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Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine.

ABSTRACT: The reaction of a diene nitroxide precursor with dichlorophenylphosphine in a McCormac procedure afforded 1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2-oxyl. Lithiation of the protected 3-iodo-pyrroline nitroxide followed by treatment with chlorodiphenylphosphine after deprotection afforded (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine oxide, and after reduction, (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine was realized, which was also supported by X-ray single crystal diffraction measurements. This pyrroline diphenylphosphine derivative was converted to hexadecylphosphonium salt, which is an analogue of antineoplastic agent, MITO-CP.

SUBMITTER: Isbera M

PROVIDER: S-EPMC8305133 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Syntheses and Reactions of Pyrroline, Piperidine Nitroxide Phosphonates.

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| S-EPMC7287729 | biostudies-literature

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| S-EPMC2532528 | biostudies-literature

Superoxide radical anion adduct of 5,5-dimethyl-1-pyrroline N-oxide. 6. Redox properties.

Project description:Cyclic nitrones have been employed for decades as spin trapping reagents for the detection and identification of transient radicals, and have been employed as pharmacological agent against ROS-mediated toxicity. The short half-life of the nitrone-superoxide adducts limits the application of nitrones in biological millieu, and therefore investigaton of the redox properties of the superoxide adducts is important. Moreover, computational investigation of the redox properties of the nitrones and their corresponding spin adducts may provide new insights into the nature of their pharmacological activity against ROS-induced toxicity. In general, electron-withdrawing group substitution at the C-5 position results in higher EAs and IPs making these substituted nitrones more susceptible to reduction but more difficult to oxidize compared to DMPO. One-electron reduction and oxidation of nitrones both resulted in elongated N-C(2) bonds indicating the tendency of radical anion and cation forms of nitrone to undergo ring-opening. The EAs and IPs of various O(2)(*-) adducts indicate that DEPMPO-O(2)H is the most difficult to reduce and oxidize compared to the O(2)(*-) adducts of DMPO, EMPO, and AMPO. In general, nitroxides gave higher EAs compared to nitrones making them more suceptible to reduction. One-electron oxidation of nitroxides leads to elongation of the N-C(2) bond but not for their reduction. The energetics of redox reaction of O(2)(*-) adducts was also explored. Results indicate that the reduction of O(2)(*-) adducts with O(2)(*-) is preferred followed by their oxidation by O(2) and then by O(2)(*-), but the maximum difference between these free energies of redox reactions in aqueous solution is only 0.21 kcal/mol. The preferred decomposition pathways for the one-electron oxidation and reduction of nitroxides was also explored, and formation of potentially biologically active products such as NO, H(2)O(2), and hydroxamic acid was predicted.

| S-EPMC2818661 | biostudies-literature

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| S-EPMC5355805 | biostudies-literature

The nitrone spin trap 5,5-dimethyl-1-pyrroline N-oxide dampens lipopolysaccharide-induced transcriptomic changes in macrophages.

Project description:OBJECTIVE:M1-like inflammatory phenotype of macrophages plays a critical role in tissue damage in chronic inflammatory diseases. Previously, we found that the nitrone spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) dampens lipopolysaccharide (LPS)-triggered inflammatory priming of RAW 264.7 cells. Herein, we tested whether DMPO by itself can induce changes in macrophage transcriptome, and that these effects may prevent LPS-induced activation of macrophages. MATERIALS AND METHODS:To test our hypothesis, we performed a transcriptomic and bioinformatics analysis in RAW 264.7 cells incubated with or without LPS, in the presence or in the absence of DMPO. RESULTS:Functional data analysis showed 79 differentially expressed genes (DEGs) when comparing DMPO vs Control. We used DAVID databases for identifying enriched gene ontology terms and Ingenuity Pathway Analysis for functional analysis. Our data showed that DMPO vs Control comparison of DEGs is related to downregulation immune-system processes among others. Functional analysis indicated that interferon-response factor 7 and toll-like receptor were related (predicted inhibitions) to the observed transcriptomic effects of DMPO. Functional data analyses of the DMPO?+?LPS vs LPS DEGs were consistent with DMPO-dampening LPS-induced inflammatory transcriptomic profile in RAW 264.7. These changes were confirmed using Nanostring technology. CONCLUSIONS:Taking together our data, surprisingly, indicate that DMPO by itself affects gene expression related to regulation of immune system and that DMPO dampens LPS-triggered MyD88- and TRIF-dependent signaling pathways. Our research provides critical data for further studies on the possible use of DMPO as a structural platform for the design of novel mechanism-based anti-inflammatory drugs.

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| S-EPMC4317054 | biostudies-literature

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies.

Project description:With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5-7, where the ArP(O)Ph2 group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5-7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5-7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined.

| S-EPMC8069430 | biostudies-literature

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