[1] Naphthalene endoperoxides as generators of singlet oxygen in biological media

Pierlot, Christel; Aubry, Jean‐Marie; Briviba, Karlis; Sies, H.; Mascio, Paolo Di

doi:10.1016/s0076-6879(00)19003-2

Cited by 105 publications

(124 citation statements)

References 41 publications

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“…Among the excited species, singlet oxygen O 2 ( 1 ⌬ g ) is of particular interest because of its high electrophilicity and relatively long lifetime (2-4 s in H 2 O and ϳ700 s in CCl 4 ) (5). This excited species, which can be generated by an energy transfer mechanism (6,7), exhibits high reactivity and can be produced in biological systems (8,9). In mammalian cells, O 2 ( 1 ⌬ g ) can be generated during oxidative stress, and it is able to attack DNA, protein thiol groups, and membrane lipids (11)(12)(13)(14)(15)(16)(17)(18)(19)(20).…”

mentioning

confidence: 99%

Changes in the Spin State and Reactivity of Cytochrome c Induced by Photochemically Generated Singlet Oxygen and Free Radicals

Estevam

Nascimento

Baptista

et al. 2004

Journal of Biological Chemistry

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This work compares the effect of photogenerated singlet oxygen (O 2 ( 1 ⌬ g )) (type II mechanism) and free radicals (type I mechanism) on cytochrome c structure and reactivity. Both reactive species were obtained by photoexcitation of methylene blue (MB ؉ ) in the monomer and dimer forms, respectively. The monomer form is predominant at low dye concentrations (up to 8 M) or in the presence of an excess of SDS micelles, while dimers are predominant at 0.7 mM SDS. Over a pH range in which cytochrome c is in the native form, O 2 ( 1 ⌬ g ) and free radicals induced a Soret band blue shift (from 409 to 405 nm), predominantly. EPR measurements revealed that the blue shift of the Soret band was compatible with conversion of the heme iron from its native low spin state to a high spin state with axial symmetry (g ϳ 6.0). Soret band bleaching, due to direct attack on the heme group, was only detected under conditions that favored free radical production (MB ؉ dimer in SDS micelles) or in the presence of a less structured form of the protein (above pH 9.3). Matrix-assisted laser desorption ionization time-of-flight mass spectrometry of the heme group and the polypeptide chain of cytochrome c with Soret band at 405 nm (cytc405) revealed no alterations in the mass of the cytc405 heme group but oxidative modifications on methionine (Met 65 and Met 80 ) and tyrosine (Tyr 74 ) residues. Damage of cytc405 tyrosine residue impaired its reduction by diphenylacetaldehyde, but not by ␤-mercaptoethanol, which was able to reduce cytc405, generating cytochrome c Fe(II) in the high spin state (spin 2).

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confidence: 99%

Changes in the Spin State and Reactivity of Cytochrome c Induced by Photochemically Generated Singlet Oxygen and Free Radicals

Estevam

Nascimento

Baptista

et al. 2004

Journal of Biological Chemistry

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“…O 2 was generated by thermal decomposition of an endoperoxide (NDPO 2 ) of 3,3Ј-(1,4-naphthylidine) dipropionate (NDP), 13) which is a product of Merck-Calbiochem (Darmstadt, Germany). According to the manufacturer's technical inserts, NDP was activated to NDPO 2 by using Na 2 MoO 4 and H 2 O 2 at pH 10.…”

Section: )mentioning

confidence: 99%

11-Tungstophosphate with Iron(II) and Hydrogen Peroxide Efficiently Detached Bacterial Biofilm

Tsutsumi

Takagi

Nakajima

et al. 2009

Biological & Pharmaceutical Bulletin

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“…1,2 The corresponding light-mediated O 2 -adducts of such systems have been utilized for the targeted release of reactive oxygen species such as singlet oxygen. 3,4 Furthermore, the photochemical generation of oxygen-based biradical species from aromatic endoperoxide species has also been investigated in some detail.…”

Section: Introductionmentioning

confidence: 99%

“…3,4 Furthermore, the photochemical generation of oxygen-based biradical species from aromatic endoperoxide species has also been investigated in some detail. 5,6 Important biomedical and chemotherapeutic applications of such systems include the delayed triggering of singlet oxygen release, which can induce cellular damage in malignant tissue, 1 and the potential utilization of biomimetic endoperoxide-bond cleavage processes for the controlled deactivation of bacteria, viruses 7 and parasites such as Plasmodium falciparum, which is known to be responsible for the majority of fatal malaria infections. 8,9 In this context it is quite surprising that besides water solubility, relatively little attention has been paid to the optimization of the molecular properties of such naphthalene-based carriers for the controlled release of reactive oxygen species.…”

Section: Introductionmentioning

confidence: 99%

Functionalized derivatives of 1,4-dimethylnaphthalene as precursors for biomedical applications: synthesis, structures, spectroscopy and photochemical activation in the presence of dioxygen

et al. 2012

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Decomposition of endoperoxide containing molecules is an attractive approach for the delayed release of singlet oxygen under mild reaction conditions. Here we describe a new method for the adaptation of the corresponding decay times by controlling the supramolecular functional structure of the surrounding matrix in the immediate vicinity of embedded singlet oxygen precursors. Thus, a significant prolongation of the lifetime of the endoperoxide species is possible by raising the energy barrier of the thermal 1 O 2 -releasing step via a restriction of the free volume of the applied carrier material. Enabling such a prolonged decomposition period is crucial for potential biomedical applications of endoperoxide containing molecules, since sufficient time for appropriate cell uptake and transport to the desired target region must be available under physiological conditions before the tissue damaging-power of the reactive oxygen species formed is completely exhausted. Two novel polyaromatic systems for the intermediate storage and transport of endoperoxides and the controlled release of singlet oxygen in the context of anticancer and antibiotic activity have been prepared and characterized. These compounds are based on functionalized derivatives of the 1,4-dimethylnaphthalene family which are readily forming metastable endoperoxide species in the presence of dioxygen, a photosensitizer molecule such as methylene blue and visible light. In contrast to previously known systems of similar photoreactivity, the endoperoxide carrying molecules have been designed with optimized molecular properties in terms of potential chemotherapeutic applications. These include modifications of polarity to improve their incorporation into various biocompatible carrier materials, the introduction of hydrogen bonding motifs to additionally influence the endoperoxide decay kinetics, and the synthesis of bifunctional derivatives to enable synergistic effects of multiple singlet oxygen binding sites with an enhanced local concentration of reactive species. With these compounds, a promising degree of endoperoxide stability adjustment within the carrier matrix has been achieved ( polymer films or nanoparticles), which now opens the stage for appropriate targeting of the corresponding pro-drugs into live cells. First results on cytocidal and cytostatic properties of these compounds embedded in ethylcellulose nanoparticles are presented. Furthermore, an efficient low-cost method for the photochemical production of reactive endoperoxides based on high-power 660 nm LED excitation at room temperature and ambient conditions in ethanol solution is reported.

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[1] Naphthalene endoperoxides as generators of singlet oxygen in biological media

Cited by 105 publications

References 41 publications

Changes in the Spin State and Reactivity of Cytochrome c Induced by Photochemically Generated Singlet Oxygen and Free Radicals

Changes in the Spin State and Reactivity of Cytochrome c Induced by Photochemically Generated Singlet Oxygen and Free Radicals

11-Tungstophosphate with Iron(II) and Hydrogen Peroxide Efficiently Detached Bacterial Biofilm

Functionalized derivatives of 1,4-dimethylnaphthalene as precursors for biomedical applications: synthesis, structures, spectroscopy and photochemical activation in the presence of dioxygen

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