous sodium acetate and platinum chloride were obtained from Aldrich (Milwaukee, WI).…”

Section: Experimental Reagentsmentioning

confidence: 99%

Poly(decyl methacrylate)-based fluorescent PEBBLE swarm nanosensors for measuring dissolved oxygen in biosamples

Cao

Koo

Kopelman

2004

Analyst

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150-250 nm Poly(decyl methacrylate)(PDMA) fluorescent ratiometric nanosensors for dissolved oxygen have been developed. Platinum octaethylporphine ketone (PtOEPK), the oxygen-sensitive dye, and octaethylporphyrin (OEP), the oxygen-insensitive dye, have been incorporated into PDMA nanoparticles to make the sensors ratiometric. Based on the corresponding Stern-Volmer plot, these nanosensors exhibit almost complete linearity over the whole range of dissolved molecular oxygen from 0 to 42.5 ppm (deoxygenated to pure oxygen-bubbled water). The overall quenching response is up to 97.5%, the best so far for all dissolved oxygen optical sensors. These PEBBLE nanosensors also show very good reversibility and stability to leaching and photobleaching, as well as very short response times and no perturbation by proteins. In human plasma they demonstrate a robust oxygen sensing capability, little affected by light scattering and autofluorescence. Potential applications include intracellular oxygen imaging and microresolved pressure profiles in biological and other heterogenous environments.

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“…No significant deviations from planarity are observed elsewhere, which is comparable to that of the unsubstituted bacteriochlorin BC12 (Chart 3) [59]. While significant structural changes of the macrocycle appear to be absent in BC6, the presence of hydroxy group(s) at the pyrroline ring(s) of a bacteriochlorin is known to cause a hypsochromic shift of the Q y absorption band [68][69][70][71][72][73][74]. Evidence in support of this statement stems from comparison of the spectra of meso-tetraphenylbacteriochlorin (H 2 TPBC) and cis-diol-substituted analogs thereof (Chart 5).…”

Section: Spectral Properties Of New Bacteriochlorinsmentioning

confidence: 99%

Elaboration of an unexplored substitution site in synthetic bacteriochlorins

Zhang

Reddy

Jiang

et al. 2015

J. Porphyrins Phthalocyanines

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The ability to introduce substituents at designated sites about the perimeter of synthetic bacteriochlorins -analogs of bacteriochlorophylls of bacterial photosynthesis -remains a subject of ongoing study. Here, the self-condensation of a dihydrodipyrrin-dioxolane affords a 5-[2-(trimethylsiloxy) ethoxy]bacteriochlorin. Like a 5-methoxybacteriochlorin, the latter undergoes regioselective bromination at the 15-position, directed by the distal 5-alkoxy group. On the other hand, attempted bromination of a bacteriochlorin bearing a 5-(2-hydroxyethoxy) group resulted in intramolecular ether formation with the adjacent b-pyrroline position to give an annulated dioxepine ring (confirmed by single-crystal X-ray structural analysis). The hydroxyethoxy group at the 5-position can be derivatized by acylation. In addition, the installation of auxochromes (methoxycarbonyl, phenylethynyl) at the b-pyrrole rings causes a substantial bathochromic shift of the long-wavelength absorption band (812 nm) and companion fluorescence emission band (821 nm). Taken together, the modification of the 5-substituent complements existing methods for installing a single substituent on the bacteriochlorin macrocycle. J. Porphyrins Phthalocyanines 2015.19:887-902. Downloaded from www.worldscientific.com by EMORY UNIVERSITY on 07/30/15. For personal use only. G1 G2 2 A J K Scheme 5. Proposed mechanism leading to the 5-(2-alkoxyethoxy)bacteriochlorin J (top) and balanced equation (bottom) J. Porphyrins Phthalocyanines 2015.19:887-902. Downloaded from www.worldscientific.com by EMORY UNIVERSITY on 07/30/15. For personal use only.

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Syntheses of oxygen analogues of sulfhemes-A and -C

Cited by 17 publications

References 55 publications

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Poly(decyl methacrylate)-based fluorescent PEBBLE swarm nanosensors for measuring dissolved oxygen in biosamples

Elaboration of an unexplored substitution site in synthetic bacteriochlorins

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