129018-26-4Relevant articles and documents
Proton-and redox-controlled switching of photo-and electrochemiluminescence in thiophenyl-substituted boron-dipyrromethene dyes
Roehr, Holger,Trieflinger, Christian,Rurack, Knut,Daub, Joerg
, p. 689 - 700 (2006)
A luminescent molecular switch in which the active thiol/disulfide switching element is attached to a meso-phenyl-substituted boron-dipyr-romethene (BDP) chromophore as the signalling unit is presented. The combination of these two functional units offers great versatility for multimodal switching of luminescence: 1)deprotonation/protonation of the thiol/thiolate moiety allows the highly fluorescent meso-p-thiophenol-BDP and its non-fluorescent thiolate analogue to be chemically and reversibly interconverted, 2) electrochemical oxidation of the monomeric dyes yields the fluorescent disulfide-bridged bichromophoric dimer, also in a fully reversible process, and 3) besides conventional photoexcitation, the well separated redox potentials of the BDP also allow the excited BDP state to be generated electro-chemically (i.e., processes 1) and 2) can be employed to control both photo-and electrochemiluminescence (ECL) of the BDP). The paper introduces and characterizes the various states of the switch and discusses the underlying mechanisms. Investigation of the ortho analogue of the dimer provided insight into potential chromophore-chromophore interactions in such bichromophoric architectures in both the ground and the excited state. Comparison of the optical and redox properties of the two disulfide dimers further revealed structural requirements both for redox switches and for ECL-active molecular ensembles. By employing thiol/disulfide switching chemistry and BDP luminescence features, it was possible to create a prototype molecular ensemble that shows both fully reversible proton-and redox-gated electrochemiluminescence.
12-EPI PLEUROMUTILINS
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Paragraph 0396, (2016/12/01)
A compound selected from 14-O-[((Alkyl-, cycloalkyl-, heterocycloalkyl-, heteoroaryl-, or aryl)-sulfanyl)-acetyl]-12-epi-mutilins, or 14-O-[((Alkyl-, cycloalkyl-, heterocycloalkyl-, heteoroaryl-, or aryl)-oxy)-acetyl]-12-epi-mutilins, wherein 12-epi-mutilin is characterized in that the mutilin ring at position 12 is substituted by two substituents, the first substituent at position 12 of the mutilin ring is a methyl group which methyl group has the inverse stereochemistry compared with the stereochemistry of the methyl group at position 12 of the naturally occurring pleuromutilin ring, the second substituent at position 12 of the mutilin ring is a hydrocarbon group comprising at least one nitrogen atom and all other substituents of the mutilin ring having the same stereochemistry compared with the stereochemistry of the substituents at the corresponding positions in the naturally occurring pleuromutilin ring; optionally in the form of a salt and/or solvate, wherein the naturally occurring pleuromutilin is of formula processes for the preparation of such compounds and their use as pharmaceuticals.
12-EPI-PLEUROMUTILINS
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Page/Page column 46, (2015/08/06)
A compound selected from 14-O-[((Alkyl-, cycloalkyl-, heterocycloalkyl-, heteoroaryl-, or aryl)-sulfanyl)-acetyl]-12-epi-mutilins, or 14-0-[((Alkyl-, cycloalkyl-, heterocycloalkyl-, heteoroaryl-, or aryl)-oxy)-acetyl]-12-epi-mutilins, wherein 12-epi-mutilin is characterized in that the mutilin ring at position 12 is substituted by two substituents, the first substituent at position 12 of the mutilin ring is a methyl group which methyl group has the inverse stereochemistry compared with the stereochemistry of the methyl group at position 12 of the naturally occurring pleuromutilin ring, the second substituent at position 12 of the mutilin ring is a hydrocarbon group comprising at least one nitrogen atom and all other substituents of the mutilin ring having the same stereochemistry compared with the stereochemistry of the substituents at the corresponding positions in the naturally occurring pleuromutilin ring; optionally in the form of a salt and/or solvate, wherein the naturally occurring pleuromutilin is of formula PLEU, processes for the preparation of such compounds and their use as pharmaceuticals.
Synthesis of Tetranuclear Iron-Sulphur Protein Analogues with Tetrathiol Ligands attached to Macrocycles which provide Intramolecular Hydrophobic Domains
Okuno, Hiroaki (Yohmei),Uoto, Kouichi,Tomohiro, Takenori,Youinou, Marie-Therese
, p. 3375 - 3381 (2007/10/02)
A new type of active-site analogues for 4Fe-4S iron-sulphur proteins is introduced, where the active site core is surrounded by an intramolecular hydrophobic domain formed by a 36-membered ring consisting of a methylene backbone.An efficient synthesis of the macrocyclic ligands 1,10,19,28-tetra(4-mercaptobenzoyl)-1,10,19,28-tetra-azacyclohexatriacontane and 1,10,19,28--1,10,19,28-tetra-azacyclohexatriacontane and 1,10,19,28-tetra-(3-mercapto-3-methylbutanoyl)-1,10,19,28-tetra-azacyclohexatriacontane is described.Their reaction with t)4>2- afforded novel clusters in good yields (70 - 90percent) as black powders with m.p. > 300 deg C.They dissolve in dimethylformamide, dimethyl sulphoxide, and propylene carbonate.Complex formation with Fe4S4 clusters was mainly demonstrated by u.v.-visible and n.m.r. studies and the properties of the new clusters are discussed.
