481-39-0Relevant articles and documents
Synthesis and photosensitizing properties of porphycene with imidazolium tag
Shimakoshi, Hisashi,Sasaki, Kenichi,Iseki, Yusuke,Hisaeda, Yoshio
, p. 530 - 536 (2012)
Porphycene having an imidazolium cation tag was synthesized and characterized by elemental analysis, UV-vis, NMR and ESI-mass spectroscopies. This porphycene derivative easily dissolves in various ionic liquids and produces singlet oxygen under irradiation by visible light (λ 460 nm). The photophysical parameters of the porphycene in ionic liquids were determined and the values were compared to those in acetonitrile. Photosensitizing reactions using this new porphycene for the oxidation of 1,5-dihydroxynaphthalene in ionic liquids were investigated and found to form 5-hydroxy-1,4-naphthoquinone. The recycled use of the porphycene was efficiently achieved in N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)amide ([TMPA][TFSA]) and N-methyl-N-propyl-piperidinium bis(trifluoromethanesulfonyl) amide ([P13][TFSA]).
(-)-REGIOLONE, AN α-TETRALONE FROM JUGLANS REGIA: STRUCTURE, STEREOCHEMISTRY AND CONFORMATION
Talapatra, Sunil K.,Karmacharya, Bimala,De, Shambhu C.,Talapatra, Bani
, p. 3929 - 3932 (1988)
A new α-tetralone derivative designated (-)-regiolone has been isolated with juglone, betullic acid and sitosterol from the stem-bark of Juglans regia. (-)-Regiolone has been shown to be 4,8-dihydroxy-1-tetralone on the basis of its spectral data and chemical transformation to juglone.Its conformation has been deduced from the 1H NMR spectral data.The absolute stereochemistry of its only chiral centre has been shown to be S by the application of the dibenzoate chirality rule.
A luminescent poly(amidoamine)-iridium complex as a new singlet-oxygen sensitizer for photodynamic therapy
Maggioni, Daniela,Galli, Marco,D'Alfonso, Laura,Inverso, Donato,Dozzi, Maria Vittoria,Sironi, Laura,Iannacone, Matteo,Collini, Maddalena,Ferruti, Paolo,Ranucci, Elisabetta,D'Alfonso, Giuseppe
, p. 544 - 553 (2015)
A polymer complex (1P) was synthesized by binding bis(cyclometalated) Ir(ppy)2+ fragments (ppy = 2-phenylpyridyl) to phenanthroline (phen) pendants of a poly(amidoamine) copolymer (PhenISA, in which the phen pendants involved 6% of the repeating units). The corresponding molecular complex [Ir(ppy)2(bap)]+ (1M, bap = 4-(butyl-4-amino)-1,10-phenanthroline) was also prepared for comparison. In water solution 1P gives nanoaggregates with a hydrodynamic diameter of 30 nm in which the lipophilic metal centers are presumed to be segregated within polymer tasks to reduce their interaction with water. Such confinement, combined with the dilution of triplet emitters along the polymer chains, led to 1P having a photoluminescence quantum yield greater than that of 1M (0.061 vs 0.034, respectively, in an aerated water solution) with a longer lifetime of the 3MLCT excited states and a blue-shifted emission (595 nm vs 604 nm, respectively). NMR data supported segregation of the metal centers. Photoreaction of O2 with 1,5-dihydroxynaphthalene showed that 1P is able to sensitize 1O2 generation but with half the quantum yield of 1M. Cellular uptake experiments showed that both 1M and 1P are efficient cell staining agents endowed with two-photon excitation (TPE) imaging capability. TPE microscopy at 840 nm indicated that both complexes penetrate the cellular membrane of HeLa cells, localizing in the perinuclear region. Cellular photodynamic therapy tests showed that both 1M and 1P are able to induce cell apoptosis upon exposure to Xe lamp irradiation. The fraction of apoptotic cells for 1M was higher than that for 1P (74 and 38%, respectively) 6 h after being irradiated for 5 min, but cells incubated with 1P showed much lower levels of necrosis as well as lower toxicity in the absence of irradiation. More generally, the results indicate that cell damage induced by 1M was avoided by binding the iridium sensitizers to the poly(amidoamine).
Directing energy transfer in panchromatic platinum complexes for dual Vis-Near-IR or dual visible emission from σ-bonded BODIPY dyes
Geist, Fabian,Jackel, Andrej,Irmler, Peter,Linseis, Michael,Malzkuhn, Sabine,Kuss-Petermann, Martin,Wenger, Oliver S.,Winter, Rainer F.
, p. 914 - 930 (2017)
We report on the platinum complexes trans- Pt(BODIPY)(8-ethynyl-BODIPY)(PEt3)2 (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR3)2 (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two diffe
Porphyrin-Hyperbranched Copolymer Films as Recyclable Photooxidation Catalysts for 1,5-Dihydroxynaphthalene
Sun, Kaifang,Guo, Lintong,Cai, Cheng,Hou, Zongsheng,Ren, Qizhi
, p. 4465 - 4469 (2017)
Novel and stable films were easily assembled at the water–chloroform interface by noncovalent interaction between meso-tetrakis(4-sulfonatophenyl)porphyrins (H2TPPS, FeTPPS, and ZnTPPS) and polypeptide-containing hyperbranched copolymers of various molecular weights. These films could be used as recyclable heterogeneous photocatalysts for the oxidation of 1,5-dihydroxynaphthalene. Conversion yields of 91 and 88 % were obtained for H2TPPS and FeTPPS, respectively, and these values were much higher than those obtained for the corresponding porphyrin systems without polymers. These films could be easily utilized over 10 catalytic runs with only a slight decrease in the catalytic activity and low porphyrin loss. No separation or purification of either the catalyst or product was necessary, which proved that these porphyrin–hyperbranched copolymer films could be efficient, robust, and recyclable photooxidation catalysts.
Structure-property relationships and 1O2 photosensitisation in sterically encumbered diimine PtII acetylide complexes
Nolan, Deanne,Gil, Belen,Wang, Longsheng,Zhao, Jianzhang,Draper, Sylvia M.
, p. 15615 - 15626 (2013)
A series of sterically encumbered [Pt(L)(σ-acetylide)2] complexes were prepared in which L, a dendritic polyaromatic diimine ligand, was held constant (L=1-(2,2′-bipyrid-6-yl)-2,3,4,5-tetrakis(4-tert- butylphenyl)benzene) and the cis ethynyl co-ligands were varied. The optical properties of the complexes were tuned by changing the electronic character, extent of π conjugation and steric bulk of the ethynyl ligands. Replacing electron-withdrawing phenyl-CF3 substituents (4) with electron-donating pyrenes (5) resulted in a red shift of both the lowest-energy absorption (ΔE=3300cm-1, 61nm) and emission bands (ΔE=1930cm-1, 64nm). The emission, assigned in each case as phosphorescence on the basis of the excited-state lifetimes, switched from being 3MMLL′CT-derived (mixed metal-ligand-to-ligand charge transfer) when phenyl/polyphenylene substituents (3, 4, 6) were present, to ligand-centred 3ππ* when the substituents were more conjugated aromatic platforms [pyrene (5) or hexa-peri-hexabenzocoronene (7)]. The novel PtII acetylide complexes 5 and 7 absorb strongly in the visible region of the electromagnetic spectrum, which along with their long triplet excited-state lifetimes suggested they would be good candidates for use as singlet-oxygen photosensitisers. Determined by in situ photooxidation of 1,5-dihydroxynaphthalene (DHN), the photooxidation rate with pyrenyl-5 as sensitiser (kobs=39.3×10-3min-1) was over half that of the known 1O2 sensitiser tetraphenylporphyrin (kobs=78.6×10-3min -1) under the same conditions. Measured 1O2 quantum yields of complexes 5 and 7 were half and one-third, respectively, of that of TPP, and thus reveal an efficient triplet-triplet energy-transfer process in both cases. A polyarylated bipyridine ligand was used to prepare a series of sterically encumbered [Pt(L)(σ-acetylide)2] complexes (L=1-(2,2′-bipyrid-6-yl)-2,3,4,5-tetrakis(4-tert-butylphenyl)benzene), the optical properties of which were tuned effectively by changing the electronic character, extent of π-conjugation, and steric bulk of the cis ethynyl co-ligands. Singlet-oxygen photosensitising properties were also explored (see figure). Copyright
Green synthetic approaches to furoylnaphthohydroquinone and juglone
Benites, Julio,Cortes, Michael,Miranda, Luis,Estela, Cynthia,Rios, David,Valderrama, Jaime A.,Arenas, Jorge
, p. 2455 - 2457 (2014)
The synthesis of two valuable precursors of biological active compounds named 2-(furan-2-yl)-1,4-dihydroxynapthohydroquinone 2 and 5-hydroxy-1,4-naphthoquinone (4, juglone) via solar photo-induced reactions from 1,4-naphthoquinone 1 and 1,5-dihydroxynaphthalene 3 in green solvent media is reported. When t-butyl alcohol and the binary t-ButOH/DMK and ternary i-PrOAc/DMK/MEK solvent mixtures were used, acylhydroquinone 2 was isolated in yields of 80, 83 and 77%, respectively. The sensitized photooxygenation of 3 "on water" and in water containing sodium dodecyl sulfate produce juglone 4 in 81 and 39% yields respectively.
Phosphorescent rhenium-dipyrrinates: efficient photosensitizers for singlet oxygen generation
Manav, Neha,Kesavan, Praseetha E.,Ishida, Masatoshi,Mori, Shigeki,Yasutake, Yuhsuke,Fukatsu, Susumu,Furuta, Hiroyuki,Gupta, Iti
, p. 2467 - 2478 (2019)
A series of rhenium(i) dipyrrinato complexes (Re1-Re8) have been prepared and characterized; their crystal structures, phosphorescence and singlet oxygen generation studies are reported. The aromatic substituents, such as thienyl, p-bromophenyl, p-fluorop
Photophysical and photosensitizing properties of brominated porphycenes
Shimakoshi, Hisashi,Baba, Tatsushi,Iseki, Yusuke,Aritome, Isao,Endo, Ayataka,Adachi, Chihaya,Hisaeda, Yoshio
, p. 2882 - 2884 (2008)
A heavy atom, bromine, was directly substituted into the porphycene macrocycle to promote intersystem crossing by way of spin-orbit coupling. The singlet oxygen production ability of the porphycene is dramatically enhanced, and the highest value of 0.95 for the quantum yield of singlet oxygen generation (ΦΔ) was obtained for the dibrominated porphycene by visible light excitation. The Royal Society of Chemistry.
Green photochemistry: The use of microemulsions as green media in photooxygenation reactions
Coyle, Emma E.,Joyce, Kieran,Nolan, Kieran,Oelgemoeller, Michael
, p. 1544 - 1547 (2010)
The use of 'green' microemulsions of ethyl acetate and water, using sodium dodecyl sulfate and alcoholic co-surfactants as a reaction medium, in photooxygenation reactions was investigated. This work looked at the optimisation of the microemulsion (the optimum ratio of components), an investigation of the effect of changing co-surfactant and optimisation of the reaction work-up for the synthesis of 5-hydroxy-1,4-naphthoquinone, Juglone. Isolated yields of 36-88% were achieved in just 4 h of irradiation. Microemulsions also allowed the usage of the sensitiser tetraphenylporphyrin (TPP) in a benign environment. The optimised procedure was furthermore applied to the synthesis of 5-amido-1,4-naphthoquinones, and moderate yields were achieved.
